Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency

PubMed Central

Pihosh, Yuriy; Turkevych, Ivan; Mawatari, Kazuma; Uemura, Jin; Kazoe, Yutaka; Kosar, Sonya; Makita, Kikuo; Sugaya, Takeyoshi; Matsui, Takuya; Fujita, Daisuke; Tosa, Masahiro; Kondo, Michio; Kitamori, Takehiko

2015-01-01

Efficient photocatalytic water splitting requires effective generation, separation and transfer of photo-induced charge carriers that can hardly be achieved simultaneously in a single material. Here we show that the effectiveness of each process can be separately maximized in a nanostructured heterojunction with extremely thin absorber layer. We demonstrate this concept on WO3/BiVO4+CoPi core-shell nanostructured photoanode that achieves near theoretical water splitting efficiency. BiVO4 is characterized by a high recombination rate of photogenerated carriers that have much shorter diffusion length than the thickness required for sufficient light absorption. This issue can be resolved by the combination of BiVO4 with more conductive WO3 nanorods in a form of core-shell heterojunction, where the BiVO4 absorber layer is thinner than the carrier diffusion length while it’s optical thickness is reestablished by light trapping in high aspect ratio nanostructures. Our photoanode demonstrates ultimate water splitting photocurrent of 6.72 mA cm−2 under 1 sun illumination at 1.23 VRHE that corresponds to ~90% of the theoretically possible value for BiVO4. We also demonstrate a self-biased operation of the photoanode in tandem with a double-junction GaAs/InGaAsP photovoltaic cell with stable water splitting photocurrent of 6.56 mA cm−2 that corresponds to the solar to hydrogen generation efficiency of 8.1%. PMID:26053164

Photocatalytic generation of hydrogen by core-shell WO3/BiVO4 nanorods with ultimate water splitting efficiency

NASA Astrophysics Data System (ADS)

Pihosh, Yuriy; Turkevych, Ivan; Mawatari, Kazuma; Uemura, Jin; Kazoe, Yutaka; Kosar, Sonya; Makita, Kikuo; Sugaya, Takeyoshi; Matsui, Takuya; Fujita, Daisuke; Tosa, Masahiro; Kondo, Michio; Kitamori, Takehiko

2015-06-01

Efficient photocatalytic water splitting requires effective generation, separation and transfer of photo-induced charge carriers that can hardly be achieved simultaneously in a single material. Here we show that the effectiveness of each process can be separately maximized in a nanostructured heterojunction with extremely thin absorber layer. We demonstrate this concept on WO3/BiVO4+CoPi core-shell nanostructured photoanode that achieves near theoretical water splitting efficiency. BiVO4 is characterized by a high recombination rate of photogenerated carriers that have much shorter diffusion length than the thickness required for sufficient light absorption. This issue can be resolved by the combination of BiVO4 with more conductive WO3 nanorods in a form of core-shell heterojunction, where the BiVO4 absorber layer is thinner than the carrier diffusion length while it’s optical thickness is reestablished by light trapping in high aspect ratio nanostructures. Our photoanode demonstrates ultimate water splitting photocurrent of 6.72 mA cm-2 under 1 sun illumination at 1.23 VRHE that corresponds to ~90% of the theoretically possible value for BiVO4. We also demonstrate a self-biased operation of the photoanode in tandem with a double-junction GaAs/InGaAsP photovoltaic cell with stable water splitting photocurrent of 6.56 mA cm-2 that corresponds to the solar to hydrogen generation efficiency of 8.1%.

Heterogeneous Bimetallic Phosphide/Sulfide Nanocomposite for Efficient Solar-Energy-Driven Overall Water Splitting.

PubMed

Xin, Yanmei; Kan, Xiang; Gan, Li-Yong; Zhang, Zhonghai

2017-10-24

Solar-driven overall water splitting is highly desirable for hydrogen generation with sustainable energy sources, which need efficient, earth-abundant, robust, and bifunctional electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, we propose a heterogeneous bimetallic phosphide/sulfide nanocomposite electrocatalyst of NiFeSP on nickel foam (NiFeSP/NF), which shows superior electrocatalytic activity of low overpotentials of 91 mV at -10 mA cm -2 for HER and of 240 mV at 50 mA cm -2 for OER in 1 M KOH solution. In addition, the NiFeSP/NF presents excellent overall water splitting performance with a cell voltage as low as 1.58 V at a current density of 10 mA cm -2 . Combining with a photovoltaic device of a Si solar cell or integrating into photoelectrochemical (PEC) systems, the bifunctional NiFeSP/NF electrocatalyst implements unassisted solar-driven water splitting with a solar-to-hydrogen conversion efficiency of ∼9.2% and significantly enhanced PEC performance, respectively.

Improving the efficiency of water splitting in dye-sensitized solar cells by using a biomimetic electron transfer mediator

PubMed Central

Zhao, Yixin; Swierk, John R.; Megiatto, Jackson D.; Sherman, Benjamin; Youngblood, W. Justin; Qin, Dongdong; Lentz, Deanna M.; Moore, Ana L.; Moore, Thomas A.; Gust, Devens; Mallouk, Thomas E.

2012-01-01

Photoelectrochemical water splitting directly converts solar energy to chemical energy stored in hydrogen, a high energy density fuel. Although water splitting using semiconductor photoelectrodes has been studied for more than 40 years, it has only recently been demonstrated using dye-sensitized electrodes. The quantum yield for water splitting in these dye-based systems has, so far, been very low because the charge recombination reaction is faster than the catalytic four-electron oxidation of water to oxygen. We show here that the quantum yield is more than doubled by incorporating an electron transfer mediator that is mimetic of the tyrosine-histidine mediator in Photosystem II. The mediator molecule is covalently bound to the water oxidation catalyst, a colloidal iridium oxide particle, and is coadsorbed onto a porous titanium dioxide electrode with a Ruthenium polypyridyl sensitizer. As in the natural photosynthetic system, this molecule mediates electron transfer between a relatively slow metal oxide catalyst that oxidizes water on the millisecond timescale and a dye molecule that is oxidized in a fast light-induced electron transfer reaction. The presence of the mediator molecule in the system results in photoelectrochemical water splitting with an internal quantum efficiency of approximately 2.3% using blue light. PMID:22547794

Solar Water Splitting at λ=600 nm: A Step Closer to Sustainable Hydrogen Production.

PubMed

Zhang, Jinshui; Wang, Xinchen

2015-06-15

Overall water splitting with a semiconductor photocatalyst under visible-light irradiation is considered as a "dream reaction" in chemistry. The development of a 600 nm photocatalyst for solar water splitting highlighted here is not only an important milestone towards sustainable hydrogen production, but also a new starting point for artificial photosynthesis. STH=solar-to-hydrogen energy conversion efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient generation of H2 by splitting water with an isothermal redox cycle.

PubMed

Muhich, Christopher L; Evanko, Brian W; Weston, Kayla C; Lichty, Paul; Liang, Xinhua; Martinek, Janna; Musgrave, Charles B; Weimer, Alan W

2013-08-02

Solar thermal water-splitting (STWS) cycles have long been recognized as a desirable means of generating hydrogen gas (H2) from water and sunlight. Two-step, metal oxide-based STWS cycles generate H2 by sequential high-temperature reduction and water reoxidation of a metal oxide. The temperature swings between reduction and oxidation steps long thought necessary for STWS have stifled STWS's overall efficiency because of thermal and time losses that occur during the frequent heating and cooling of the metal oxide. We show that these temperature swings are unnecessary and that isothermal water splitting (ITWS) at 1350°C using the "hercynite cycle" exhibits H2 production capacity >3 and >12 times that of hercynite and ceria, respectively, per mass of active material when reduced at 1350°C and reoxidized at 1000°C.

Polyaniline as a new type of hole-transporting material to significantly increase the solar water splitting performance of BiVO4 photoanodes

NASA Astrophysics Data System (ADS)

Wang, Xiaojun; Ye, Kai-Hang; Yu, Xiang; Zhu, Jiaqian; Zhu, Yi; Zhang, Yuanming

2018-07-01

Polyaniline (PANI), with its low cost, chemical stability and high conductivity, is used as a hole transporting layer to fabricate NiOOH/PANI/BiVO4 (NPB) photoanode, of which the photoelectrochemical (PEC) water splitting performance is significantly enhanced. The remarkable water oxidation photocurrent of NPB photoanode achieves 3.31 mA cm-2 at 1.23 V vs. RHE under AM 1.5G solar light irradiation, which is greatly increased compared with that of pristine BiVO4 (0.89 mA cm-2 under the same condition). The maximal incident photon-to-current conversion efficiency achieves 83.3% at 430 nm at 1.23 V vs. RHE and the maximal applied bias photo-to-current efficiency reaches 1.20% at 0.68 V vs. RHE, which are nearly five and ten times higher than that of pristine BiVO4 photoanode, respectively. This NPB photoanode exhibits excellent stability with about 97.22% Faraday efficiency after PEC water splitting for 3 h. The exciting results demonstrate that PANI shows great potential as a hole-transporting layer for photoanode and NPB is an efficient and stable photoanode material with a great potential application in PEC water splitting. Overall, this work provides an excellent reference on designing and fabricating photoanode materials for the future.

Direct selenylation of mixed Ni/Fe metal-organic frameworks to NiFe-Se/C nanorods for overall water splitting

NASA Astrophysics Data System (ADS)

Xu, Bo; Yang, He; Yuan, Lincheng; Sun, Yiqiang; Chen, Zhiming; Li, Cuncheng

2017-10-01

Development of low-cost, highly active bifunctional catalyst for efficient overall water splitting based on earth-abundant metals is still a great challenging task. In this work, we report a NiFe-Se/C composite nanorod as efficient non-precious-metal electrochemical catalyst derived from direct selenylation of a mixed Ni/Fe metal-organic framework. The as-obtained catalyst requires low overpotential to drive 10 mA cm-2 for HER (160 mV) and OER (240 mV) in 1.0 M KOH, respectively, and its catalytic activity is maintained for at least 20 h. Moreover, water electrolysis using this catalyst achieves high water splitting current density of 10 mA cm-2 at cell voltage of 1.68 V.

All solution-processed lead halide perovskite-BiVO4 tandem assembly for photolytic solar fuels production.

PubMed

Chen, Yong-Siou; Manser, Joseph S; Kamat, Prashant V

2015-01-21

The quest for economic, large-scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. Here we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons, and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard AM 1.5G illumination, the photoanode-photovoltaic architecture, in conjunction with an earth-abundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially promising new frontier for solar water splitting research.

Efficient electrolyzer for CO2 splitting in neutral water using earth-abundant materials.

PubMed

Tatin, Arnaud; Comminges, Clément; Kokoh, Boniface; Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

2016-05-17

Low-cost, efficient CO2-to-CO+O2 electrochemical splitting is a key step for liquid-fuel production for renewable energy storage and use of CO2 as a feedstock for chemicals. Heterogeneous catalysts for cathodic CO2-to-CO associated with an O2-evolving anodic reaction in high-energy-efficiency cells are not yet available. An iron porphyrin immobilized into a conductive Nafion/carbon powder layer is a stable cathode producing CO in pH neutral water with 90% faradaic efficiency. It is coupled with a water oxidation phosphate cobalt oxide anode in a home-made electrolyzer by means of a Nafion membrane. Current densities of approximately 1 mA/cm(2) over 30-h electrolysis are achieved at a 2.5-V cell voltage, splitting CO2 and H2O into CO and O2 with a 50% energy efficiency. Remarkably, CO2 reduction outweighs the concurrent water reduction. The setup does not prevent high-efficiency proton transport through the Nafion membrane separator: The ohmic drop loss is only 0.1 V and the pH remains stable. These results demonstrate the possibility to set up an efficient, low-voltage, electrochemical cell that converts CO2 into CO and O2 by associating a cathodic-supported molecular catalyst based on an abundant transition metal with a cheap, easy-to-prepare anodic catalyst oxidizing water into O2.

Anti-reflective nanoporous silicon for efficient hydrogen production

DOEpatents

Oh, Jihun; Branz, Howard M

2014-05-20

Exemplary embodiments are disclosed of anti-reflective nanoporous silicon for efficient hydrogen production by photoelectrolysis of water. A nanoporous black Si is disclosed as an efficient photocathode for H.sub.2 production from water splitting half-reaction.

Efficient carbon dots/NiFe-layered double hydroxide/BiVO4 photoanodes for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Lv, Xiaowei; Xiao, Xin; Cao, Minglei; Bu, Yi; Wang, Chuanqing; Wang, Mingkui; Shen, Yan

2018-05-01

Modification of semiconductor photoanodes with oxygen evolution catalyst (OEC) is an effective approach for improving photoelectrochemical (PEC) water splitting efficiency. In the configuration, how to increase the activity of OEC is crucial to further improve PEC performance. Herein, a ternary photoanode system was designed to enhance PEC efficiency of photoelectrodes through introducing carbon dots (CDs), NiFe-layered double hydroxide (NiFe-LDH) nanosheets on BiVO4 particles. Systematic research shows that NiFe-LDH serves as an OEC which accelerates oxygen evolution kinetics, while the introduction of CDs can further reduce charge transfer resistance and overpotential for oxygen evolution. Under the synergistic effect of NiFe-LDH and CDs, the photocurrent and incident photon to current conversion efficiency (IPCE) of the resulting CDs/NiFe-LDH/BiVO4 photoanode is improved significantly than those of the NiFe-LDH/BiVO4 electrode. Consequently, such a ternary heterostructure could be an alternative way to further enhance PEC water splitting performance.

Improvement of efficiency in graphene/gallium nitride nanowire on Silicon photoelectrode for overall water splitting

NASA Astrophysics Data System (ADS)

Bae, Hyojung; Rho, Hokyun; Min, Jung-Wook; Lee, Yong-Tak; Lee, Sang Hyun; Fujii, Katsushi; Lee, Hyo-Jong; Ha, Jun-Seok

2017-11-01

Gallium nitride (GaN) nanowires are one of the most promising photoelectrode materials due to their high stability in acidic and basic electrolytes, and tunable band edge potentials. In this study, GaN nanowire arrays (GaN NWs) were prepared by molecular beam epitaxy (MBE); their large surface area enhanced the solar to hydrogen conversion efficiency. More significantly, graphene was grown by chemical vapor deposition (CVD), which enhanced the electron transfer between NWs for water splitting and protected the GaN NW surface. Structural characterizations of the prepared composite were performed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photocurrent density of Gr/GaN NWs exhibited a two-fold increase over pristine GaN NWs and sustained water splitting up to 70 min. These improvements may accelerate possible applications for hydrogen generation with high solar to hydrogen conversion efficiency.

Water splitting-biosynthetic system with CO₂ reduction efficiencies exceeding photosynthesis.

PubMed

Liu, Chong; Colón, Brendan C; Ziesack, Marika; Silver, Pamela A; Nocera, Daniel G

2016-06-03

Artificial photosynthetic systems can store solar energy and chemically reduce CO2 We developed a hybrid water splitting-biosynthetic system based on a biocompatible Earth-abundant inorganic catalyst system to split water into molecular hydrogen and oxygen (H2 and O2) at low driving voltages. When grown in contact with these catalysts, Ralstonia eutropha consumed the produced H2 to synthesize biomass and fuels or chemical products from low CO2 concentration in the presence of O2 This scalable system has a CO2 reduction energy efficiency of ~50% when producing bacterial biomass and liquid fusel alcohols, scrubbing 180 grams of CO2 per kilowatt-hour of electricity. Coupling this hybrid device to existing photovoltaic systems would yield a CO2 reduction energy efficiency of ~10%, exceeding that of natural photosynthetic systems. Copyright © 2016, American Association for the Advancement of Science.

Tantalum-based semiconductors for solar water splitting.

PubMed

Zhang, Peng; Zhang, Jijie; Gong, Jinlong

2014-07-07

Solar energy utilization is one of the most promising solutions for the energy crises. Among all the possible means to make use of solar energy, solar water splitting is remarkable since it can accomplish the conversion of solar energy into chemical energy. The produced hydrogen is clean and sustainable which could be used in various areas. For the past decades, numerous efforts have been put into this research area with many important achievements. Improving the overall efficiency and stability of semiconductor photocatalysts are the research focuses for the solar water splitting. Tantalum-based semiconductors, including tantalum oxide, tantalate and tantalum (oxy)nitride, are among the most important photocatalysts. Tantalum oxide has the band gap energy that is suitable for the overall solar water splitting. The more negative conduction band minimum of tantalum oxide provides photogenerated electrons with higher potential for the hydrogen generation reaction. Tantalates, with tunable compositions, show high activities owning to their layered perovskite structure. (Oxy)nitrides, especially TaON and Ta3N5, have small band gaps to respond to visible-light, whereas they can still realize overall solar water splitting with the proper positions of conduction band minimum and valence band maximum. This review describes recent progress regarding the improvement of photocatalytic activities of tantalum-based semiconductors. Basic concepts and principles of solar water splitting will be discussed in the introduction section, followed by the three main categories regarding to the different types of tantalum-based semiconductors. In each category, synthetic methodologies, influencing factors on the photocatalytic activities, strategies to enhance the efficiencies of photocatalysts and morphology control of tantalum-based materials will be discussed in detail. Future directions to further explore the research area of tantalum-based semiconductors for solar water splitting are also discussed.

3D WO3 /BiVO4 /Cobalt Phosphate Composites Inverse Opal Photoanode for Efficient Photoelectrochemical Water Splitting.

PubMed

Zhang, Haifeng; Zhou, Weiwei; Yang, Yaping; Cheng, Chuanwei

2017-04-01

A novel 3D WO 3 /BiVO 4 /cobalt phosphate composite inverse opal is designed for photoeletrochemical (PEC) water splitting, yielding a significantly improved PEC performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient solar-driven water splitting by nanocone BiVO4-perovskite tandem cells

PubMed Central

Qiu, Yongcai; Liu, Wei; Chen, Wei; Chen, Wei; Zhou, Guangmin; Hsu, Po-Chun; Zhang, Rufan; Liang, Zheng; Fan, Shoushan; Zhang, Yuegang; Cui, Yi

2016-01-01

Bismuth vanadate (BiVO4) has been widely regarded as a promising photoanode material for photoelectrochemical (PEC) water splitting because of its low cost, its high stability against photocorrosion, and its relatively narrow band gap of 2.4 eV. However, the achieved performance of the BiVO4 photoanode remains unsatisfactory to date because its short carrier diffusion length restricts the total thickness of the BiVO4 film required for sufficient light absorption. We addressed the issue by deposition of nanoporous Mo-doped BiVO4 (Mo:BiVO4) on an engineered cone-shaped nanostructure, in which the Mo:BiVO4 layer with a larger effective thickness maintains highly efficient charge separation and high light absorption capability, which can be further enhanced by multiple light scattering in the nanocone structure. As a result, the nanocone/Mo:BiVO4/Fe(Ni)OOH photoanode exhibits a high water-splitting photocurrent of 5.82 ± 0.36 mA cm−2 at 1.23 V versus the reversible hydrogen electrode under 1-sun illumination. We also demonstrate that the PEC cell in tandem with a single perovskite solar cell exhibits unassisted water splitting with a solar-to-hydrogen conversion efficiency of up to 6.2%. PMID:27386565

Efficient Visible-Light-Driven Z-Scheme Overall Water Splitting Using a MgTa2O(6-x)N(y)/TaON Heterostructure Photocatalyst for H2 Evolution.

PubMed

Chen, Shanshan; Qi, Yu; Hisatomi, Takashi; Ding, Qian; Asai, Tomohiro; Li, Zheng; Ma, Su Su Khine; Zhang, Fuxiang; Domen, Kazunari; Li, Can

2015-07-13

An (oxy)nitride-based heterostructure for powdered Z-scheme overall water splitting is presented. Compared with the single MgTa2O(6-x)N(y) or TaON photocatalyst, a MgTa2O(6-x)N(y)/TaON heterostructure fabricated by a simple one-pot nitridation route was demonstrated to effectively suppress the recombination of carriers by efficient spatial charge separation and decreased defect density. By employing Pt-loaded MgTa2O(6-x)N(y)/TaON as a H2-evolving photocatalyst, a Z-scheme overall water splitting system with an apparent quantum efficiency (AQE) of 6.8% at 420 nm was constructed (PtO(x)-WO3 and IO3(-)/I(-) pairs were used as an O2-evolving photocatalyst and a redox mediator, respectively), the activity of which is circa 7 or 360 times of that using Pt-TaON or Pt-MgTa2O(6-x)N)y) as a H2-evolving photocatalyst, respectively. To the best of our knowledge, this is the highest AQE among the powdered Z-scheme overall water splitting systems ever reported. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Photocarrier Separation in Hierarchical Graphitic-C3N4-Supported CuInS2 for Noble-Metal-Free Z-Scheme Photocatalytic Water Splitting.

PubMed

Li, Xiaoxue; Xie, Keyu; Song, Long; Zhao, Mengjia; Zhang, Zhipan

2017-07-26

The effective separation of photogenerated electrons and holes in photocatalysts is a prerequisite for efficient photocatalytic water splitting. CuInS 2 (CIS) is a widely used light absorber that works properly in photovoltaics but only shows limited performance in solar-driven hydrogen evolution due to its intrinsically severe charge recombination. Here, we prepare hierarchical graphitic C 3 N 4 -supported CuInS 2 (denoted as GsC) by an in situ growth of CIS directly on exfoliated thin graphitic C 3 N 4 nanosheets (g-C 3 N 4 NS) and demonstrate efficient separation of photoinduced charge carriers in the GsC by forming the Z-scheme system for the first time in CIS-catalyzed water splitting. Under visible light illumination, the GsC features an enhanced hydrogen evolution rate up to 1290 μmol g -1 h -1 , which is 3.3 and 6.1 times higher than that of g-C 3 N 4 NS and bare-CIS, respectively, thus setting a new performance benchmark for CIS-based water-splitting photocatalysts.

Semiconductor-based photoelectrochemical water splitting at the limit of very wide depletion region

DOE PAGES

Liu, Mingzhao; Lyons, John L.; Yan, Danhua H.; ...

2015-11-23

In semiconductor-based photoelectrochemical (PEC) water splitting, carrier separation and delivery largely relies on the depletion region formed at the semiconductor/water interface. As a Schottky junction device, the trade-off between photon collection and minority carrier delivery remains a persistent obstacle for maximizing the performance of a water splitting photoelectrode. Here, it is demonstrated that the PEC water splitting efficiency for an n-SrTiO 3 (n-STO) photoanode is improved very significantly despite its weak indirect band gap optical absorption (α < 10⁴ cm⁻¹), by widening the depletion region through engineering its doping density and profile. Graded doped n-SrTiO 3 photoanodes are fabricated withmore » their bulk heavily doped with oxygen vacancies but their surface lightly doped over a tunable depth of a few hundred nanometers, through a simple low temperature re-oxidation technique. The graded doping profile widens the depletion region to over 500 nm, thus leading to very efficient charge carrier separation and high quantum efficiency (>70%) for the weak indirect transition. As a result, this simultaneous optimization of the light absorption, minority carrier (hole) delivery, and majority carrier (electron) transport by means of a graded doping architecture may be useful for other indirect band gap photocatalysts that suffer from a similar problem of weak optical absorption.« less

Highly Efficient and Robust Nickel Phosphides as Bifunctional Electrocatalysts for Overall Water-Splitting.

PubMed

Li, Jiayuan; Li, Jing; Zhou, Xuemei; Xia, Zhaoming; Gao, Wei; Ma, Yuanyuan; Qu, Yongquan

2016-05-04

To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.

Interplay of oxygen-evolution kinetics and photovoltaic power curves on the construction of artificial leaves

PubMed Central

Surendranath, Yogesh; Bediako, D. Kwabena; Nocera, Daniel G.

2012-01-01

An artificial leaf can perform direct solar-to-fuels conversion. The construction of an efficient artificial leaf or other photovoltaic (PV)-photoelectrochemical device requires that the power curve of the PV material and load curve of water splitting, composed of the catalyst Tafel behavior and cell resistances, be well-matched near the thermodynamic potential for water splitting. For such a condition, we show here that the current density-voltage characteristic of the catalyst is a key determinant of the solar-to-fuels efficiency (SFE). Oxidic Co and Ni borate (Co-Bi and Ni-Bi) thin films electrodeposited from solution yield oxygen-evolving catalysts with Tafel slopes of 52 mV/decade and 30 mV/decade, respectively. The consequence of the disparate Tafel behavior on the SFE is modeled using the idealized behavior of a triple-junction Si PV cell. For PV cells exhibiting similar solar power-conversion efficiencies, those displaying low open circuit voltages are better matched to catalysts with low Tafel slopes and high exchange current densities. In contrast, PV cells possessing high open circuit voltages are largely insensitive to the catalyst’s current density-voltage characteristics but sacrifice overall SFE because of less efficient utilization of the solar spectrum. The analysis presented herein highlights the importance of matching the electrochemical load of water-splitting to the onset of maximum current of the PV component, drawing a clear link between the kinetic profile of the water-splitting catalyst and the SFE efficiency of devices such as the artificial leaf. PMID:22689962

Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muzzillo, Christopher; Klein, Walter E; Li, Zhen

Photoelectrochemical (PEC) water splitting is an elegant method of converting sunlight and water into H2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient, and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV andmore » decreased saturated photocurrent density from 18 to 8 mA/cm2 as measured by chopped-light current-voltage (CLIV) measurements in a 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa3Se5) and 1.86 eV band gaps had exceptional durability and continuously split water for 17 days (~12 mA/cm2 at -1 V vs RHE). This is equivalent to ~17 200 C/cm2, which is a world record for any polycrystalline PEC absorber. These results indicate that CuGa3Se5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.« less

Low-Cost, Efficient, and Durable H2 Production by Photoelectrochemical Water Splitting with CuGa3Se5 Photocathodes.

PubMed

Muzzillo, Christopher P; Klein, W Ellis; Li, Zhen; DeAngelis, Alexander Daniel; Horsley, Kimberly; Zhu, Kai; Gaillard, Nicolas

2018-06-13

Photoelectrochemical (PEC) water splitting is an elegant method of converting sunlight and water into H 2 fuel. To be commercially advantageous, PEC devices must become cheaper, more efficient, and much more durable. This work examines low-cost polycrystalline chalcopyrite films, which are successful as photovoltaic absorbers, for application as PEC absorbers. In particular, Cu-Ga-Se films with wide band gaps can be employed as top cell photocathodes in tandem devices as a realistic route to high efficiencies. In this report, we demonstrate that decreasing Cu/Ga composition from 0.66 to 0.31 in Cu-Ga-Se films increased the band gap from 1.67 to 1.86 eV and decreased saturated photocurrent density from 18 to 8 mA/cm 2 as measured by chopped-light current-voltage (CLIV) measurements in a 0.5 M sulfuric acid electrolyte. Buffer and catalyst surface treatments were not applied to the Cu-Ga-Se films, and they exhibited promising stability, evidenced by unchanged CLIV after 9 months of storage in air. Finally, films with Cu/Ga = 0.36 (approximately stoichiometric CuGa 3 Se 5 ) and 1.86 eV band gaps had exceptional durability and continuously split water for 17 days (∼12 mA/cm 2 at -1 V vs RHE). This is equivalent to ∼17 200 C/cm 2 , which is a world record for any polycrystalline PEC absorber. These results indicate that CuGa 3 Se 5 films are prime candidates for cheaply achieving efficient and durable PEC water splitting.

Copper Oxide Nanograss for Efficient and Stable Photoelectrochemical Hydrogen Production by Water Splitting

NASA Astrophysics Data System (ADS)

Borkar, Rajnikant; Dahake, Rashmi; Rayalu, Sadhana; Bansiwal, Amit

2018-03-01

A biphasic copper oxide thin film of grass-like appendage morphology is synthesized by two-step electro-deposition method and later investigated for photoelectrochemical (PEC) water splitting for hydrogen production. Further, the thin film was characterized by UV-Visible spectroscopy, x-ray diffraction (XRD), Scanning electron microscopy (SEM) and PEC techniques. The XRD analysis confirms formation of biphasic copper oxide phases, and SEM reveals high surface area grass appendage-like morphology. These grass appendage structures exhibit a high cathodic photocurrent of - 1.44 mAcm-2 at an applied bias of - 0.7 (versus Ag/AgCl) resulting in incident to photon current efficiency (IPCE) of ˜ 10% at 400 nm. The improved light harvesting and charge transport properties of grass appendage structured biphasic copper oxides makes it a potential candidate for PEC water splitting for hydrogen production.

Space-Confined Earth-Abundant Bifunctional Electrocatalyst for High-Efficiency Water Splitting.

PubMed

Tang, Yanqun; Fang, Xiaoyu; Zhang, Xin; Fernandes, Gina; Yan, Yong; Yan, Dongpeng; Xiang, Xu; He, Jing

2017-10-25

Hydrogen generation from water splitting could be an alternative way to meet increasing energy demands while also balancing the impact of energy being supplied by fossil-based fuels. The efficacy of water splitting strongly depends on the performance of electrocatalysts. Herein, we report a unique space-confined earth-abundant electrocatalyst having the bifunctionality of simultaneous hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), leading to high-efficiency water splitting. Outperforming Pt/C or RuO 2 catalysts, this mesoscopic, space-confined, bifunctional configuration is constructed from a monolithic zeolitic imidazolate framework@layered double hydroxide (ZIF@LDH) precursor on Ni foam. Such a confinement leads to a high dispersion of ultrafine Co 3 O 4 nanoparticles within the N-doped carbon matrix by temperature-dependent calcination of the ZIF@LDH. We demonstrate that the OER has an overpotential of 318 mV at a current density of 10 mA cm -2 , while that of HER is -106 mV @ -10 mA cm -2 . The voltage applied to a two-electrode cell for overall water splitting is 1.59 V to achieve a stable current density of 10 mA cm -2 while using the monolithic catalyst as both the anode and the cathode. It is anticipated that our space-confined method, which focuses on earth-abundant elements with structural integrity, may provide a novel and economically sound strategy for practical energy conversion applications.

Decades After Developing Technology, NREL Sets New Solar-to-Hydrogen Record

Science.gov Websites

recently achieved 16.2% solar-to-hydrogen conversion efficiency. Photo by Dennis Schroeder Innovation is to split water into hydrogen and oxygen. Photo by Dennis Schroeder Photo shows a photoelectrochemical device to split water into hydrogen and oxygen. Photo by Dennis Schroeder Second Look Leads to Record

Facile fabrication of an efficient BiVO4 thin film electrode for water splitting under visible light irradiation.

PubMed

Jia, Qingxin; Iwashina, Katsuya; Kudo, Akihiko

2012-07-17

An efficient BiVO(4) thin film electrode for overall water splitting was prepared by dipping an F-doped SnO(2) (FTO) substrate electrode in an aqueous nitric acid solution of Bi(NO(3))(3) and NH(4)VO(3), and subsequently calcining it. X-ray diffraction of the BiVO(4) thin film revealed that a photocatalytically active phase of scheelite-monoclinic BiVO(4) was obtained. Scanning electron microscopy images showed that the surface of an FTO substrate was uniformly coated with the BiVO(4) film with 300-400 nm of the thickness. The BiVO(4) thin film electrode gave an excellent anodic photocurrent with 73% of an IPCE at 420 nm at 1.0 V vs. Ag/AgCl. Modification with CoO on the BiVO(4) electrode improved the photoelectrochemical property. A photoelectrochemical cell consisting of the BiVO(4) thin film electrode with and without CoO, and a Pt counter electrode was constructed for water splitting under visible light irradiation and simulated sunlight irradiation. Photocurrent due to water splitting to form H(2) and O(2) was confirmed with applying an external bias smaller than 1.23 V that is a theoretical voltage for electrolysis of water. Water splitting without applying external bias under visible light irradiation was demonstrated using a SrTiO(3)Rh photocathode and the BiVO(4) photoanode.

Thermodynamic Analysis of the Use a Chemical Heat Pump to Link a Supercritical Water-Cooled Nuclear Reactor and a Thermochemical Water-Splitting Cycle for Hydrogen Production

NASA Astrophysics Data System (ADS)

Granovskii, Mikhail; Dincer, Ibrahim; Rosen, Marc A.; Pioro, Igor

Increases in the power generation efficiency of nuclear power plants (NPPs) are mainly limited by the permissible temperatures in nuclear reactors and the corresponding temperatures and pressures of the coolants in reactors. Coolant parameters are limited by the corrosion rates of materials and nuclear-reactor safety constraints. The advanced construction materials for the next generation of CANDU reactors, which employ supercritical water (SCW) as a coolant and heat carrier, permit improved “steam” parameters (outlet temperatures up to 625°C and pressures of about 25 MPa). An increase in the temperature of steam allows it to be utilized in thermochemical water splitting cycles to produce hydrogen. These methods are considered by many to be among the most efficient ways to produce hydrogen from water and to have advantages over traditional low-temperature water electrolysis. However, even lower temperature water splitting cycles (Cu-Cl, UT-3, etc.) require an intensive heat supply at temperatures higher than 550-600°C. A sufficient increase in the heat transfer from the nuclear reactor to a thermochemical water splitting cycle, without jeopardizing nuclear reactor safety, might be effectively achieved by application of a heat pump, which increases the temperature of the heat supplied by virtue of a cyclic process driven by mechanical or electrical work. Here, a high-temperature chemical heat pump, which employs the reversible catalytic methane conversion reaction, is proposed. The reaction shift from exothermic to endothermic and back is achieved by a change of the steam concentration in the reaction mixture. This heat pump, coupled with the second steam cycle of a SCW nuclear power generation plant on one side and a thermochemical water splitting cycle on the other, increases the temperature of the “nuclear” heat and, consequently, the intensity of heat transfer into the water splitting cycle. A comparative preliminary thermodynamic analysis is conducted of the combined system comprising a SCW nuclear power generation plant and a chemical heat pump, which provides high-temperature heat to a thermochemical water splitting cycle for hydrogen production. It is concluded that the proposed chemical heat pump permits the utilization efficiency of nuclear energy to be improved by at least 2% without jeopardizing nuclear reactor safety. Based on this analysis, further research appears to be merited on the proposed advanced design of a nuclear power generation plant combined with a chemical heat pump, and implementation in appropriate applications seems worthwhile.

ZnO/CuO/M (M = Ag, Au) Hierarchical Nanostructure by Successive Photoreduction Process for Solar Hydrogen Generation.

PubMed

Kwon, Jinhyeong; Cho, Hyunmin; Jung, Jinwook; Lee, Habeom; Hong, Sukjoon; Yeo, Junyeob; Han, Seungyong; Ko, Seung Hwan

2018-05-12

To date, solar energy generation devices have been widely studied to meet a clean and sustainable energy source. Among them, water splitting photoelectrochemical cell is regarded as a promising energy generation way for splitting water molecules and generating hydrogen by sunlight. While many nanostructured metal oxides are considered as a candidate, most of them have an improper bandgap structure lowering energy transition efficiency. Herein, we introduce a novel wet-based, successive photoreduction process that can improve charge transfer efficiency by surface plasmon effect for a solar-driven water splitting device. The proposed process enables to fabricate ZnO/CuO/Ag or ZnO/CuO/Au hierarchical nanostructure, having an enhanced electrical, optical, photoelectrochemical property. The fabricated hierarchical nanostructures are demonstrated as a photocathode in the photoelectrochemical cell and characterized by using various analytic tools.

ZnO/CuO/M (M = Ag, Au) Hierarchical Nanostructure by Successive Photoreduction Process for Solar Hydrogen Generation

PubMed Central

Kwon, Jinhyeong; Cho, Hyunmin; Jung, Jinwook; Lee, Habeom; Han, Seungyong

2018-01-01

To date, solar energy generation devices have been widely studied to meet a clean and sustainable energy source. Among them, water splitting photoelectrochemical cell is regarded as a promising energy generation way for splitting water molecules and generating hydrogen by sunlight. While many nanostructured metal oxides are considered as a candidate, most of them have an improper bandgap structure lowering energy transition efficiency. Herein, we introduce a novel wet-based, successive photoreduction process that can improve charge transfer efficiency by surface plasmon effect for a solar-driven water splitting device. The proposed process enables to fabricate ZnO/CuO/Ag or ZnO/CuO/Au hierarchical nanostructure, having an enhanced electrical, optical, photoelectrochemical property. The fabricated hierarchical nanostructures are demonstrated as a photocathode in the photoelectrochemical cell and characterized by using various analytic tools. PMID:29757225

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

PubMed

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

Natural and Artificial Mn4 Ca Cluster for the Water Splitting Reaction.

PubMed

Chen, Changhui; Li, Yanxi; Zhao, Guoqing; Yao, Ruoqing; Zhang, Chunxi

2017-11-23

The oxygen-evolving center (OEC) in photosystem II (PSII) is a unique biological catalyst that splits water into electrons, protons, and O 2 by using solar energy. Recent crystallographic studies have revealed that the structure of the OEC is an asymmetric Mn 4 Ca cluster, which provides a blueprint to develop man-made water-splitting catalysts for artificial photosynthesis. Although it is a great challenge to mimic the whole structure and function of the OEC in the laboratory, significant advances have recently been achieved. In this Minireview, recent progress on mimicking the natural OEC is discussed. New strategies are suggested to construct more stable and efficient new generation of catalytic materials for the water splitting reaction based on the artificial Mn 4 Ca cluster in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A review on g-C3N4 for photocatalytic water splitting and CO2 reduction

NASA Astrophysics Data System (ADS)

Ye, Sheng; Wang, Rong; Wu, Ming-Zai; Yuan, Yu-Peng

2015-12-01

Solar fuel generation through water splitting and CO2 photoreduction is an ideal route to provide the renewable energy sources and mitigate global warming. The main challenge in photocatalysis is finding a low-cost photocatalyst that can work efficiently to split water into hydrogen and reduce CO2 to hydrocarbon fuels. Metal-free g-C3N4 photocatalyst shows great potentials for solar fuel production. In this mini review, we summarize the most current advances on novel design idea and new synthesis strategy for g-C3N4 preparation, insightful ideas on extending optical absorption of pristine g-C3N4, overall water splitting and CO2 photoreduction over g-C3N4 based systems. The research challenges and perspectives on g-C3N4 based photocatalysts were also suggested.

Modelling heterogeneous interfaces for solar water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pham, Tuan Anh; Ping, Yuan; Galli, Giulia

2017-01-09

The generation of hydrogen from water and sunlight others a promising approach for producing scalable and sustainable carbon-free energy. The key of a successful solar-to-fuel technology is the design of efficient, long-lasting and low-cost photoelectrochemical cells, which are responsible for absorbing sunlight and driving water splitting reactions. To this end, a detailed understanding and control of heterogeneous interfaces between photoabsorbers, electrolytes and catalysts present in photoelectrochemical cells is essential. Here we review recent progress and open challenges in predicting physicochemical properties of heterogeneous interfaces for solar water splitting applications using first-principles-based approaches, and highlights the key role of these calculationsmore » in interpreting increasingly complex experiments.« less

Efficiency limits for photoelectrochemical water-splitting

DOE PAGES

Fountaine, Katherine T.; Lewerenz, Hans Joachim; Atwater, Harry A.

2016-12-02

Theoretical limiting efficiencies have a critical role in determining technological viability and expectations for device prototypes, as evidenced by the photovoltaics community’s focus on detailed balance. However, due to their multicomponent nature, photoelectrochemical devices do not have an equivalent analogue to detailed balance, and reported theoretical efficiency limits vary depending on the assumptions made. Here we introduce a unified framework for photoelectrochemical device performance through which all previous limiting efficiencies can be understood and contextualized. Ideal and experimentally realistic limiting efficiencies are presented, and then generalized using five representative parameters—semiconductor absorption fraction, external radiative efficiency, series resistance, shunt resistance andmore » catalytic exchange current density—to account for imperfect light absorption, charge transport and catalysis. Finally, we discuss the origin of deviations between the limits discussed herein and reported water-splitting efficiencies. This analysis provides insight into the primary factors that determine device performance and a powerful handle to improve device efficiency.« less

Solar Water Splitting and Nitrogen Fixation with Layered Bismuth Oxyhalides.

PubMed

Li, Jie; Li, Hao; Zhan, Guangming; Zhang, Lizhi

2017-01-17

Hydrogen and ammonia are the chemical molecules that are vital to Earth's energy, environmental, and biological processes. Hydrogen with renewable, carbon-free, and high combustion-enthalpy hallmarks lays the foundation of next-generation energy source, while ammonia furnishes the building blocks of fertilizers and proteins to sustain the lives of plants and organisms. Such merits fascinate worldwide scientists in developing viable strategies to produce hydrogen and ammonia. Currently, at the forefronts of hydrogen and ammonia syntheses are solar water splitting and nitrogen fixation, because they go beyond the high temperature and pressure requirements of methane stream reforming and Haber-Bosch reaction, respectively, as the commercialized hydrogen and ammonia production routes, and inherit the natural photosynthesis virtues that are green and sustainable and operate at room temperature and atmospheric pressure. The key to propelling such photochemical reactions lies in searching photocatalysts that enable water splitting into hydrogen and nitrogen fixation to make ammonia efficiently. Although the past 40 years have witnessed significant breakthroughs using the most widely studied TiO 2 , SrTiO 3 , (Ga 1-x Zn x )(N 1-x O x ), CdS, and g-C 3 N 4 for solar chemical synthesis, two crucial yet still unsolved issues challenge their further progress toward robust solar water splitting and nitrogen fixation, including the inefficient steering of electron transportation from the bulk to the surface and the difficulty of activating the N≡N triple bond of N 2 . This Account details our endeavors that leverage layered bismuth oxyhalides as photocatalysts for efficient solar water splitting and nitrogen fixation, with a focus on addressing the above two problems. We first demonstrate that the layered structures of bismuth oxyhalides can stimulate an internal electric field (IEF) that is capable of efficiently separating electrons and holes after their formation and of precisely channeling their migration from the bulk to the surface along the different directions, thus enabling more electrons to reach the surface for water splitting and nitrogen fixation. Simultaneously, their oxygen termination feature and the strain differences between interlayers and intralayers render the easy generation of surface oxygen vacancies (OVs) that afford Lewis-base and unsaturated-unsaturated sites for nitrogen activation. With these rationales as the guideline, we can obtain striking visible-light hydrogen- and ammonia-evolving rates without using any noble-metal cocatalysts. Then we show how to utilize IEF and OV based strategies to improve the solar water splitting and nitrogen fixation performances of bismuth oxyhalide photocatalysts. Finally, we highlight the challenges remaining in using bismuth oxyhalides for solar hydrogen and ammonia syntheses, and the prospect of further development of this research field. We believe that our mechanistic insights could serve as a blueprint for the design of more efficient solar water splitting and nitrogen fixation systems, and layered bismuth oxyhalides might open up new photocatalyst paradigm for such two solar chemical syntheses.

H2 evolution at Si-based metal-insulator-semiconductor photoelectrodes enhanced by inversion channel charge collection and H spillover.

PubMed

Esposito, Daniel V; Levin, Igor; Moffat, Thomas P; Talin, A Alec

2013-06-01

Photoelectrochemical (PEC) water splitting represents a promising route for renewable production of hydrogen, but trade-offs between photoelectrode stability and efficiency have greatly limited the performance of PEC devices. In this work, we employ a metal-insulator-semiconductor (MIS) photoelectrode architecture that allows for stable and efficient water splitting using narrow bandgap semiconductors. Substantial improvement in the performance of Si-based MIS photocathodes is demonstrated through a combination of a high-quality thermal SiO2 layer and the use of bilayer metal catalysts. Scanning probe techniques were used to simultaneously map the photovoltaic and catalytic properties of the MIS surface and reveal the spillover-assisted evolution of hydrogen off the SiO2 surface and lateral photovoltage driven minority carrier transport over distances that can exceed 2 cm. The latter finding is explained by the photo- and electrolyte-induced formation of an inversion channel immediately beneath the SiO2/Si interface. These findings have important implications for further development of MIS photoelectrodes and offer the possibility of highly efficient PEC water splitting.

Proton-Induced Trap States, Injection and Recombination Dynamics in Water-Splitting Dye-Sensitized Photoelectrochemical Cells.

PubMed

McCool, Nicholas S; Swierk, John R; Nemes, Coleen T; Saunders, Timothy P; Schmuttenmaer, Charles A; Mallouk, Thomas E

2016-07-06

Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) utilize a sensitized metal oxide and a water oxidation catalyst in order to generate hydrogen and oxygen from water. Although the Faradaic efficiency of water splitting is close to unity, the recombination of photogenerated electrons with oxidized dye molecules causes the quantum efficiency of these devices to be low. It is therefore important to understand recombination mechanisms in order to develop strategies to minimize them. In this paper, we discuss the role of proton intercalation in the formation of recombination centers. Proton intercalation forms nonmobile surface trap states that persist on time scales that are orders of magnitude longer than the electron lifetime in TiO2. As a result of electron trapping, recombination with surface-bound oxidized dye molecules occurs. We report a method for effectively removing the surface trap states by mildly heating the electrodes under vacuum, which appears to primarily improve the injection kinetics without affecting bulk trapping dynamics, further stressing the importance of proton control in WS-DSPECs.

Hybrid bio-photo-electro-chemical cells for solar water splitting

PubMed Central

Pinhassi, Roy I.; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-01-01

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm−2. Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel. PMID:27550091

Hybrid bio-photo-electro-chemical cells for solar water splitting.

PubMed

Pinhassi, Roy I; Kallmann, Dan; Saper, Gadiel; Dotan, Hen; Linkov, Artyom; Kay, Asaf; Liveanu, Varda; Schuster, Gadi; Adir, Noam; Rothschild, Avner

2016-08-23

Photoelectrochemical water splitting uses solar power to decompose water to hydrogen and oxygen. Here we show how the photocatalytic activity of thylakoid membranes leads to overall water splitting in a bio-photo-electro-chemical (BPEC) cell via a simple process. Thylakoids extracted from spinach are introduced into a BPEC cell containing buffer solution with ferricyanide. Upon solar-simulated illumination, water oxidation takes place and electrons are shuttled by the ferri/ferrocyanide redox couple from the thylakoids to a transparent electrode serving as the anode, yielding a photocurrent density of 0.5 mA cm(-2). Hydrogen evolution occurs at the cathode at a bias as low as 0.8 V. A tandem cell comprising the BPEC cell and a Si photovoltaic module achieves overall water splitting with solar to hydrogen efficiency of 0.3%. These results demonstrate the promise of combining natural photosynthetic membranes and man-made photovoltaic cells in order to convert solar power into hydrogen fuel.

Water Splitting via Decoupled Photocatalytic Water Oxidation and Electrochemical Proton Reduction Mediated by Electron-Coupled-Proton Buffer.

PubMed

Li, Fei; Yu, Fengshou; Du, Jian; Wang, Yong; Zhu, Yong; Li, Xiaona; Sun, Licheng

2017-10-18

Water splitting mediated by electron-coupled-proton buffer (ECPB) provides an efficient way to avoid gas mixing by separating oxygen evolution from hydrogen evolution in space and time. Though electrochemical and photoelectrochemcial water oxidation have been incorporated in such a two-step water splitting system, alternative ways to reduce the cost and energy input for decoupling two half-reactions are desired. Herein, we show the feasibility of photocatalytic oxygen evolution in a powder system with BiVO 4 as a photocatalyst and polyoxometalate H 3 PMo 12 O 40 as an electron and proton acceptor. The resulting reaction mixture was allowed to be directly used for the subsequent hydrogen evolution with the reduced H 3 PMo 12 O 40 as electron and proton donors. Our system exhibits excellent stability in repeated oxygen and hydrogen evolution, which brings considerable convenience to decoupled water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Roles of Bi, M and VO{sub 4} tetrahedron in photocatalytic properties of novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions for overall water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Hui; Research Center for Combustion and Environment Technology, Shanghai Jiao Tong University, shanghai 200240; Faculty of Engineering Sciences, Kyushu University, Fukuoka 816-8580

2012-02-15

Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (BMV; M=La, Eu, Sm and Y) solid solutions were prepared and studied in this paper. All the samples were proved to produce H{sub 2} and O{sub 2} simultaneously from pure water under the irradiation of UV light. M-O bond lengths were proved to increase with M cations by refining cell parameters and atomic positions. Besides, band gaps, energy gaps and photocatalytic activities of BMV also changed with M cations. Both of M-O and V-O bond lengths were suggested to account for this phenomenon. Inactive A{sub 0.5}Y{sub 0.5}VO{sub 4} (A=La, Ce) for water splitting proved incorporationmore » of Bi rather than distortion of VO{sub 4} tetrahedron was a critical factor for improving efficiency of overall water splitting by facilitating the generation of electron and hole with lighter effective masses. Replacement of Bi by M cations not only gave indirect effect on band structure but also raised position of conduction band minimum to meet requirement of H{sub 2} production. - Graphical abstract: Novel Bi{sub 0.5}M{sub 0.5}VO{sub 4} (M=La, Eu, Sm and Y) solid solutions showed the high and stable photocatalytic activities for overall water splitting with their crystal radii of M elements. Highlights: Black-Right-Pointing-Pointer BMV solid solutions were novel highly efficient V-based photocatalysts for overall water splitting. Black-Right-Pointing-Pointer Photocatalytic activity of BMV solid solution related to the effective ionic radii of M cations. Black-Right-Pointing-Pointer Incorporation of Bi is one of key factors for the highly efficient activity of BMV solid solution. Black-Right-Pointing-Pointer Incorporation of Y is dispensable for H{sub 2} production.« less

Decorating CoP and Pt Nanoparticles on Graphitic Carbon Nitride Nanosheets to Promote Overall Water Splitting by Conjugated Polymers.

PubMed

Pan, Zhiming; Zheng, Yun; Guo, Fangsong; Niu, Pingping; Wang, Xinchen

2017-01-10

The splitting of water into H 2 and O 2 using solar energy is one of the key steps in artificial photosynthesis for the future production of renewable energy. Here, we show the first use of CoP and Pt nanoparticles as dual co-catalysts to modify graphitic carbon nitride (g-C 3 N 4 ) polymer to achieve overall water splitting under visible light irradiation. Our findings demonstrate that loading dual co-catalysts on delaminated g-C 3 N 4 imparts surface redox sites on the g-C 3 N 4 nanosheets that can not only promote catalytic kinetics but also promote charge separation and migration in the soft interface, thus improving the photocatalytic efficiency for overall water splitting. This robust, abundant, and stable photocatalyst based on covalent organic frameworks is demonstrated to hold great promise by forming heterojunctions with CoP and Pt for catalyzing the direct splitting of water into stoichiometric H 2 and O 2 using energy from photons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanistic Understanding of the Plasmonic Enhancement for Solar Water Splitting.

PubMed

Zhang, Peng; Wang, Tuo; Gong, Jinlong

2015-09-23

H2 generation by solar water splitting is one of the most promising solutions to meet the increasing energy demands of the fast developing society. However, the efficiency of solar-water-splitting systems is still too low for practical applications, which requires further enhancement via different strategies such as doping, construction of heterojunctions, morphology control, and optimization of the crystal structure. Recently, integration of plasmonic metals to semiconductor photocatalysts has been proved to be an effective way to improve their photocatalytic activities. Thus, in-depth understanding of the enhancement mechanisms is of great importance for better utilization of the plasmonic effect. This review describes the relevant mechanisms from three aspects, including: i) light absorption and scattering; ii) hot-electron injection and iii) plasmon-induced resonance energy transfer (PIRET). Perspectives are also proposed to trigger further innovative thinking on plasmonic-enhanced solar water splitting. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enabling unassisted solar water splitting by iron oxide and silicon

DOE PAGES

Jang, Ji-Wook; Du, Chun; Ye, Yifan; ...

2015-06-16

A solution for large-scale solar energy storage is photoelectrochemical (PEC) water splitting. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. We show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversiblemore » hydrogen electrode) is achieved. In conclusion, this result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.« less

FeS2 /CoS2 Interface Nanosheets as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Li, Yuxuan; Yin, Jie; An, Li; Lu, Min; Sun, Ke; Zhao, Yong-Qin; Gao, Daqiang; Cheng, Fangyi; Xi, Pinxian

2018-05-28

Electrochemical water splitting to produce hydrogen and oxygen, as an important reaction for renewable energy storage, needs highly efficient and stable catalysts. Herein, FeS 2 /CoS 2 interface nanosheets (NSs) as efficient bifunctional electrocatalysts for overall water splitting are reported. The thickness and interface disordered structure with rich defects of FeS 2 /CoS 2 NSs are confirmed by atomic force microscopy and high-resolution transmission electron microscopy. Furthermore, extended X-ray absorption fine structure spectroscopy clarifies that FeS 2 /CoS 2 NSs with sulfur vacancies, which can further increase electrocatalytic performance. Benefiting from the interface nanosheets' structure with abundant defects, the FeS 2 /CoS 2 NSs show remarkable hydrogen evolution reaction (HER) performance with a low overpotential of 78.2 mV at 10 mA cm -2 and a superior stability for 80 h in 1.0 m KOH, and an overpotential of 302 mV at 100 mA cm -2 for the oxygen evolution reaction (OER). More importantly, the FeS 2 /CoS 2 NSs display excellent performance for overall water splitting with a voltage of 1.47 V to achieve current density of 10 mA cm -2 and maintain the activity for at least 21 h. The present work highlights the importance of engineering interface nanosheets with rich defects based on transition metal dichalcogenides for boosting the HER and OER performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photocatalytic water splitting over titania supported copper and nickel oxide in photoelectrochemical cell; optimization of photoconversion efficiency

NASA Astrophysics Data System (ADS)

Muti Mohamed, Norani; Bashiri, Robabeh; Kait, Chong Fai; Sufian, Suriati

2018-04-01

we investigated the influence of fluctuating the preparation variables of TiO2 on the efficiency of photocatalytic water splitting in photoelectrochemical (PEC) cell. Hydrothermal associated sol-gel technique was applied to synthesis modified TiO2 with nickel and copper oxide. The variation of water (mL), acid (mL) and total metal loading (%) were mathematically modelled using central composite design (CCD) from the response surface method (RSM) to explore the single and combined effects of parameters on the system performance. The experimental data were fitted using quadratic polynomial regression model from analysis of variance (ANOVA). The coefficient of determination value of 98% confirms the linear relationship between the experimental and predicted values. The amount of water had maximum effect on the photoconversion efficiency due to a direct effect on the crystalline and the number of defects on the surface of photocatalyst. The optimal parameter ratios with maximum photoconversion efficiency were 16 mL, 3 mL and 5 % for water, acid and total metal loading, respectively.

The GA sulfur-iodine water-splitting process - A status report

NASA Astrophysics Data System (ADS)

Besenbruch, G. E.; Chiger, H. D.; McCorkle, K. H.; Norman, J. H.; Rode, J. S.; Schuster, J. R.; Trester, P. W.

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

The GA sulfur-iodine water-splitting process - A status report

NASA Technical Reports Server (NTRS)

Besenbruch, G. E.; Chiger, H. D.; Mccorkle, K. H.; Norman, J. H.; Rode, J. S.; Schuster, J. R.; Trester, P. W.

1981-01-01

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

Printed assemblies of GaAs photoelectrodes with decoupled optical and reactive interfaces for unassisted solar water splitting

DOE PAGES

Kang, Dongseok; Young, James L.; Lim, Haneol; ...

2017-03-27

Despite their excellent photophysical properties and record-high solar-to-hydrogen conversion efficiency, the high cost and limited stability of III-V compound semiconductors prohibit their practical application in solar-driven photoelectrochemical water splitting. Here in this paper we present a strategy for III-V photocatalysis that can circumvent these difficulties via printed assemblies of epitaxially grown compound semiconductors. A thin film stack of GaAs-based epitaxial materials is released from the growth wafer and printed onto a non-native transparent substrate to form an integrated photocatalytic electrode for solar hydrogen generation. The heterogeneously integrated electrode configuration together with specialized epitaxial design serve to decouple the material interfacesmore » for illumination and electrocatalysis. Subsequently, this allows independent control and optimization of light absorption, carrier transport, charge transfer, and material stability. Using this approach, we construct a series-connected wireless tandem system of GaAs photoelectrodes and demonstrate 13.1% solar-to-hydrogen conversion efficiency of unassisted-mode water splitting.« less

Printed assemblies of GaAs photoelectrodes with decoupled optical and reactive interfaces for unassisted solar water splitting

NASA Astrophysics Data System (ADS)

Kang, Dongseok; Young, James L.; Lim, Haneol; Klein, Walter E.; Chen, Huandong; Xi, Yuzhou; Gai, Boju; Deutsch, Todd G.; Yoon, Jongseung

2017-03-01

Despite their excellent photophysical properties and record-high solar-to-hydrogen conversion efficiency, the high cost and limited stability of III-V compound semiconductors prohibit their practical application in solar-driven photoelectrochemical water splitting. Here we present a strategy for III-V photocatalysis that can circumvent these difficulties via printed assemblies of epitaxially grown compound semiconductors. A thin film stack of GaAs-based epitaxial materials is released from the growth wafer and printed onto a non-native transparent substrate to form an integrated photocatalytic electrode for solar hydrogen generation. The heterogeneously integrated electrode configuration together with specialized epitaxial design serve to decouple the material interfaces for illumination and electrocatalysis. Subsequently, this allows independent control and optimization of light absorption, carrier transport, charge transfer, and material stability. Using this approach, we construct a series-connected wireless tandem system of GaAs photoelectrodes and demonstrate 13.1% solar-to-hydrogen conversion efficiency of unassisted-mode water splitting.

Electrodeposition of Ni-Mo alloy coatings for water splitting reaction

NASA Astrophysics Data System (ADS)

Shetty, Akshatha R.; Hegde, Ampar Chitharanjan

2018-04-01

The present study reports the development of Ni-Mo alloy coatings for water splitting applications, using a citrate bath the inducing effect of Mo (reluctant metal) on electrodeposition, its relationship with their electrocatalytic efficiency were studied. The alkaline water splitting efficiency of Ni-Mo alloy coatings, for both hydrogen evolution reaction (HER) and oxygen evolution reaction were tested using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. Moreover, the practical utility of these electrode materials were evaluated by measuring the amount of H2 and O2 gas evolved. The variation in electrocatalytic activity with composition, structure, and morphology of the coatings were examined using XRD, SEM, and EDS analyses. The experimental results showed that Ni-Mo alloy coating is the best electrode material for alkaline HER and OER reactions, at lower and higher deposition current densities (c. d.'s) respectively. This behavior is attributed by decreased Mo and increased Ni content of the alloy coating and the number of electroactive centers.

Unravelling Photocarrier Dynamics beyond the Space Charge Region for Photoelectrochemical Water Splitting

DOE PAGES

Zhang, Wenrui; Yan, Danhua; Appavoo, Kannatassen; ...

2017-04-18

Semiconductor photoelectrodes for photoelectrochemical (PEC) water splitting require efficient carrier generation, separation, and transport at and beyond the space charge region (SCR) formed at the aqueous interface. The trade-off between photon collection and minority carrier delivery governs the photoelectrode design and implies maximum water splitting efficiency at an electrode thickness equivalent to the light absorption depth. Here, using planar ZnO thin films as a model system, we identify the photocarriers beyond the SCR as another significant source to substantially enhance the PEC performance. The high-quality ZnO films synthesized by pulsed laser deposition feature very few deep trap states and supportmore » a long photocarrier lifetime. Combined with photoelectrochemical characterization, ultrafast spectroscopy, and numerical calculations, it is revealed that engineering the exciton concentration gradient by film thickness facilitates the inward diffusion of photocarriers from the neighboring illuminated region to the SCR and, therefore, achieves a record high quantum efficiency over 80% at a thickness far beyond its light absorption depth and the SCR width. Furthermore, these results elucidate the important role of the photocarriers beyond SCR for the PEC process and provide new insight into exploring the full potential for efficient photoelectrode materials with large exciton diffusivity.« less

Charge transfer mechanism in titanium-doped microporous silica for photocatalytic water-splitting applications

DOE PAGES

Sapp, Wendi; Koodali, Ranjit; Kilin, Dmitri

2016-02-29

Solar energy conversion into chemical form is possible using artificial means. One example of a highly-efficient fuel is solar energy used to split water into oxygen and hydrogen. Efficient photocatalytic water-splitting remains an open challenge for researchers across the globe. Despite significant progress, several aspects of the reaction, including the charge transfer mechanism, are not fully clear. Density functional theory combined with density matrix equations of motion were used to identify and characterize the charge transfer mechanism involved in the dissociation of water. A simulated porous silica substrate, using periodic boundary conditions, with Ti 4+ ions embedded on the innermore » pore wall was found to contain electron and hole trap states that could facilitate a chemical reaction. A trap state was located within the silica substrate that lengthened relaxation time, which may favor a chemical reaction. A chemical reaction would have to occur within the window of photoexcitation; therefore, the existence of a trapping state may encourage a chemical reaction. Furthermore, this provides evidence that the silica substrate plays an integral part in the electron/hole dynamics of the system, leading to the conclusion that both components (photoactive materials and support) of heterogeneous catalytic systems are important in optimization of catalytic efficiency.« less

Water splitting on semiconductor catalysts under visible-light irradiation.

PubMed

Navarro Yerga, Rufino M; Alvarez Galván, M Consuelo; del Valle, F; Villoria de la Mano, José A; Fierro, José L G

2009-01-01

Sustainable hydrogen production is a key target for the development of alternative, future energy systems that will provide a clean and affordable energy supply. The Sun is a source of silent and precious energy that is distributed fairly all over the Earth daily. However, its tremendous potential as a clean, safe, and economical energy source cannot be exploited unless the energy is accumulated or converted into more useful forms. The conversion of solar energy into hydrogen via the water-splitting process, assisted by photo-semiconductor catalysts, is one of the most promising technologies for the future because large quantities of hydrogen can potentially be generated in a clean and sustainable manner. This Minireview provides an overview of the principles, approaches, and research progress on solar hydrogen production via the water-splitting reaction on photo-semiconductor catalysts. It presents a survey of the advances made over the last decades in the development of catalysts for photochemical water splitting under visible-light irradiation. The Minireview also analyzes the energy requirements and main factors that determine the activity of photocatalysts in the conversion of water into hydrogen and oxygen using sunlight. Remarkable progress has been made since the pioneering work by Fujishima and Honda in 1972, but he development of photocatalysts with improved efficiencies for hydrogen production from water using solar energy still faces major challenges. Research strategies and approaches adopted in the search for active and efficient photocatalysts, for example through new materials and synthesis methods, are presented and analyzed.

Water Splitting with Series-Connected Polymer Solar Cells.

PubMed

Esiner, Serkan; van Eersel, Harm; van Pruissen, Gijs W P; Turbiez, Mathieu; Wienk, Martijn M; Janssen, René A J

2016-10-12

We investigate light-driven electrochemical water splitting with series-connected polymer solar cells using a combined experimental and modeling approach. The expected maximum solar-to-hydrogen conversion efficiency (η STH ) for light-driven water splitting is modeled for two, three, and four series-connected polymer solar cells. In the modeling, we assume an electrochemical water splitting potential of 1.50 V and a polymer solar cell for which the external quantum efficiency and fill factor are both 0.65. The minimum photon energy loss (E loss ), defined as the energy difference between the optical band gap (E g ) and the open-circuit voltage (V oc ), is set to 0.8 eV, which we consider a realistic value for polymer solar cells. Within these approximations, two series-connected single junction cells with E g = 1.73 eV or three series-connected cells with E g = 1.44 eV are both expected to give an η STH of 6.9%. For four series-connected cells, the maximum η STH is slightly less at 6.2% at an optimal E g = 1.33 eV. Water splitting was performed with series-connected polymer solar cells using polymers with different band gaps. PTPTIBDT-OD (E g = 1.89 eV), PTB7-Th (E g = 1.56 eV), and PDPP5T-2 (E g = 1.44 eV) were blended with [70]PCBM as absorber layer for two, three, and four series-connected configurations, respectively, and provide η STH values of 4.1, 6.1, and 4.9% when using a retroreflective foil on top of the cell to enhance light absorption. The reasons for deviations with experiments are analyzed and found to be due to differences in E g and E loss . Light-driven electrochemical water splitting was also modeled for multijunction polymer solar cells with vertically stacked photoactive layers. Under identical assumptions, an η STH of 10.0% is predicted for multijunction cells.

Hydrogenated TiO2 nanotube photonic crystals for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Meng, Ming; Zhou, Sihua; Yang, Lun; Gan, Zhixing; Liu, Kuili; Tian, Fengshou; Zhu, Yu; Li, ChunYang; Liu, Weifeng; Yuan, Honglei; Zhang, Yan

2018-04-01

We report the design, fabrication and characterization of novel TiO2 nanotube photonic crystals with a crystalline core/disordered shell structure as well as substantial oxygen vacancies for photoelectrochemical (PEC) water splitting. The novel TiO2 nanotube photonic crystals are fabricated by annealing of anodized TiO2 nanotube photonic crystals in hydrogen atmosphere at various temperatures. The optimized novel TiO2 nanotube photonic crystals produce a maximal photocurrent density of 2.2 mA cm-2 at 0.22 V versus Ag/AgCl, which is two times higher that of the TiO2 nanotube photonic crystals annealed in air. Such significant PEC performance improvement can be ascribed to synergistic effects of the disordered surface layer and oxygen vacancies. The reduced band gap owing to the disordered surface layer and localized states induced by oxygen vacancies can enhance the efficient utilization of visible light. In addition, the disordered surface layer and substantial oxygen vacancies can promote the efficiency for separation and transport of the photogenerated carriers. This work may open up new opportunities for the design and construction of the high efficient and low-cost PEC water splitting system.

Hydrogenated TiO2 nanotube photonic crystals for enhanced photoelectrochemical water splitting.

PubMed

Meng, Ming; Zhou, Sihua; Yang, Lun; Gan, Zhixing; Liu, Kuili; Tian, Fengshou; Zhu, Yu; Li, ChunYang; Liu, Weifeng; Yuan, Honglei; Zhang, Yan

2018-04-02

We report the design, fabrication and characterization of novel TiO 2 nanotube photonic crystals with a crystalline core/disordered shell structure as well as substantial oxygen vacancies for photoelectrochemical (PEC) water splitting. The novel TiO 2 nanotube photonic crystals are fabricated by annealing of anodized TiO 2 nanotube photonic crystals in hydrogen atmosphere at various temperatures. The optimized novel TiO 2 nanotube photonic crystals produce a maximal photocurrent density of 2.2 mA cm -2 at 0.22 V versus Ag/AgCl, which is two times higher that of the TiO 2 nanotube photonic crystals annealed in air. Such significant PEC performance improvement can be ascribed to synergistic effects of the disordered surface layer and oxygen vacancies. The reduced band gap owing to the disordered surface layer and localized states induced by oxygen vacancies can enhance the efficient utilization of visible light. In addition, the disordered surface layer and substantial oxygen vacancies can promote the efficiency for separation and transport of the photogenerated carriers. This work may open up new opportunities for the design and construction of the high efficient and low-cost PEC water splitting system.

Light Modulation and Water Splitting Enhancement Using a Composite Porous GaN Structure.

PubMed

Yang, Chao; Xi, Xin; Yu, Zhiguo; Cao, Haicheng; Li, Jing; Lin, Shan; Ma, Zhanhong; Zhao, Lixia

2018-02-14

On the basis of the laterally porous GaN, we designed and fabricated a composite porous GaN structure with both well-ordered lateral and vertical holes. Compared to the plane GaN, the composite porous GaN structure with the combination of the vertical holes can help to reduce UV reflectance and increase the saturation photocurrent during water splitting by a factor of ∼4.5. Furthermore, we investigated the underlying mechanism for the enhancement of the water splitting performance using a finite-difference time-domain method. The results show that the well-ordered vertical holes can not only help to open the embedded pore channels to the electrolyte at both sides and reduce the migration distance of the gas bubbles during the water splitting reactions but also help to modulate the light field. Using this composite porous GaN structure, most of the incident light can be modulated and trapped into the nanoholes, and thus the electric fields localized in the lateral pores can increase dramatically as a result of the strong optical coupling. Our findings pave a new way to develop GaN photoelectrodes for highly efficient solar water splitting.

Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Prabir K.

2001-09-30

Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

Anodically Grown Binder-Free Nickel Hexacyanoferrate Film: Toward Efficient Water Reduction and Hexacyanoferrate Film Based Full Device for Overall Water Splitting.

PubMed

Bui, Hoa Thi; Shrestha, Nabeen K; Khadtare, Shubhangi; Bathula, Chinna D; Giebeler, Lars; Noh, Yong-Young; Han, Sung-Hwan

2017-05-31

One of the challenges in obtaining hydrogen economically by electrochemical water splitting is to identify and substitute cost-effective earth-abundant materials for the traditionally used precious-metal-based water-splitting electrocatalysts. Herein, we report the electrochemical formation of a thin film of nickel-based Prussian blue analogue hexacyanoferrate (Ni-HCF) through the anodization of a nickel substrate in ferricyanide electrolyte. As compared to the traditionally used Nafion-binder-based bulk film, the anodically obtained binder-free Ni-HCF film demonstrates superior performance in the electrochemical hydrogen evolution reaction (HER), which is highly competitive with that shown by a Pt-plate electrode. The HER onset and the benchmark cathodic current density of 10 mA cm -2 were achieved at small overpotentials of 15 mV and 0.2 V (not iR-corrected), respectively, in 1 M KOH electrolyte, together with the long-term electrochemical durability of the film. Further, a metal-HCF-electrode-based full water-splitting device consisting of the binder-free Ni-HCF film on a Ni plate and a one-dimensional Co-HCF film on carbon paper as the electrodes for the HER and the oxygen evolution reaction (OER), respectively, was designed and was found to demonstrate very promising performance for overall water splitting.

Photo-catalysis water splitting by platinum-loaded zeolite A

NASA Astrophysics Data System (ADS)

Cheng, Jing; Gao, Changda; Jing, Ming; Lu, Jian; Lin, Hui; Han, Zhaoxia; Ni, Zhengji; Zhang, Dawei

2018-05-01

Under the λ≥420 nm visible light illumination, the Pt4+ ions exchanged LTA zeolite powders without further heat-treatment presented H2 evolution at a rate of 5 μl/(15 mg·h) via photocatalysis water splitting. It was shown that the efficiency of H2 generation by the Pt4+ exchanged LTA zeolite powders without further heat-treatment was higher than the counterpart of the samples with heat treatment. In addition, the samples with lower Pt loading concentration showed higher H2 evolution rate than those of higher Pt loading did. The higher H2 evolution efficiency can be attributed to the effective isolation of water molecules and Pt at the atomic or the few atom ‘cluster’ scale by LTA zeolite’s periodical porous structure, which ensures a more efficient electron transfer efficiency for H2 evolution. However, after extra heat treatment, the Pt atoms reduced from Pt4+ in LTA zeolite’s cavities may tend to migrate to the surface and then form nano-particles, which led to the lower H2 evolution efficiency.

3D structured Mo-doped Ni3S2 nanosheets as efficient dual-electrocatalyst for overall water splitting

NASA Astrophysics Data System (ADS)

Wu, Chengrong; Liu, Bitao; Wang, Jun; Su, Yongyao; Yan, Hengqing; Ng, Chuntan; Li, Cheng; Wei, Jumeng

2018-05-01

Searching for a cost-effective, high efficient and stable bifunctional electrocatalyst for overall water-splitting is critical to renewable energy systems. In this study, three-dimensional (3D) curved nanosheets of Mo-doped Ni3S2 grown on nickel foam were successfully synthesized via a one-step hydrothermal process. The hydrogen-evolution reaction (HER) and the oxygen-evolution reaction (OER) in alkaline environment of this 3D catalyst are investigated in detail. The results show that it possesses lower overpotential, high current densities and small Tafel slopes both in OER and HER. For HER, the catalysts show excellent electrochemical performance, demonstrating a low over-potential of 212 mV at 10 mA cm-2 with a large decrease of 127 mV compared to the undoped Ni3S2. And it also shows a lower overpotential of 260 mV at 10 mA cm-2 which decreases 30 mV for OER. In addition, it is only need 1.67 V for the overall water splitting at 10 mA cm-2 which is 70 mV. It found that the Mo element would change the morphology of Ni3S2 and induce much more active sites for HER and OER. The as-prepared Mo-doped Ni3S2 bi-functional electrocatalyst could act as the promising electrode materials for water splitting.

Surface modifications of chalcopyrite CuInS2 thin films for photochatodes in photoelectrochemical water splitting under sunlight irradiation

NASA Astrophysics Data System (ADS)

Gunawan; Haris, A.; Widiyandari, H.; Septina, W.; Ikeda, S.

2017-02-01

Copper chalcopyrite semiconductors include a wide range of compounds that are of interest for photoelectrochemical water splitting which enables them to be used as photochatodes for H2 generation. Among them, CuInS2 is one of the most important materials due to its optimum band gap energy for sunlight absorption. In the present study, we investigated the application of CuInS2 fabricated by electrodeposition as photochatodes for water splitting. Thin film of CuInS2 chalcopyrite was formed on Mo-coated glass substrate by stacked electrodeposition of copper and indium followed by sulfurization under H2S flow. The films worked as a H2 liberation electrode under cathodic polarization from a solution containing Na2SO4 after loading Pt deposits on the film. Introduction of an n-type CdS layer by chemical bath deposition on the CuInS2 surface before the Pt loading resulted appreciable improvements of H2 liberation efficiency and a higher photocurrent onset potential. Moreover, the use of In2S3 layer as an alternative n-type layer to the CdS significantly improved the H2 liberation performance: the CuInS2 film modified with In2S3 and Pt deposits worked as an efficient photocathode for photoelectrochemical water splitting.

Visible light water splitting using dye-sensitized oxide semiconductors.

PubMed

Youngblood, W Justin; Lee, Seung-Hyun Anna; Maeda, Kazuhiko; Mallouk, Thomas E

2009-12-21

Researchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO(2) to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts. Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process. This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy)(3)](2+) derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA(2-)) or non-sacrificial donors (I(-)). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO(2).nH(2)O nanoparticles, a dye-sensitized TiO(2) electrode becomes the photoanode of a water-splitting photoelectrochemical cell. Although this system is an interesting proof-of-concept, the performance of these cells is still poor (approximately 1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain.

NREL Establishes World Record for Solar Hydrogen Production | News | News |

Science.gov Websites

acid/water solution (electrolyte) where the water-splitting reaction occurs to form hydrogen and oxygen efficiency and to partially protect the critical underlying layers from the corrosive electrolyte solution

Pulsed Reductive Doping in Titanium Dioxide: An Easy Way for Multiplying the Efficiency of Solar H2 Production from Water

NASA Astrophysics Data System (ADS)

Seferlis, Andreas K.; Neophytides, Stylianos G.

2014-08-01

Solar photoelectrochemical water splitting on TiO2 for H2 production has been investigated for many years and is still considered very promising. Despite the many advantages, Titania's UV-only absorption, limits its terrestrial practical applications. In space though, with the lack of ozone's natural UV filter, this handicap is lifted, rendering TiO2 an attractive candidate as photoelectrocatalyst in space applications. Reductive doping of TiO2 has been investigated over the years for its impressive results but, till now, without practical application due to the impermanent nature of the doping. In this work we present a method that not only multiplies TiO2 water splitting efficiency, but also is facile, stable and easily applied in working conditions.

Cobalt-embedded nitrogen-rich carbon nanotubes efficiently catalyze hydrogen evolution reaction at all pH values.

PubMed

Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup; Silva, Rafael; Sathe, Bhaskar R; Mikmeková, Eliška; Asefa, Tewodros

2014-04-22

Despite being technically possible, splitting water to generate hydrogen is still practically unfeasible due mainly to the lack of sustainable and efficient catalysts for the half reactions involved. Herein we report the synthesis of cobalt-embedded nitrogen-rich carbon nanotubes (NRCNTs) that 1) can efficiently electrocatalyze the hydrogen evolution reaction (HER) with activities close to that of Pt and 2) function well under acidic, neutral or basic media alike, allowing them to be coupled with the best available oxygen-evolving catalysts-which also play crucial roles in the overall water-splitting reaction. The materials are synthesized by a simple, easily scalable synthetic route involving thermal treatment of Co(2+) -embedded graphitic carbon nitride derived from inexpensive starting materials (dicyandiamide and CoCl2 ). The materials' efficient catalytic activity is mainly attributed to their nitrogen dopants and concomitant structural defects. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Status of research and development on photoelectrochemical hydrogen production in Korea

NASA Astrophysics Data System (ADS)

Kim, Jong Won; Lee, Jae S.; Baeg, Jin-Ook

2010-08-01

Conversion of solar energy into hydrogen is one of the most promising renewable energy technologies. Photocatalytic production of hydrogen from water, H2S and organic wastes using semiconductors is one of the potential strategies for converting the sunlight energy into chemical energy. Korea government paid great attention to the hydrogen economy and launched the HERC (Hydrogen Energy R&D Center) for supporting the R&D topics on hydrogen related technologies. The key issue for realizing the commercial application of solar water splitting hydrogen production technique is to find an efficient, stable and low-cost photocatalyst. Our research groups have continuously investigated to find oxide and composite photocatalysts for photoelectrochemical cell with high efficiency using computational design and synthesis method. But, fundamental research on semiconductor doping for band gap shifting and surface chemistry modification is still required. Various reaction media containing sacrificial agents should be developed to match with high activity photocatalysts to further improve the system efficiency. Water containing organic/inorganic waste and sea water are particularly suggested in the consideration that all these water sources are the most available water on the earth to the final commercial application of photocatalytic water splitting technique.

Nano-engineering of p-n CuFeO2-ZnO heterojunction photoanode with improved light absorption and charge collection for photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Karmakar, Keshab; Sarkar, Ayan; Mandal, Kalyan; Gopal Khan, Gobinda

2017-08-01

The effective utilization of abundant visible solar light for photoelectrochemical water splitting is a green approach for energy harvesting, to reduce the enormous rise of carbon content in the atmosphere. Here, a novel efficient design strategy for p-n type nano-heterojunction photoanodes is demonstrated, with the goal of improving water splitting efficiency by growing low band gap p-CuFeO2 nanolayers on n-ZnO nanorods by an easy and scalable electrochemical route. The photoconversion efficiency of p-n CuFeO2/ZnO photoanodes is found to be ˜450% higher than that of pristine ZnO nanorod electrodes under visible solar light illumination (λ > 420 nm, intensity 10 mW cm-2). The p-n CuFeO2/ZnO nano-engineering not only boosts the visible light absorption but also resolves limitations regarding effective charge carrier separation and transportation due to interfacial band alignment. This photoanode also shows remarkably enhanced stability, where the formation of p-n nano-heterojunction enhances the easy migration of holes to the electrode/electrolyte interface, and of electrons to the counter electrode (Pt) for hydrogen generation. Therefore, this work demonstrates that p-n nano-engineering is a potential strategy to design light-harvesting electrodes for water splitting and clean energy generation.

Mediator- and co-catalyst-free direct Z-scheme composites of Bi2WO6-Cu3P for solar-water splitting.

PubMed

Rauf, Ali; Ma, Ming; Kim, Sungsoon; Sher Shah, Md Selim Arif; Chung, Chan-Hwa; Park, Jong Hyeok; Yoo, Pil J

2018-02-08

Exploring new single, active photocatalysts for solar-water splitting is highly desirable to expedite current research on solar-chemical energy conversion. In particular, Z-scheme-based composites (ZBCs) have attracted extensive attention due to their unique charge transfer pathway, broader redox range, and stronger redox power compared to conventional heterostructures. In the present report, we have for the first time explored Cu 3 P, a new, single photocatalyst for solar-water splitting applications. Moreover, a novel ZBC system composed of Bi 2 WO 6 -Cu 3 P was designed employing a simple method of ball-milling complexation. The synthesized materials were examined and further investigated through various microscopic, spectroscopic, and surface area characterization methods, which have confirmed the successful hybridization between Bi 2 WO 6 and Cu 3 P and the formation of a ZBC system that shows the ideal position of energy levels for solar-water splitting. Notably, the ZBC composed of Bi 2 WO 6 -Cu 3 P is a mediator- and co-catalyst-free photocatalyst system. The improved photocatalytic efficiency obtained with this system compared to other ZBC systems assisted by mediators and co-catalysts establishes the critical importance of interfacial solid-solid contact and the well-balanced position of energy levels for solar-water splitting. The promising solar-water splitting under optimum composition conditions highlighted the relationship between effective charge separation and composition.

Higher-efficiency photoelectrochemical electrodes of titanium dioxide-based nanoarrays sensitized simultaneously with plasmonic silver nanoparticles and multiple metal sulfides photosensitizers

NASA Astrophysics Data System (ADS)

Guo, Keying; Liu, Zhifeng; Han, Jianhua; Zhang, Xueqi; Li, Yajun; Hong, Tiantian; Zhou, Cailou

2015-07-01

This paper describes a novel design of high-efficiency photoelectrochemical water splitting electrode, i.e., ordered TiO2 nanorod arrays (NRs) sensitized simultaneously with noble metal (Ag), binary metal sulfides (Ag2S) and ternary metal sulfides (Ag3CuS2) multiple photosensitizers for the first time. The TiO2/Ag/Ag2S/Ag3CuS2 NRs heterostructure is successfully synthesized through successive ion layer adsorption and reaction (SILAR) and a simple ion-exchange process based on ionic reaction mechanism. On the basis of an optimal quantity of Ag, Ag2S and Ag3CuS2 nanoparticles, such TiO2/Ag/Ag2S/Ag3CuS2 NRs exhibit a higher photoelectrochemical activity ever reported for TiO2-based nanoarrays in PEC water splitting, the photocurrent density is up to 9.82 mA cm-2 at 0.47 V versus Ag/AgCl, respectively. This novel architecture is able to increase electron collection efficiency and suppress carrier recombination via (i) a higher efficiency of light-harvesting through these multiple photosensitizers (Ag, Ag2S and Ag3CuS2); (ii) the efficient separation of photo-induced electrons and holes due to the direct electrical pathways; (iii) the surface plasmon resonance (SPR) effect of Ag nanoparticles, which enhances the efficient charge separation and high carrier mobility. This work is useful to explore feasible routes to further enhance the performance of oxide semiconductors for PEC water splitting to produce clean H2 energy.

Mimicking Natural Photosynthesis: Solar to Renewable H2 Fuel Synthesis by Z-Scheme Water Splitting Systems

PubMed Central

2018-01-01

Visible light-driven water splitting using cheap and robust photocatalysts is one of the most exciting ways to produce clean and renewable energy for future generations. Cutting edge research within the field focuses on so-called “Z-scheme” systems, which are inspired by the photosystem II–photosystem I (PSII/PSI) coupling from natural photosynthesis. A Z-scheme system comprises two photocatalysts and generates two sets of charge carriers, splitting water into its constituent parts, hydrogen and oxygen, at separate locations. This is not only more efficient than using a single photocatalyst, but practically it could also be safer. Researchers within the field are constantly aiming to bring systems toward industrial level efficiencies by maximizing light absorption of the materials, engineering more stable redox couples, and also searching for new hydrogen and oxygen evolution cocatalysts. This review provides an in-depth survey of relevant Z-schemes from past to present, with particular focus on mechanistic breakthroughs, and highlights current state of the art systems which are at the forefront of the field. PMID:29676566

Value added transformation of ubiquitous substrates into highly efficient and flexible electrodes for water splitting.

PubMed

Sahasrabudhe, Atharva; Dixit, Harsha; Majee, Rahul; Bhattacharyya, Sayan

2018-05-22

Herein, we present an innovative approach for transforming commonly available cellulose paper into a flexible and catalytic current collector for overall water splitting. A solution processed soak-and-coat method of electroless plating was used to render a piece of paper conducting by conformably depositing metallic nickel nanoparticles, while still retaining the open macroporous framework. Proof-of-concept paper-electrodes are realized by modifying nickel-paper current collector with model electrocatalysts nickel-iron oxyhydroxide and nickel-molybdenum bimetallic alloy through electrodeposition route. The paper-electrodes demonstrate exceptional activities towards oxygen evolution reaction and hydrogen evolution reaction, requiring overpotentials of 240 and 32 mV at 50 and -10 mA cm -2 , respectively, even as they endure extreme mechanical stress. The generality of this approach is demonstrated by fabricating similar electrodes on cotton fabric, which also show high activity. Finally, a two-electrode paper-electrolyzer is constructed which can split water with an efficiency of 98.01%, and exhibits robust stability for more than 200 h.

Hierarchical honeycomb-like Co3O4 pores coating on CoMoO4 nanosheets as bifunctional efficient electrocatalysts for overall water splitting

NASA Astrophysics Data System (ADS)

Pei, Zhihao; Xu, Li; Xu, Wei

2018-03-01

Efficient electrocatalytic water splitting is one of the most effective ways to solve the global energy crisis. In this paper, we report on a novel self-assembled hierarchical structure of Co3O4/CoMoO4 grown in situ on a bare nickel foam. The unique, three-dimensional honeycomb-like Co3O4 pores were constructed from one-dimensional nanowires and coated on two-dimensional CoMoO4 nanosheets structures grown on nickel foam. The synthesis involved a step-wise solvothermal method followed by an annealing treatment. Benefiting from the synergistic effect of the hierarchical nanostructures, the materials had more reaction active sites and a smaller electron transfer impedance, and they exhibited excellent electrocatalytic performances for the HER and OER of 143 and 244 mV, respectively, at 10 mA cm-2 in an alkaline solution. Furthermore, the materials remained stable during the long electrolysis period, over 10 h, presenting promising application prospects in the field of electrocatalytic water splitting.

Mimicking Natural Photosynthesis: Solar to Renewable H2 Fuel Synthesis by Z-Scheme Water Splitting Systems.

PubMed

Wang, Yiou; Suzuki, Hajime; Xie, Jijia; Tomita, Osamu; Martin, David James; Higashi, Masanobu; Kong, Dan; Abe, Ryu; Tang, Junwang

2018-05-23

Visible light-driven water splitting using cheap and robust photocatalysts is one of the most exciting ways to produce clean and renewable energy for future generations. Cutting edge research within the field focuses on so-called "Z-scheme" systems, which are inspired by the photosystem II-photosystem I (PSII/PSI) coupling from natural photosynthesis. A Z-scheme system comprises two photocatalysts and generates two sets of charge carriers, splitting water into its constituent parts, hydrogen and oxygen, at separate locations. This is not only more efficient than using a single photocatalyst, but practically it could also be safer. Researchers within the field are constantly aiming to bring systems toward industrial level efficiencies by maximizing light absorption of the materials, engineering more stable redox couples, and also searching for new hydrogen and oxygen evolution cocatalysts. This review provides an in-depth survey of relevant Z-schemes from past to present, with particular focus on mechanistic breakthroughs, and highlights current state of the art systems which are at the forefront of the field.

Plasmon-induced artificial photosynthesis

PubMed Central

Ueno, Kosei; Oshikiri, Tomoya; Shi, Xu; Zhong, Yuqing; Misawa, Hiroaki

2015-01-01

We have successfully developed a plasmon-induced artificial photosynthesis system that uses a gold nanoparticle-loaded oxide semiconductor electrode to produce useful chemical energy as hydrogen and ammonia. The most important feature of this system is that both sides of a strontium titanate single-crystal substrate are used without an electrochemical apparatus. Plasmon-induced water splitting occurred even with a minimum chemical bias of 0.23 V owing to the plasmonic effects based on the efficient oxidation of water and the use of platinum as a co-catalyst for reduction. Photocurrent measurements were performed to determine the electron transfer between the gold nanoparticles and the oxide semiconductor. The efficiency of water oxidation was determined through spectroelectrochemical experiments aimed at elucidating the electron density in the gold nanoparticles. A set-up similar to the water-splitting system was used to synthesize ammonia via nitrogen fixation using ruthenium instead of platinum as a co-catalyst. PMID:26052419

Photocatalytic overall water splitting promoted by an α-β phase junction on Ga2O3.

PubMed

Wang, Xiang; Xu, Qian; Li, Mingrun; Shen, Shuai; Wang, Xiuli; Wang, Yaochuan; Feng, Zhaochi; Shi, Jingying; Han, Hongxian; Li, Can

2012-12-21

When Alpha met Beta: a tuneable α-β surface phase junction on Ga(2)O(3) can significantly improve photocatalytic overall water splitting into H(2) and O(2) over individual α-Ga(2)O(3) or β-Ga(2)O(3) surface phases. This enhanced photocatalytic performance is mainly attributed to the efficient charge separation and transfer across the α-β phase junction. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D FTO/FTO-Nanocrystal/TiO2 Composite Inverse Opal Photoanode for Efficient Photoelectrochemical Water Splitting.

PubMed

Wang, Zhiwei; Li, Xianglin; Ling, Han; Tan, Chiew Kei; Yeo, Loo Pin; Grimsdale, Andrew Clive; Tok, Alfred Iing Yoong

2018-05-01

A 3D fluorine-doped SnO 2 (FTO)/FTO-nanocrystal (NC)/TiO 2 inverse opal (IO) structure is designed and fabricated as a new "host and guest" type of composite photoanode for efficient photoelectrochemical (PEC) water splitting. In this novel photoanode design, the highly conductive and porous FTO/FTO-NC IO acts as the "host" skeleton, which provides direct pathways for faster electron transport, while the conformally coated TiO 2 layer acts as the "guest" absorber layer. The unique composite IO structure is fabricated through self-assembly of colloidal spheres template, a hydrothermal method and atomic layer deposition (ALD). Owing to its large surface area and efficient charge collection, the FTO/FTO-NC/TiO 2 composite IO photoanode shows excellent photocatalytic properties for PEC water splitting. With optimized dimensions of the SnO 2 nanocrystals and the thickness of the ALD TiO 2 absorber layers, the 3D FTO/FTO-NC/TiO 2 composite IO photoanode yields a photocurrent density of 1.0 mA cm -2 at 1.23 V versus reversible hydrogen electrode (RHE) under AM 1.5 illumination, which is four times higher than that of the FTO/TiO 2 IO reference photoanode. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ni nanotube array-based electrodes by electrochemical alloying and de-alloying for efficient water splitting.

PubMed

Teng, Xue; Wang, Jianying; Ji, Lvlv; Lv, Yaokang; Chen, Zuofeng

2018-05-17

The design of cost-efficient earth-abundant catalysts with superior performance for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is extremely important for future renewable energy production. Herein, we report a facile strategy for constructing Ni nanotube arrays (NTAs) on a Ni foam (NF) substrate through cathodic deposition of NiCu alloy followed by anodic stripping of metallic Cu. Based on Ni NTAs, the as-prepared NiSe2 NTA electrode by NiSe2 electrodeposition and the NiFeOx NTA electrode by dipping in Fe3+ solution exhibit excellent HER and OER performance in alkaline conditions. In these systems, Ni NTAs act as a binder-free multifunctional inner layer to support the electrocatalysts, offer a large specific surface area and serve as a fast electron transport pathway. Moreover, an alkaline electrolyzer has been constructed using NiFeOx NTAs as the anode and NiSe2 NTAs as the cathode, which only demands a cell voltage of 1.78 V to deliver a water-splitting current density of 500 mA cm-2, and demonstrates remarkable stability during long-term electrolysis. This work provides an attractive method for the design and fabrication of nanotube array-based catalyst electrodes for highly efficient water-splitting.

Surface Passivation of GaN Nanowires for Enhanced Photoelectrochemical Water-Splitting.

PubMed

Varadhan, Purushothaman; Fu, Hui-Chun; Priante, Davide; Retamal, Jose Ramon Duran; Zhao, Chao; Ebaid, Mohamed; Ng, Tien Khee; Ajia, Idirs; Mitra, Somak; Roqan, Iman S; Ooi, Boon S; He, Jr-Hau

2017-03-08

Hydrogen production via photoelectrochemical water-splitting is a key source of clean and sustainable energy. The use of one-dimensional nanostructures as photoelectrodes is desirable for photoelectrochemical water-splitting applications due to the ultralarge surface areas, lateral carrier extraction schemes, and superior light-harvesting capabilities. However, the unavoidable surface states of nanostructured materials create additional charge carrier trapping centers and energy barriers at the semiconductor-electrolyte interface, which severely reduce the solar-to-hydrogen conversion efficiency. In this work, we address the issue of surface states in GaN nanowire photoelectrodes by employing a simple and low-cost surface treatment method, which utilizes an organic thiol compound (i.e., 1,2-ethanedithiol). The surface-treated photocathode showed an enhanced photocurrent density of -31 mA/cm 2 at -0.2 V versus RHE with an incident photon-to-current conversion efficiency of 18.3%, whereas untreated nanowires yielded only 8.1% efficiency. Furthermore, the surface passivation provides enhanced photoelectrochemical stability as surface-treated nanowires retained ∼80% of their initial photocurrent value and produced 8000 μmol of gas molecules over 55 h at acidic conditions (pH ∼ 0), whereas the untreated nanowires demonstrated only <4 h of photoelectrochemical stability. These findings shed new light on the importance of surface passivation of nanostructured photoelectrodes for photoelectrochemical applications.

Efficient tungsten oxide/bismuth oxyiodide core/shell photoanode for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Ma, Haipeng; Zhang, Jing; Liu, Zhifeng

2017-11-01

The novel WO3 nanorods (NRs)/BiOI core/shell structure composite is used as an efficient photoanode applied in photoelectrochemical (PEC) water splitting for the first time. It is synthesized via facile hydrothermal method and, successive ionic layer adsorption and reaction (SILAR) process. This facile synthesis route can achieve uniform WO3/BiOI core/shell composite nanostructures and obtain varied BiOI morphologies simultaneously. The WO3 NRs/BiOI-20 composite exhibits enhanced PEC activity compared to pristine WO3 with a photocurrent density of 0.79 mA cm-2 measured at 0.8 V vs. RHE under AM 1.5G. This excellent performance benefits from the broader absorption spectrum and suppressed electron-hole recombination. This novel core/shell composite may provide insight in developing more efficient solar driven photoelectrodes.

Superaerophobic P-doped Ni(OH)2/NiMoO4 hierarchical nanosheet arrays grown on Ni foam for electrocatalytic overall water splitting.

PubMed

Xi, Wenguang; Yan, Gang; Tan, Huaqiao; Xiao, Liguang; Cheng, Sihang; Khan, Shifa Ullah; Wang, Yonghui; Li, Yangguang

2018-06-19

Transition metal (TM) oxides and hydroxides are one of the important candidates for the development of durable and low-cost electrocatalysts towards water splitting. The key issue is exploring effective methods to improve their electrocatalytic activity. Herein, we report a new type of P-doped Ni(OH)2/NiMoO4 hierarchical nanosheet array (abbr. P-Ni(OH)2/NiMoO4) grown on Ni foam (NF), which can act as a highly efficient electrocatalyst towards overall water splitting. Such a composite was obtained by a three-step preparation process. In the first two hydrothermal reactions, the crystalline Ni(OH)2 hierarchical nanosheet arrays were grown on NF and then the low crystallinity NiMoO4 was grafted on the Ni(OH)2 nanosheets. In the third phosphorization step, P element was doped into the composite Ni(OH)2/NiMoO4. Electrocatalytic experiments show that P-Ni(OH)2/NiMoO4 possesses a smaller overpotential (60 mV) and lower Tafel slope (130 mV dec-1) toward HER in 1 M KOH. When it was employed as an integrated water splitting catalyst, only a potential of 1.55 V was required to achieve a current density of 10 mA cm-2. This catalytic activity is even better than those of electrolyzers constructed with noble metals Pt/C∥IrO2. The superior electrocatalytic performance of P-Ni(OH)2/NiMoO4 can be attributed to the high quality of crystalline Ni(OH)2 nanosheet arrays grown on NF, which dramatically improve the conductivity. Furthermore, the hierarchical structure not only increases the surface area and exposes more catalytically active sites, but also provides a superaerophobic surface, which helps to accelerate the release of generated bubbles. Moreover, the synergistic effects between P-Ni(OH)2 and P-NiMoO4 efficiently promote the HER and OER processes also. This work may suggest new a way to explore TM oxide/hydroxide-based durable electrocatalysts with highly efficient electrocatalytic activities towards overall water splitting.

Photoelectrochemical water splitting in separate oxygen and hydrogen cells

NASA Astrophysics Data System (ADS)

Landman, Avigail; Dotan, Hen; Shter, Gennady E.; Wullenkord, Michael; Houaijia, Anis; Maljusch, Artjom; Grader, Gideon S.; Rothschild, Avner

2017-06-01

Solar water splitting provides a promising path for sustainable hydrogen production and solar energy storage. One of the greatest challenges towards large-scale utilization of this technology is reducing the hydrogen production cost. The conventional electrolyser architecture, where hydrogen and oxygen are co-produced in the same cell, gives rise to critical challenges in photoelectrochemical water splitting cells that directly convert solar energy and water to hydrogen. Here we overcome these challenges by separating the hydrogen and oxygen cells. The ion exchange in our cells is mediated by auxiliary electrodes, and the cells are connected to each other only by metal wires, enabling centralized hydrogen production. We demonstrate hydrogen generation in separate cells with solar-to-hydrogen conversion efficiency of 7.5%, which can readily surpass 10% using standard commercial components. A basic cost comparison shows that our approach is competitive with conventional photoelectrochemical systems, enabling safe and potentially affordable solar hydrogen production.

Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review

PubMed Central

Roeb, Martin; Neises, Martina; Monnerie, Nathalie; Call, Friedemann; Simon, Heike; Sattler, Christian; Schmücker, Martin; Pitz-Paal, Robert

2012-01-01

Thermochemical multistep water- and CO2-splitting processes are promising options to face future energy problems. Particularly, the possible incorporation of solar power makes these processes sustainable and environmentally attractive since only water, CO2 and solar power are used; the concentrated solar energy is converted into storable and transportable fuels. One of the major barriers to technological success is the identification of suitable active materials like catalysts and redox materials exhibiting satisfactory durability, reactivity and efficiencies. Moreover, materials play an important role in the construction of key components and for the implementation in commercial solar plants. The most promising thermochemical water- and CO2-splitting processes are being described and discussed with respect to further development and future potential. The main materials-related challenges of those processes are being analyzed. Technical approaches and development progress in terms of solving them are addressed and assessed in this review.

Photocatalytic Water-Splitting Enhancement by Sub-Bandgap Photon Harvesting.

PubMed

Monguzzi, Angelo; Oertel, Amadeus; Braga, Daniele; Riedinger, Andreas; Kim, David K; Knüsel, Philippe N; Bianchi, Alberto; Mauri, Michele; Simonutti, Roberto; Norris, David J; Meinardi, Francesco

2017-11-22

Upconversion is a photon-management process especially suited to water-splitting cells that exploit wide-bandgap photocatalysts. Currently, such catalysts cannot utilize 95% of the available solar photons. We demonstrate here that the energy-conversion yield for a standard photocatalytic water-splitting device can be enhanced under solar irradiance by using a low-power upconversion system that recovers part of the unutilized incident sub-bandgap photons. The upconverter is based on a sensitized triplet-triplet annihilation mechanism (sTTA-UC) obtained in a dye-doped elastomer and boosted by a fluorescent nanocrystal/polymer composite that allows for broadband light harvesting. The complementary and tailored optical properties of these materials enable efficient upconversion at subsolar irradiance, allowing the realization of the first prototype water-splitting cell assisted by solid-state upconversion. In our proof-of concept device the increase of the performance is 3.5%, which grows to 6.3% if concentrated sunlight (10 sun) is used. Our experiments show how the sTTA-UC materials can be successfully implemented in technologically relevant devices while matching the strict requirements of clean-energy production.

Photoelectrochemical devices for solar water splitting - materials and challenges.

PubMed

Jiang, Chaoran; Moniz, Savio J A; Wang, Aiqin; Zhang, Tao; Tang, Junwang

2017-07-31

It is widely accepted within the community that to achieve a sustainable society with an energy mix primarily based on solar energy we need an efficient strategy to convert and store sunlight into chemical fuels. A photoelectrochemical (PEC) device would therefore play a key role in offering the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The past five years have seen a surge in the development of promising semiconductor materials. In addition, low-cost earth-abundant co-catalysts are ubiquitous in their employment in water splitting cells due to the sluggish kinetics of the oxygen evolution reaction (OER). This review commences with a fundamental understanding of semiconductor properties and charge transfer processes in a PEC device. We then describe various configurations of PEC devices, including single light-absorber cells and multi light-absorber devices (PEC, PV-PEC and PV/electrolyser tandem cell). Recent progress on both photoelectrode materials (light absorbers) and electrocatalysts is summarized, and important factors which dominate photoelectrode performance, including light absorption, charge separation and transport, surface chemical reaction rate and the stability of the photoanode, are discussed. Controlling semiconductor properties is the primary concern in developing materials for solar water splitting. Accordingly, strategies to address the challenges for materials development in this area, such as the adoption of smart architectures, innovative device configuration design, co-catalyst loading, and surface protection layer deposition, are outlined throughout the text, to deliver a highly efficient and stable PEC device for water splitting.

Methods for pore water extraction from unsaturated zone tuff, Yucca Mountain, Nevada

USGS Publications Warehouse

Scofield, K.M.

2006-01-01

Assessing the performance of the proposed high-level radioactive waste repository at Yucca Mountain, Nevada, requires an understanding of the chemistry of the water that moves through the host rock. The uniaxial compression method used to extract pore water from samples of tuffaceous borehole core was successful only for nonwelded tuff. An ultracentrifugation method was adopted to extract pore water from samples of the densely welded tuff of the proposed repository horizon. Tests were performed using both methods to determine the efficiency of pore water extraction and the potential effects on pore water chemistry. Test results indicate that uniaxial compression is most efficient for extracting pore water from nonwelded tuff, while ultracentrifugation is more successful in extracting pore water from densely welded tuff. Pore water splits collected from a single nonwelded tuff core during uniaxial compression tests have shown changes in pore water chemistry with increasing pressure for calcium, chloride, sulfate, and nitrate. Pore water samples collected from the intermediate pressure ranges should prevent the influence of re-dissolved, evaporative salts and the addition of ion-deficient water from clays and zeolites. Chemistry of pore water splits from welded and nonwelded tuffs using ultracentrifugation indicates that there is no substantial fractionation of solutes.

In-Situ Formed Hydroxide Accelerating Water Dissociation Kinetics on Co3N for Hydrogen Production in Alkaline Solution.

PubMed

Xu, Zhe; Li, Wenchao; Yan, Yadong; Wang, HongXu; Zhu, Heng; Zhao, Meiming; Yan, Shicheng; Zou, Zhigang

2018-06-21

Sluggish water dissociation kinetics on nonprecious metal electrocatalysts limits the development of economical hydrogen production from water-alkali electrolyzers. Here, using Co 3 N electrocatalyst as a prototype, we find that during water splitting in alkaline electrolyte a cobalt-containing hydroxide formed on the surface of Co 3 N, which greatly decreased the activation energy of water dissociation (Volmer step, a main rate-determining step for water splitting in alkaline electrolytes). Combining the cobalt ion poisoning test and theoretical calculations, the efficient hydrogen production on Co 3 N electrocatalysts would benefit from favorable water dissociation on in-situ formed cobalt-containing hydroxide and low hydrogen production barrier on the nitrogen sites of Co 3 N. As a result, the Co 3 N catalyst exhibits a low water-splitting activation energy (26.57 kJ mol -1 ) that approaches the value of platinum electrodes (11.69 kJ mol -1 ). Our findings offer new insight into understanding the catalytic mechanism of nitride electrocatalysts, thus contributing to the development of economical hydrogen production in alkaline electrolytes.

A novel theoretical probe of the SrTiO3 surface under water-splitting conditions

NASA Astrophysics Data System (ADS)

Letchworth-Weaver, Kendra; Gunceler, Deniz; Arias, Tomás; Plaza, Manuel; Huang, Xin; Brock, Joel; Rodriguez-López, Joaquin; Abruña, Hector

2014-03-01

Understanding the reaction mechanisms required to generate hydrogen fuel by photoelectrolysis of water is essential to energy conversion research. These reaction pathways are strongly influenced by the geometry and electronic structure of the electrode surface under water-splitting conditions. Electrochemical microscopy has demonstrated that biasing a SrTiO3 (001) surface can lead to an increase in water-splitting activity. In operando X-ray reflectivity measurements at the Cornell High Energy Synchrotron Source (CHESS) correlate this increase in activity to a significant reorganization in the surface structure but are unable to determine the exact nature of this change. Joint Density-Functional Theory (JDFT), a rigorous yet computationally efficient alternative to molecular dynamics, provides a quantum-mechanical description of an electrode surface in contact with an aqueous environment, and a microscopically detailed description of the interfacial liquid structure. Our JDFT calculations determine the structure of the activated SrTiO3 surface and explore why it is correlated with higher activity for water splitting. With no empirical parameters whatsoever, we predict the X-ray crystal truncation rods for SrTiO3, finding excellent agreement with experiment. Funded by the Energy Materials Center at Cornell (EMC2).

Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

NASA Astrophysics Data System (ADS)

Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

2018-01-01

Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

Inorganic perovskite photocatalysts for solar energy utilization.

PubMed

Zhang, Guan; Liu, Gang; Wang, Lianzhou; Irvine, John T S

2016-10-24

The development and utilization of solar energy in environmental remediation and water splitting is being intensively studied worldwide. During the past few decades, tremendous efforts have been devoted to developing non-toxic, low-cost, efficient and stable photocatalysts for water splitting and environmental remediation. To date, several hundreds of photocatalysts mainly based on metal oxides, sulfides and (oxy)nitrides with different structures and compositions have been reported. Among them, perovskite oxides and their derivatives (layered perovskite oxides) comprise a large family of semiconductor photocatalysts because of their structural simplicity and flexibility. This review specifically focuses on the general background of perovskite and its related materials, summarizes the recent development of perovskite photocatalysts and their applications in water splitting and environmental remediation, discusses the theoretical modelling and calculation of perovskite photocatalysts and presents the key challenges and perspectives on the research of perovskite photocatalysts.

Field-Assisted Splitting of Pure Water Based on Deep-Sub-Debye-Length Nanogap Electrochemical Cells.

PubMed

Wang, Yifei; Narayanan, S R; Wu, Wei

2017-08-22

Owing to the low conductivity of pure water, using an electrolyte is common for achieving efficient water electrolysis. In this paper, we have fundamentally broken through this common sense by using deep-sub-Debye-length nanogap electrochemical cells to achieve efficient electrolysis of pure water (without any added electrolyte) at room temperature. A field-assisted effect resulted from overlapped electrical double layers can greatly enhance water molecules ionization and mass transport, leading to electron-transfer limited reactions. We have named this process "virtual breakdown mechanism" (which is completely different from traditional mechanisms) that couples the two half-reactions together, greatly reducing the energy losses arising from ion transport. This fundamental discovery has been theoretically discussed in this paper and experimentally demonstrated in a group of electrochemical cells with nanogaps between two electrodes down to 37 nm. On the basis of our nanogap electrochemical cells, the electrolysis current density from pure water can be significantly larger than that from 1 mol/L sodium hydroxide solution, indicating the much better performance of pure water splitting as a potential for on-demand clean hydrogen production.

Highly efficient binuclear ruthenium catalyst for water oxidation.

PubMed

Sander, Anett C; Maji, Somnath; Francàs, Laia; Böhnisch, Torben; Dechert, Sebastian; Llobet, Antoni; Meyer, Franc

2015-05-22

Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce(IV) )-by means of manometry and a Clark electrode for monitoring the dioxygen production-and electrochemically with impressive activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Review of solar fuel-producing quantum conversion processes

NASA Technical Reports Server (NTRS)

Peterson, D. B.; Biddle, J. R.; Fujita, T.

1984-01-01

The status and potential of fuel-producing solar photochemical processes are discussed. Research focused on splitting water to produce dihydrogen and is at a relatively early stage of development. Current emphasis is primarily directed toward understanding the basic chemistry underlying such quantum conversion processes. Theoretical analyses by various investigators predict a limiting thermodynamic efficiency of 31% for devices with a single photosystem operating with unfocused sunlight at 300 K. When non-idealities are included, it appears unlikely that actual devices will have efficiencies greater than 12 to 15%. Observed efficiencies are well below theoretical limits. Cyclic homogeneous photochemical processes for splitting water have efficiencies considerably less than 1%. Efficiency can be significantly increased by addition of a sacrificial reagent; however, such systems are no longer cyclic and it is doubtful that they would be economical on a commercial scale. The observed efficiencies for photoelectrochemical processes are also low but such systems appear more promising than homogeneous photochemical systems. Operating and systems options, including operation at elevated temperature and hybrid and coupled quantum-thermal conversion processes, are also considered.

Systematic Bandgap Engineering of Graphene Quantum Dots and Applications for Photocatalytic Water Splitting and CO2 Reduction.

PubMed

Yan, Yibo; Chen, Jie; Li, Nan; Tian, Jingqi; Li, Kaixin; Jiang, Jizhou; Liu, Jiyang; Tian, Qinghua; Chen, Peng

2018-04-24

Graphene quantum dots (GQDs), which is the latest addition to the nanocarbon material family, promise a wide spectrum of applications. Herein, we demonstrate two different functionalization strategies to systematically tailor the bandgap structures of GQDs whereby making them snugly suitable for particular applications. Furthermore, the functionalized GQDs with a narrow bandgap and intramolecular Z-scheme structure are employed as the efficient photocatalysts for water splitting and carbon dioxide reduction under visible light. The underlying mechanisms of our observations are studied and discussed.

A hole inversion layer at the BiVO4/Bi4V2O11 interface produces a high tunable photovoltage for water splitting

NASA Astrophysics Data System (ADS)

Dos Santos, Wayler S.; Rodriguez, Mariandry; Afonso, André S.; Mesquita, João P.; Nascimento, Lucas L.; Patrocínio, Antônio O. T.; Silva, Adilson C.; Oliveira, Luiz C. A.; Fabris, José D.; Pereira, Márcio C.

2016-08-01

The conversion of solar energy into hydrogen fuel by splitting water into photoelectrochemical cells (PEC) is an appealing strategy to store energy and minimize the extensive use of fossil fuels. The key requirement for efficient water splitting is producing a large band bending (photovoltage) at the semiconductor to improve the separation of the photogenerated charge carriers. Therefore, an attractive method consists in creating internal electrical fields inside the PEC to render more favorable band bending for water splitting. Coupling ferroelectric materials exhibiting spontaneous polarization with visible light photoactive semiconductors can be a likely approach to getting higher photovoltage outputs. The spontaneous electric polarization tends to promote the desirable separation of photogenerated electron- hole pairs and can produce photovoltages higher than that obtained from a conventional p-n heterojunction. Herein, we demonstrate that a hole inversion layer induced by a ferroelectric Bi4V2O11 perovskite at the n-type BiVO4 interface creates a virtual p-n junction with high photovoltage, which is suitable for water splitting. The photovoltage output can be boosted by changing the polarization by doping the ferroelectric material with tungsten in order to produce the relatively large photovoltage of 1.39 V, decreasing the surface recombination and enhancing the photocurrent as much as 180%.

A hole inversion layer at the BiVO4/Bi4V2O11 interface produces a high tunable photovoltage for water splitting

PubMed Central

dos Santos, Wayler S.; Rodriguez, Mariandry; Afonso, André S.; Mesquita, João P.; Nascimento, Lucas L.; Patrocínio, Antônio O. T.; Silva, Adilson C.; Oliveira, Luiz C. A.; Fabris, José D.; Pereira, Márcio C.

2016-01-01

The conversion of solar energy into hydrogen fuel by splitting water into photoelectrochemical cells (PEC) is an appealing strategy to store energy and minimize the extensive use of fossil fuels. The key requirement for efficient water splitting is producing a large band bending (photovoltage) at the semiconductor to improve the separation of the photogenerated charge carriers. Therefore, an attractive method consists in creating internal electrical fields inside the PEC to render more favorable band bending for water splitting. Coupling ferroelectric materials exhibiting spontaneous polarization with visible light photoactive semiconductors can be a likely approach to getting higher photovoltage outputs. The spontaneous electric polarization tends to promote the desirable separation of photogenerated electron- hole pairs and can produce photovoltages higher than that obtained from a conventional p-n heterojunction. Herein, we demonstrate that a hole inversion layer induced by a ferroelectric Bi4V2O11 perovskite at the n-type BiVO4 interface creates a virtual p-n junction with high photovoltage, which is suitable for water splitting. The photovoltage output can be boosted by changing the polarization by doping the ferroelectric material with tungsten in order to produce the relatively large photovoltage of 1.39 V, decreasing the surface recombination and enhancing the photocurrent as much as 180%. PMID:27503274

Oxygen-Evolving Porous Glass Plates Containing the Photosynthetic Photosystem II Pigment-Protein Complex.

PubMed

Noji, Tomoyasu; Kawakami, Keisuke; Shen, Jian-Ren; Dewa, Takehisa; Nango, Mamoru; Kamiya, Nobuo; Itoh, Shigeru; Jin, Tetsuro

2016-08-09

The development of artificial photosynthesis has focused on the efficient coupling of reaction at photoanode and cathode, wherein the production of hydrogen (or energy carriers) is coupled to the electrons derived from water-splitting reactions. The natural photosystem II (PSII) complex splits water efficiently using light energy. The PSII complex is a large pigment-protein complex (20 nm in diameter) containing a manganese cluster. A new photoanodic device was constructed incorporating stable PSII purified from a cyanobacterium Thermosynechococcus vulcanus through immobilization within 20 or 50 nm nanopores contained in porous glass plates (PGPs). PSII in the nanopores retained its native structure and high photoinduced water splitting activity. The photocatalytic rate (turnover frequency) of PSII in PGP was enhanced 11-fold compared to that in solution, yielding a rate of 50-300 mol e(-)/(mol PSII·s) with 2,6-dichloroindophenol (DCIP) as an electron acceptor. The PGP system realized high local concentrations of PSII and DCIP to enhance the collisional reactions in nanotubes with low disturbance of light penetration. The system allows direct visualization/determination of the reaction inside the nanotubes, which contributes to optimize the local reaction condition. The PSII/PGP device will substantively contribute to the construction of artificial photosynthesis using water as the ultimate electron source.

Efficient Suppression of Electron–Hole Recombination in Oxygen-Deficient Hydrogen-Treated TiO2 Nanowires for Photoelectrochemical Water Splitting

PubMed Central

2013-01-01

There is an increasing level of interest in the use of black TiO2 prepared by thermal hydrogen treatments (H:TiO2) due to the potential to enhance both the photocatalytic and the light-harvesting properties of TiO2. Here, we examine oxygen-deficient H:TiO2 nanotube arrays that have previously achieved very high solar-to-hydrogen (STH) efficiencies due to incident photon-to-current efficiency (IPCE) values of >90% for photoelectrochemical water splitting at only 0.4 V vs RHE under UV illumination. Our transient absorption (TA) mechanistic study provides strong evidence that the improved electrical properties of oxygen-deficient TiO2 enables remarkably efficient spatial separation of electron–hole pairs on the submicrosecond time scale at moderate applied bias, and this coupled to effective suppression of microsecond to seconds charge carrier recombination is the primary factor behind the dramatically improved photoelectrochemical activity. PMID:24376902

Photoelectrochemical and theoretical investigations of spinel type ferrites (MxFe3-xO4) for water splitting: a mini-review

NASA Astrophysics Data System (ADS)

Taffa, Dereje H.; Dillert, Ralf; Ulpe, Anna C.; Bauerfeind, Katharina C. L.; Bredow, Thomas; Bahnemann, Detlef W.; Wark, Michael

2017-01-01

Solar-assisted water splitting using photoelectrochemical cells (PECs) is one of the promising pathways for the production of hydrogen for renewable energy storage. The nature of the semiconductor material is the primary factor that controls the overall energy conversion efficiency. Finding semiconductor materials with appropriate semiconducting properties (stability, efficient charge separation and transport, abundant, visible light absorption) is still a challenge for developing materials for solar water splitting. Owing to the suitable bandgap for visible light harvesting and the abundance of iron-based oxide semiconductors, they are promising candidates for PECs and have received much research attention. Spinel ferrites are subclasses of iron oxides derived from the classical magnetite (FeIIFe2IIIO4) in which the FeII is replaced by one (some cases two) additional divalent metals. They are generally denoted as MxFe3-xO4 (M=Ca, Mg, Zn, Co, Ni, Mn, and so on) and mostly crystallize in spinel or inverse spinel structures. In this mini review, we present the current state of research in spinel ferrites as photoelectrode materials for PECs application. Strategies to improve energy conversion efficiency (nanostructuring, surface modification, and heterostructuring) will be presented. Furthermore, theoretical findings related to the electronic structure, bandgap, and magnetic properties will be presented and compared with experimental results.

Water splitting: Taking cobalt in isolation

NASA Astrophysics Data System (ADS)

Wang, Aiqin; Zhang, Tao

2016-01-01

The sustainable production of hydrogen is key to the delivery of clean energy in a hydrogen economy; however, lower-cost alternatives to platinum electrocatalysts are needed. Now, isolated, earth-abundant cobalt atoms dispersed over nitrogen-doped graphene are shown to efficiently electrolyse water to generate hydrogen.

Facile fabrication of Si-doped TiO2 nanotubes photoanode for enhanced photoelectrochemical hydrogen generation

NASA Astrophysics Data System (ADS)

Dong, Zhenbiao; Ding, Dongyan; Li, Ting; Ning, Congqin

2018-04-01

Photoelectrochemical (PEC) water splitting based doping modified one dimensional (1D) titanium dioxide (TiO2) nanostructures provide an efficient method for hydrogen generation. Here we first successfully fabricated 1D Si-doped TiO2 (Ti-Si-O) nanotube arrays through anodizing Ti-Si alloys with different Si amount, and reported the PEC properties for water splitting. The Ti-Si-O nanotube arrays fabricated on Ti-5 wt.% Si alloy and annealed at 600 °C possess higher PEC activity, yielding a higher photocurrent density of 0.83 mA/cm2 at 0 V vs. Ag/AgCl. The maximum photoconversion efficiency was 0.54%, which was 2.7 times the photoconversion efficiency of undoped TiO2.

Interfacial coupling induced direct Z scheme water splitting in metal-free photocatalyst: C3N/g-C3N4 heterojunctions.

PubMed

Wang, Jiajun; Li, Xiaoting; You, Ya; Xintong, Yang; Wang, Ying; Li, Qunxiang

2018-06-21

Mimicking the natural photosynthesis in green plants, artificial Z-scheme photocatalysis enables more efficient utilization of solar energy for photocatalytic water splitting. Most currently designed g-C3N4-based Z-scheme heterojunctions are usually based on metal-containing semiconductor photocatalysts, thus exploiting metal-free photocatalysts for Z-scheme water splitting is of huge interest. Herein, we propose two metal-free C3N/g-C3N4 heterojunctions with the C3N monolayer covering g-C3N4 sheet (monolayer or bilayer) and systematically explore their electronic structures, charge distributions and photocatalytic properties by performing extensive hybrid density functional calculations. We clearly reveal that the relative strong built-in electric fields around their respective interface regions, caused by the charge transfer from C3N monolayer to g-C3N4 monolayer or bilayer, result in the bands bending, renders the transfer of photogenerated carriers in these two heterojunctions following the Z-scheme instead of the type-II pathway. Moreover, the photogenerated electrons and holes in these two C3N/g-C3N4 heterojunctions not only can be efficiently separated, but also have strong redox abilities for water oxidation and reduction. Compared with the isolated g-C3N4 sheets, the light absorption in visible to near-infrared region are significantly enhanced in these proposed heterojunctions. These theoretical findings suggest that these proposed metal-free C3N/g-C3N4 heterojunctions are promising direct Z-scheme photocatalysts for solar water splitting. © 2018 IOP Publishing Ltd.

Chemically Modified Metal Oxide Nanostructure for Photoelectrochemical Water Splitting

NASA Astrophysics Data System (ADS)

Wang, Gongming

Hydrogen gas is chemical fuel with high energy density, and represents a clean, renewable and carbon-free burning fuel, which has the potential to solve the more and more urgent energy crisis in today's society. Inspired by natural photosynthesis, artificial photosynthesis to generate hydrogen energy has attracted a lot of attentions in the field of chemistry, physics and material. Photoelectrochemical water splitting based on semiconductors represents a green and low cost method to generate hydrogen fuel. However, the current overall efficiency of solar to hydrogen is quite low, due to some intrinsic limitations such as bandgap, diffusion distance, carrier lifetime and photostability of semiconductors. Although nanostructured semiconductors can improve their photoelectrochemical water splitting performance to some extent, by increasing electrolyte accessible area and shortening minority carrier diffusion distance, nanostructure engineering cannot change their intrinsic electronic properties. Recent development in chemically modified nanostructures such as surface catalyst decoration, element doping, plasmonic modification and interfacial hetero-junction design have led to significant advancement in the photoelectrochemical water splitting, by improving surface reaction kinetics and charge separation, transportation and collection efficiency. In this thesis, I will give a detailed discussion on the chemically modified metal oxide nanostructures for photoelectrocemical hydrogen generation, with a focus on the element doping, hydrogen treatment and catalyst modification. I have demonstrated nitrogen doping on ZnO and Ti doping on hematite can improve their photoelectrochemical performance. In addition, we found hydrogen treatment is a general and effective method to improve the photocatalytic performance, by increasing their carrier desities. Hydrogen treatment has been demonstrated on TiO2, WO3 and BiVO4. In the end, we also used electrochemical catalyt to modify these metal oxide photoelectrode for waste water treatment and chemical fuel generation.

Graphene-Based Photocatalysts for Solar-Fuel Generation.

PubMed

Xiang, Quanjun; Cheng, Bei; Yu, Jiaguo

2015-09-21

The production of solar fuel through photocatalytic water splitting and CO2 reduction using photocatalysts has attracted considerable attention owing to the global energy shortage and growing environmental problems. During the past few years, many studies have demonstrated that graphene can markedly enhance the efficiency of photocatalysts for solar-fuel generation because of its unique 2D conjugated structure and electronic properties. Herein we summarize the recent advances in the application of graphene-based photocatalysts for solar-fuel production, including CO2 reduction to hydrocarbon fuel and water splitting to H2. A brief overview of the fundamental principles for splitting of water and reduction of CO2 is given. The different roles of graphene in these graphene-based photocatalysts for improving photocatalytic performance are discussed. Finally, the perspectives on the challenges and opportunities for future research in this promising area are also presented. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

García, Abraham; Cotto, María; Duconge, José

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less

Artificial photosynthesis: Where are we now? Where can we go?

DOE Office of Scientific and Technical Information (OSTI.GOV)

House, Ralph L.; Iha, Neyde Yukie Murakami; Coppo, Rodolfo L.

2015-12-01

Widespread implementation of renewable energy technologies, while preventing significant increases in greenhouse gas emissions, appears to be the only viable solution to meeting the world's energy demands for a sustainable energy future. The final energy mix will include conservation and energy efficiency, wind, geothermal, biomass, and others, but none more ubiquitous or abundant than the sun. Over several decades of development, the cost of photovoltaic cells has decreased significantly with lifetimes that exceed 25 years and there is promise for widespread implementation in the future. However, the solar input is intermittent and, to be practical at a truly large scale,more » will require an equally large capability for energy storage. One approach involves artificial photosynthesis and the use of the sun to drive solar fuel reactions for water splitting into hydrogen and oxygen or to reduce CO2 to reduced carbon fuels. An early breakthrough in this area came from an initial report by Honda and Fujishima on photoelectrochemical water splitting at TiO2 with UV excitation. Significant progress has been made since in exploiting semiconductor devices in water splitting with impressive gains in spectral coverage and solar efficiencies. An alternate, hybrid approach, which integrates molecular light absorption and catalysis with the band gap properties of oxide semiconductors, the dye-sensitized photoelectrosynthesis cell (DSPEC), has been pioneered by the University of North Carolina Energy Frontier Research Center (UNC EFRC) on Solar Fuels. By utilizing chromophore-catalyst assemblies, core/shell oxide structures, and surface stabilization, the EFRC recently demonstrated a viable DSPEC for solar water splitting.« less

C@SiNW/TiO2 Core-Shell Nanoarrays with Sandwiched Carbon Passivation Layer as High Efficiency Photoelectrode for Water Splitting

PubMed Central

Devarapalli, Rami Reddy; Debgupta, Joyashish; Pillai, Vijayamohanan K.; Shelke, Manjusha V.

2014-01-01

One-dimensional heterostructure nanoarrays are efficiently promising as high performance electrodes for photo electrochemical (PEC) water splitting applications, wherein it is highly desirable for the electrode to have a broad light absorption, efficient charge separation and redox properties as well as defect free surface with high area suitable for fast interfacial charge transfer. We present highly active and unique photoelectrode for solar H2 production, consisting of silicon nanowires (SiNWs)/TiO2 core-shell structures. SiNWs are passivated to reduce defect sites and protected against oxidation in air or water by forming very thin carbon layer sandwiched between SiNW and TiO2 surfaces. This carbon layer decreases recombination rates and also enhances the interfacial charge transfer between the silicon and TiO2. A systematic investigation of the role of SiNW length and TiO2 thickness on photocurrent reveals enhanced photocurrent density up to 5.97 mA/cm2 at 1.0 V vs.NHE by using C@SiNW/TiO2 nanoarrays with photo electrochemical efficiency of 1.17%. PMID:24810865

A miniature solar device for overall water splitting consisting of series-connected spherical silicon solar cells.

PubMed

Kageshima, Yosuke; Shinagawa, Tatsuya; Kuwata, Takaaki; Nakata, Josuke; Minegishi, Tsutomu; Takanabe, Kazuhiro; Domen, Kazunari

2016-04-18

A novel "photovoltaics (PV) + electrolyzer" concept is presented using a simple, small, and completely stand-alone non-biased device for solar-driven overall water splitting. Three or four spherical-shaped p-n junction silicon balls were successfully connected in series, named "SPHELAR." SPHELAR possessed small projected areas of 0.20 (3PVs) and 0.26 cm(2) (4PVs) and exhibited working voltages sufficient for water electrolysis. Impacts of the configuration on the PV module performance were carefully analyzed, revealing that a drastic increase in the photocurrent (≈20%) was attained by the effective utilization of a reflective sheet. Separate investigations on the electrocatalyst performance showed that non-noble metal based materials with reasonably small sizes (<0.80 cm(2)) exhibited substantial currents at the PV working voltage. By combining the observations of the PV characteristics, light management and electrocatalyst performance, solar-driven overall water splitting was readily achieved, reaching solar-to-hydrogen efficiencies of 7.4% (3PVs) and 6.4% (4PVs).

Modeling, simulation, and fabrication of a fully integrated, acid-stable, scalable solar-driven water-splitting system.

PubMed

Walczak, Karl; Chen, Yikai; Karp, Christoph; Beeman, Jeffrey W; Shaner, Matthew; Spurgeon, Joshua; Sharp, Ian D; Amashukeli, Xenia; West, William; Jin, Jian; Lewis, Nathan S; Xiang, Chengxiang

2015-02-01

A fully integrated solar-driven water-splitting system comprised of WO3 /FTO/p(+) n Si as the photoanode, Pt/TiO2 /Ti/n(+) p Si as the photocathode, and Nafion as the membrane separator, was simulated, assembled, operated in 1.0 M HClO4 , and evaluated for performance and safety characteristics under dual side illumination. A multi-physics model that accounted for the performance of the photoabsorbers and electrocatalysts, ion transport in the solution electrolyte, and gaseous product crossover was first used to define the optimal geometric design space for the system. The photoelectrodes and the membrane separators were then interconnected in a louvered design system configuration, for which the light-absorbing area and the solution-transport pathways were simultaneously optimized. The performance of the photocathode and the photoanode were separately evaluated in a traditional three-electrode photoelectrochemical cell configuration. The photocathode and photoanode were then assembled back-to-back in a tandem configuration to provide sufficient photovoltage to sustain solar-driven unassisted water-splitting. The current-voltage characteristics of the photoelectrodes showed that the low photocurrent density of the photoanode limited the overall solar-to-hydrogen (STH) conversion efficiency due to the large band gap of WO3 . A hydrogen-production rate of 0.17 mL hr(-1) and a STH conversion efficiency of 0.24 % was observed in a full cell configuration for >20 h with minimal product crossover in the fully operational, intrinsically safe, solar-driven water-splitting system. The solar-to-hydrogen conversion efficiency, ηSTH , calculated using the multiphysics numerical simulation was in excellent agreement with the experimental behavior of the system. The value of ηSTH was entirely limited by the performance of the photoelectrochemical assemblies employed in this study. The louvered design provides a robust platform for implementation of various types of photoelectrochemical assemblies, and can provide an approach to significantly higher solar conversion efficiencies as new and improved materials become available. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First principles studies on the redox ability of (Ga(1-x)Zn(x))N(1-x)O(x) solid solutions and thermal reactions for H2 and O2 production on their surfaces.

PubMed

Du, Yaojun A; Chen, Yun-Wen; Kuo, Jer-Lai

2013-12-07

The (Ga1-xZnx)N1-xOx solid solution has been emerging as an effective photocatalyst for water splitting utilizing the visible solar spectrum, regarded as a host GaN bulk doped with ZnO impurities. H2 and O2 production occur simultaneously and stoichiometrically on the surface of (Ga1-xZnx)N1-xOx particles. In this work, we characterize the redox ability of (Ga1-xZnx)N1-xOx and find that a solid solution with a ZnO concentration of 0.125 < x < 0.250 is optimal for water splitting. This is consistent with the experimental finding that the maximum photocatalytic activity of (Ga1-xZnx)N1-xOx is achieved at x = 0.13. The thermal reactions of water splitting are modeled on both the GaN and an idealized (Ga1-xZnx)N1-xOx (101[combining macron]0) surface. The computed activation barriers allow us to gain some clues on the efficiency of water splitting on a specific photocatalyst surface. Our results suggest that the non-polar (101[combining macron]0) and polar (0001) surfaces may play different roles in water splitting, i.e., the (101[combining macron]0) surface is responsible for O2 production, while hydroxyl groups could dissociate on the (0001) surface.

Nano-sized manganese oxides as biomimetic catalysts for water oxidation in artificial photosynthesis: a review

PubMed Central

Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Aro, Eva-Mari; Lee, Choon-Hwan; Allakhverdiev, Suleyman I.

2012-01-01

There has been a tremendous surge in research on the synthesis of various metal compounds aimed at simulating the water-oxidizing complex (WOC) of photosystem II (PSII). This is crucial because the water oxidation half reaction is overwhelmingly rate-limiting and needs high over-voltage (approx. 1 V), which results in low conversion efficiencies when working at current densities required for hydrogen production via water splitting. Particular attention has been given to the manganese compounds not only because manganese has been used by nature to oxidize water but also because manganese is cheap and environmentally friendly. The manganese–calcium cluster in PSII has a dimension of about approximately 0.5 nm. Thus, nano-sized manganese compounds might be good structural and functional models for the cluster. As in the nanometre-size of the synthetic models, most of the active sites are at the surface, these compounds could be more efficient catalysts than micrometre (or bigger) particles. In this paper, we focus on nano-sized manganese oxides as functional and structural models of the WOC of PSII for hydrogen production via water splitting and review nano-sized manganese oxides used in water oxidation by some research groups. PMID:22809849

Nanostructured hematite for photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Ling, Yichuan

Solar water splitting is an environmentally friendly reaction of producing hydrogen gas. Since Honda and Fujishima first demonstrated solar water splitting in 1972 by using semiconductor titanium dioxide (TiO2) as photoanode in a photoelectrochemical (PEC) cell, extensive efforts have been invested into improving the solar-to-hydrogen (STH) conversion efficiency and lower the production cost of photoelectrochemical devices. In the last few years, hematite (alpha-Fe2O3) nanostructures have been extensively studied as photoanodes for PEC water splitting. Although nanostructured hematite can improve its photoelectrochemical water splitting performance to some extent, by increasing active sites for water oxidation and shortening photogenerated hole path length to semiconductor/electrolyte interface, the photoactivity of pristine hematite nanostructures is still limited by a number of factors, such as poor electrical conductivities and slow oxygen evolution reaction kinetics. Previous studies have shown that tin (Sn) as an n-type dopant can substantially enhance the photoactivity of hematite photoanodes by modifying their optical and electrical properties. In this thesis, I will first demonstrate an unintentional Sn-doping method via high temperature annealing of hematite nanowires grown on fluorine-doped tin oxide (FTO) substrate to enhance the donor density. In addition to introducing extrinsic dopants into semiconductors, the carrier densities of hematite can also be enhanced by creating intrinsic defects. Oxygen vacancies function as shallow donors for a number of hematite. In this regard, I have investigated the influence of oxygen content on thermal decomposition of FeOOH to induce oxygen vacancies in hematite. In the end, I have studied low temperature activation of hematite nanostructures.

Evaluation of selected information on splitting devices for water samples

USGS Publications Warehouse

Capel, P.D.; Larson, S.J.

1996-01-01

Four devices for splitting water samples into representative aliquots are used by the U.S. Geological Survey's Water Resources Division. A thorough evaluation of these devices (14-liter churn, 8-liter churn, plastic cone, and Teflon cone) encompasses a wide variety of concerns, based on both chemical and physical considerations. This report surveys the existing data (as of April 1994) on cleaning efficiency and splitting capability of these devices and presents the data in a systematic framework for evaluation. From the existing data, some of these concerns are adequately or partially addressed, but the majority of concerns could not be addressed because of the lack of data. In general, the existing cleaning and transport protocols are adequate at the milligram per liter level, but the adequacy is largely unknown for trace elements and organic chemicals at lower concen- trations. The existing data indicate that better results are obtained when the splitters are cleaned in the laboratory rather than in the field. Two conclusions that can be reached on the splitting capability of solids are that more work must be done with all four devices to characterize and quantify their limitations and range of usefulness, and that the 14-liter churn (and by association, the 8-liter churn) is not useful in obtaining representative splits of sand-sized particles.

Band edge engineering of oxide photoanodes for photoelectrochemical water splitting: Integration of subsurface dipoles with atomic-scale control

DOE PAGES

Hikita, Yasuyuki; Nishio, Kazunori; Seitz, Linsey C.; ...

2016-01-22

One of the crucial parameters dictating the efficiency of photoelectrochemical water-splitting is the semiconductor band edge alignment with respect to hydrogen and oxygen redox potentials. Despite the importance of metal oxides in their use as photoelectrodes, studies to control the band edge alignment in aqueous solution have been limited predominantly to compound semiconductors with modulation ranges limited to a few hundred mV. The ability to modulate the flat band potential of oxide photoanodes by as much as 1.3 V, using the insertion of subsurface electrostatic dipoles near a Nb-doped SrTiO 3/aqueous electrolyte interface is reported. Lastly, the tunable range achievedmore » far exceeds previous reports in any semiconductor/aqueous electrolyte system and suggests a general design strategy for highly efficient oxide photoelectrodes.« less

Quantum-chemical prediction of the effects of Ni-loading on the hydrogenation and water-splitting efficiency of TiO2 nanoparticles with an experimental test

NASA Astrophysics Data System (ADS)

Lin, Cheng-Kuo; Chuang, Chung-Ching; Raghunath, Putikam; Srinivasadesikan, V.; Wang, T. T.; Lin, M. C.

2017-01-01

The effects of Ni-loading on TiO2 nanoparticles can pronouncedly reduce the barriers for dissociation of H2 from 48 kcal/mol on the pure TiO2 to as low as 1-3 kcal/mol on the loaded samples facilitating the hydrogenation of NPs. Preliminary data of our test indicate that the hydrogenation of Ni-loaded TiO2 NPs results in a significant UV-visible absorption extending well beyond 750 nm with an increase in water splitting efficiency by as much as 67 times over those of pure and hydrogenated TiO2 NPs without Ni-loading under our mild hydrogenation condition using 800 Torr of H2 at 300 °C for 3 h.

Catalysts Based on Earth-Abundant Metals for Visible Light-Driven Water Oxidation Reaction.

PubMed

Lin, Junqi; Han, Qing; Ding, Yong

2018-06-04

Exploration of water oxidation catalyst (WOC) with excellent performance is the key for the overall water splitting reaction, which is a feasible strategy to convert solar energy to chemical energy. Although some compounds composed of noble metals, mainly Ru and Ir, have been reported to catalyze water oxidation with high efficiency, catalysts based on low-cost and earth-abundant transition metals are essential for realizing economical and large-scale light-driven water splitting. Various WOCs containing earth-abundant metals (mainly Mn, Fe, Co, Ni, Cu) have been utilized for visible light-driven water oxidation in recent years. In this Personal Account, we summarize our recent developments in WOCs based on earth-abundant transition metals including polyoxometalates (POMs), metal oxides or bimetal oxides, and metal complexes containing multidentate ligand scaffolds for visible light-driven water oxidation reaction. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Periodically Ordered Nanoporous Perovskite Photoelectrode for Efficient Photoelectrochemical Water Splitting.

PubMed

Shi, Li; Zhou, Wei; Li, Zhao; Koul, Supriya; Kushima, Akihiro; Yang, Yang

2018-06-18

Nonmetallic materials with localized surface plasmon resonance (LSPR) have a great potential for solar energy harvesting applications. Exploring nonmetallic plasmonic materials is desirable yet challenging. Herein, an efficient nonmetallic plasmonic perovskite photoelectrode, namely, SrTiO 3 , with a periodically ordered nanoporous structure showing an intense LSPR in the visible light region is reported. The crystalline-core@amorphous-shell structure of the SrTiO 3 photoelectrode enables a strong LSPR due to the high charge carrier density induced by oxygen vacancies in the amorphous shell. The reversible tunability in LSPR of the SrTiO 3 photoelectrode was observed by oxidation/reduction treatment and incident angle adjusting. Such a nonmetallic plasmonic SrTiO 3 photoelectrode displays a dramatic plasmon-enhanced photoelectrochemical water splitting performance with a photocurrent density of 170.0 μA cm -2 under visible light illumination and a maximum incident photon-to-current-conversion efficiency of 4.0% in the visible light region, which are comparable to the state-of-the-art plasmonic noble metal sensitized photoelectrodes.

Turning Earth Abundant Kesterite-Based Solar Cells Into Efficient Protected Water-Splitting Photocathodes.

PubMed

Ros, Carles; Andreu, Teresa; Giraldo, Sergio; Izquierdo-Roca, Victor; Saucedo, Edgardo; Morante, Joan Ramon

2018-04-25

CZTS/Se kesterite-based solar cells have been protected by conformal atomic layer deposition (ALD)-deposited TiO 2 demonstrating its feasibility as powerful photocathodes for water splitting in highly acidic conditions (pH < 1), achieving stability with no detected degradation and with current density levels similar to photovoltaic productivities. The ALD has allowed low deposition temperatures of 200 °C for TiO 2 , preventing significant variations to the kesterite structure and CdS heterojunction, except for the pure-sulfide stoichiometry, which was studied by Raman spectroscopy. The measured photocurrent at 0 V vs reversible hydrogen electrode, 37 mA·cm -2 , is the highest reported to date, and the associated half-cell solar-to-hydrogen efficiency reached 7%, being amongst the largest presented for kesterite-based photocathodes, corroborating the possibility of using them as abundant low-cost alternative photoabsorbers as their efficiencies are improved toward those of chalcopyrites. An electrical circuit has been proposed to model the photocathode, which comprises the photon absorption, charge transfer through the protective layer, and catalytic performance, which paves the way to the design of highly efficient photoelectrodes.

Integrating a Semitransparent, Fullerene-Free Organic Solar Cell in Tandem with a BiVO4 Photoanode for Unassisted Solar Water Splitting.

PubMed

Peng, Yuelin; Govindaraju, Gokul V; Lee, Dong Ki; Choi, Kyoung-Shin; Andrew, Trisha L

2017-07-12

We report an unassisted solar water splitting system powered by a diketopyrrolopyrrole (DPP)-containing semitransparent organic solar cell. Two major merits of this fullerene-free solar cell enable its integration with a BiVO 4 photoanode. First is the high open circuit voltage and high fill factor displayed by this single junction solar cell, which yields sufficient power to effect water splitting when serially connected to an appropriate electrode/catalyst. Second, the wavelength-resolved photoaction spectrum of the DPP-based solar cell has minimal overlap with that of the BiVO 4 photoanode, thus ensuring that light collection across these two components can be optimized. The latter feature enables a new water splitting device configuration wherein the solar cell is placed first in the path of incident light, before the BiVO 4 photoanode, although BiVO 4 has a wider bandgap. This configuration is accessed by replacing the reflective top electrode of the standard DPP-based solar cell with a thin metal film and an antireflection layer, thus rendering the solar cell semitransparent. In this configuration, incident light does not travel through the aqueous electrolyte to reach the solar cell or photoanode, and therefore, photon losses due to the scattering of water are reduced. Moreover, this new configuration allows the BiVO 4 photoanode to be back-illuminated, i.e., through the BiVO 4 /back contact interface, which leads to higher photocurrents compared to front illumination. The combination of a semitransparent single-junction solar cell and a BiVO 4 photoanode coated with oxygen evolution catalysts in a new device configuration yielded an unassisted solar water splitting system with a solar-to-hydrogen conversion efficiency of 2.2% in water.

Strongly Coupled Molybdenum Carbide on Carbon Sheets as a Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Wang, Hao; Cao, Yingjie; Sun, Cheng; Zou, Guifu; Huang, Jianwen; Kuai, Xiaoxiao; Zhao, Jianqing; Gao, Lijun

2017-09-22

High-performance and affordable electrocatalysts from earth-abundant elements are desirably pursued for water splitting involving hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, a bifunctional electrocatalyst of highly crystalline Mo 2 C nanoparticles supported on carbon sheets (Mo 2 C/CS) was designed toward overall water splitting. Owing to the highly active catalytic nature of Mo 2 C nanoparticles, the high surface area of carbon sheets and efficient charge transfer in the strongly coupled composite, the designed catalysts show excellent bifunctional behavior with an onset potential of -60 mV for HER and an overpotential of 320 mV to achieve a current density of 10 mA cm -2 for OER in 1 m KOH while maintaining robust stability. Moreover, the electrolysis cell using the catalyst only requires a low cell voltage of 1.73 V to achieve a current density of 10 mA cm -2 and maintains the activity for more than 100 h when employing the Mo 2 C/CS catalyst as both anode and cathode electrodes. Such high performance makes Mo 2 C/CS a promising electrocatalyst for practical hydrogen production from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasmon-Sensitized Graphene/TiO2 Inverse Opal Nanostructures with Enhanced Charge Collection Efficiency for Water Splitting.

PubMed

Boppella, Ramireddy; Kochuveedu, Saji Thomas; Kim, Heejun; Jeong, Myung Jin; Marques Mota, Filipe; Park, Jong Hyeok; Kim, Dong Ha

2017-03-01

In this contribution we have developed TiO 2 inverse opal based photoelectrodes for photoelectrochemical (PEC) water splitting devices, in which Au nanoparticles (NPs) and reduced graphene oxide (rGO) have been strategically incorporated (TiO 2 @rGO@Au). The periodic hybrid nanostructure showed a photocurrent density of 1.29 mA cm -2 at 1.23 V vs RHE, uncovering a 2-fold enhancement compared to a pristine TiO 2 reference. The Au NPs were confirmed to extensively broaden the absorption spectrum of TiO 2 into the visible range and to reduce the onset potential of these photoelectrodes. Most importantly, TiO 2 @rGO@Au hybrid exhibited a 14-fold enhanced PEC efficiency under visible light and a 2.5-fold enrichment in the applied bias photon-to-current efficiency at much lower bias potential compared with pristine TiO 2 . Incident photon-to-electron conversion efficiency measurements highlighted a synergetic effect between Au plasmon sensitization and rGO-mediated facile charge separation/transportation, which is believed to significantly enhance the PEC activity of these nanostructures under simulated and visible light irradiation. Under the selected operating conditions the incorporation of Au NPs and rGO into TiO 2 resulted in a remarkable boost in the H 2 evolution rate (17.8 μmol/cm 2 ) compared to a pristine TiO 2 photoelectrode reference (7.6 μmol/cm 2 ). In line with these results and by showing excellent stability as a photoelectrode, these materials are herin underlined to be of promising interest in the PEC water splitting reaction.

Ni3S2 nanowires grown on nickel foam as an efficient bifunctional electrocatalyst for water splitting with greatly practical prospects.

PubMed

Zhang, Dawei; Li, Jingwei; Luo, Jiaxian; Xu, Peiman; Wei, Licheng; Zhou, Dan; Xu, Weiming; Yuan, Dingsheng

2018-06-15

It is essential to synthesize low-cost, earth-abundant bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) for water electrolysis. Herein, we present a one-step sulfurization method to fabricate Ni 3 S 2 nanowires directly grown on Ni foam (Ni 3 S 2 NWs/Ni) as such an electrocatalyst. This synthetic strategy has several advantages including facile preparation, low cost and can even be expanded to large-scale preparation for practical applications. The as-synthesized Ni 3 S 2 NWs/Ni exhibits a low overpotential of 81 and 317 mV to render a current density of 10 mA cm -2 for the HER and OER, respectively, in 1.0 mol l -1 KOH solution. The Ni 3 S 2 NWs/Ni was integrated to be the cathode and the anode in the alkaline electrolyzer for overall water splitting with a current density of 10 mA cm -2 afforded at a cell voltage of 1.63 V. More importantly, this electrolyzer maintained its electrocatalytic activity even after continual water splitting for 30 h. Owing to its simple synthesis process, the earth-abundant electrocatalyst and high performance, this versatile Ni 3 S 2 NWs/Ni electrode will become a promising electrocatalyst for water splitting.

Ni3S2 nanowires grown on nickel foam as an efficient bifunctional electrocatalyst for water splitting with greatly practical prospects

NASA Astrophysics Data System (ADS)

Zhang, Dawei; Li, Jingwei; Luo, Jiaxian; Xu, Peiman; Wei, Licheng; Zhou, Dan; Xu, Weiming; Yuan, Dingsheng

2018-06-01

It is essential to synthesize low-cost, earth-abundant bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reactions (OER) for water electrolysis. Herein, we present a one-step sulfurization method to fabricate Ni3S2 nanowires directly grown on Ni foam (Ni3S2 NWs/Ni) as such an electrocatalyst. This synthetic strategy has several advantages including facile preparation, low cost and can even be expanded to large-scale preparation for practical applications. The as-synthesized Ni3S2 NWs/Ni exhibits a low overpotential of 81 and 317 mV to render a current density of 10 mA cm‑2 for the HER and OER, respectively, in 1.0 mol l‑1 KOH solution. The Ni3S2 NWs/Ni was integrated to be the cathode and the anode in the alkaline electrolyzer for overall water splitting with a current density of 10 mA cm‑2 afforded at a cell voltage of 1.63 V. More importantly, this electrolyzer maintained its electrocatalytic activity even after continual water splitting for 30 h. Owing to its simple synthesis process, the earth-abundant electrocatalyst and high performance, this versatile Ni3S2 NWs/Ni electrode will become a promising electrocatalyst for water splitting.

New Photocatalysts for Hydrogen Production; Nuevos Fotocatalizadores para la Producción de Hidrógeno

DOE PAGES

García, Abraham; Cotto, María; Duconge, José; ...

2014-06-10

The use of hydrogen as replacement for fossil fuels, on which we depend today, is a matter of great relevance. The sustainable generation of hydrogen as fuel is relevant from an environmental and economic point of view. In this study we have explored new synthetic routes for developing new photocatalysts to be used in water splitting, for hydrogen production. Different techniques have been used to produce hydrogen, such as electrolysis, even though these processes have been found to be energetically non suitable. In this research various photocatalytic materials were presented as possible alternatives for using in water splitting processes. Characterizationmore » of the new synthesized materials has been done by using different experimental techniques including Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), surface area BET, and X-ray Diffraction (XRD). The efficiency of the synthesized photocatalysts was determined by evaluating the hydrogen evolution by the photocatalytic water splitting reaction.« less

Surface, Bulk, and Interface: Rational Design of Hematite Architecture toward Efficient Photo-Electrochemical Water Splitting.

PubMed

Li, Chengcheng; Luo, Zhibin; Wang, Tuo; Gong, Jinlong

2018-05-11

Collecting and storing solar energy to hydrogen fuel through a photo-electrochemical (PEC) cell provides a clean and renewable pathway for future energy demands. Having earth-abundance, low biotoxicity, robustness, and an ideal n-type band position, hematite (α-Fe 2 O 3 ), the most common natural form of iron oxide, has occupied the research hotspot for decades. Here, a close look into recent progress of hematite photoanodes for PEC water splitting is provided. Effective approaches are introduced, such as cocatalysts loading and surface passivation layer deposition, to improve the hematite surface reaction in thermodynamics and kinetics. Second, typical methods for enhancing light absorption and accelerating charge transport in hematite bulk are reviewed, concentrating upon doping and nanostructuring. Third, the back contact between hematite and substrate, which affects interface states and electron transfer, is deliberated. In addition, perspectives on the key challenges and future prospects for the development of hematite photoelectrodes for PEC water splitting are given. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Giant onsite electronic entropy enhances the performance of ceria for water splitting

DOE PAGES

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.; ...

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Iron-doped nickel oxide nanocrystals as highly efficient electrocatalysts for alkaline water splitting.

PubMed

Fominykh, Ksenia; Chernev, Petko; Zaharieva, Ivelina; Sicklinger, Johannes; Stefanic, Goran; Döblinger, Markus; Müller, Alexander; Pokharel, Aneil; Böcklein, Sebastian; Scheu, Christina; Bein, Thomas; Fattakhova-Rohlfing, Dina

2015-05-26

Efficient electrochemical water splitting to hydrogen and oxygen is considered a promising technology to overcome our dependency on fossil fuels. Searching for novel catalytic materials for electrochemical oxygen generation is essential for improving the total efficiency of water splitting processes. We report the synthesis, structural characterization, and electrochemical performance in the oxygen evolution reaction of Fe-doped NiO nanocrystals. The facile solvothermal synthesis in tert-butanol leads to the formation of ultrasmall crystalline and highly dispersible FexNi1-xO nanoparticles with dopant concentrations of up to 20%. The increase in Fe content is accompanied by a decrease in particle size, resulting in nonagglomerated nanocrystals of 1.5-3.8 nm in size. The Fe content and composition of the nanoparticles are determined by X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy measurements, while Mössbauer and extended X-ray absorption fine structure analyses reveal a substitutional incorporation of Fe(III) into the NiO rock salt structure. The excellent dispersibility of the nanoparticles in ethanol allows for the preparation of homogeneous ca. 8 nm thin films with a smooth surface on various substrates. The turnover frequencies (TOF) of these films could be precisely calculated using a quartz crystal microbalance. Fe0.1Ni0.9O was found to have the highest electrocatalytic water oxidation activity in basic media with a TOF of 1.9 s(-1) at the overpotential of 300 mV. The current density of 10 mA cm(-2) is reached at an overpotential of 297 mV with a Tafel slope of 37 mV dec(-1). The extremely high catalytic activity, facile preparation, and low cost of the single crystalline FexNi1-xO nanoparticles make them very promising catalysts for the oxygen evolution reaction.

Forming heterojunctions at the nanoscale for improved photoelectrochemical water splitting by semiconductor materials: case studies on hematite.

PubMed

Mayer, Matthew T; Lin, Yongjing; Yuan, Guangbi; Wang, Dunwei

2013-07-16

In order for the future energy needs of humanity to be adequately and sustainably met, alternative energy techniques such as artificial photosynthesis need to be made more efficient and therefore commercially viable. On a grand scale, the energies coming to and leaving from the earth are balanced. With the fast increasing waste heat produced by human activities, the balance may be shifted to threaten the ecosystem in which we reside. To avoid such dire consequences, it is necessary to power human activities using energy derived from the incoming source, which is predominantly solar irradiation. Indeed, most life on the surface of the earth is supported, directly or indirectly, by photosynthesis that harvests solar energy and stores it in chemical bonds for redistribution. Being able to mimic the process and perform it at high efficiencies using low-cost materials has significant implications. Such an understanding is a major intellectual driving force that motivates research by us and many others. From a thermodynamic perspective, the key energy conversion step in natural photosynthesis happens in the light reactions, where H₂O splits to give O₂ and reactive protons. The capability of carrying out direct sunlight-driven water splitting with high efficiency is therefore fundamentally important. We are particularly interested in doing so using inorganic semiconductor materials because they offer the promise of durability and low cost. In this Account, we share our recent efforts in bringing semiconductor-based water splitting reactions closer to reality. More specifically, we focus on earth-abundant oxide semiconductors such as Fe₂O₃ and work on improving the performance of these materials as photoelectrodes for photoelectrochemical reactions. Using hematite (α-Fe₂O₃) as an example, we examine how the main problems that limit the performance, namely, the short hole collection distance, poor light absorption near the band edge, and mismatch of the band edge energetics with those of water redox reactions, can in principle be addressed by adding nanoscale charge collectors, forming buried junctions, and including additional light absorbers. These results highlight the power of forming homo- or heterojunctions at the nanoscale, which permits us to engineer the band structures of semiconductors to the specific application of water splitting. The key enabling factor is our ability to synthesize materials with precise control over the dimensions, crystallinity, and, most importantly, the interface quality at the nanoscale. While being able to tailor specific properties on a simple, earth-abundant device is not straightforward, the approaches we report here take significant steps towards efficient artificial photosynthesis, an energy harvesting technique necessary for the well-being of humanity.

Fabrication of TiO2/CuO photoelectrode with enhanced solar water splitting activity

NASA Astrophysics Data System (ADS)

Atabaev, Timur Sh.; Lee, Dae Hun; Hong, Nguyen Hoa

A bilayered TiO2/CuO photoelectrode was fabricated on a fluorine-doped tin oxide FTO substrate by spin-coating and pulsed laser deposition methods. The prepared bilayered system was assessed as a photoelectrode for solar water splitting. The fabricated TiO2/CuO photoelectrode exhibited a higher photocurrent density (0.022mA/cm2 at 1.23V vs. RHE) compared to bare TiO2 photoelectrode (0.013mA/cm2 at 1.23V vs. RHE). This photocurrent density enhancement was attributed to the improved charge separation combined with the improved sunlight harvesting efficiency of a bilayered structure.

Systematic design of superaerophobic nanotube-array electrode comprised of transition-metal sulfides for overall water splitting.

PubMed

Li, Haoyi; Chen, Shuangming; Zhang, Ying; Zhang, Qinghua; Jia, Xiaofan; Zhang, Qi; Gu, Lin; Sun, Xiaoming; Song, Li; Wang, Xun

2018-06-22

Great attention has been focused on the design of electrocatalysts to enable electrochemical water splitting-a technology that allows energy derived from renewable resources to be stored in readily accessible and non-polluting chemical fuels. Herein we report a bifunctional nanotube-array electrode for water splitting in alkaline electrolyte. The electrode requires the overpotentials of 58 mV and 184 mV for hydrogen and oxygen evolution reactions respectively, meanwhile maintaining remarkable long-term durability. The prominent performance is due to the systematic optimization of chemical composition and geometric structure principally-that is, abundant electrocatalytic active sites, excellent conductivity of metallic 1T' MoS 2 , synergistic effects among iron, cobalt, nickel ions, and the superaerophobicity of electrode surface for fast mass transfer. The electrode is also demonstrated to function as anode and cathode, simultaneously, delivering 10 mA cm -2 at a cell voltage of 1.429 V. Our results demonstrate substantial improvement in the design of high-efficiency electrodes for water electrolysis.

A miniature solar device for overall water splitting consisting of series-connected spherical silicon solar cells

PubMed Central

Kageshima, Yosuke; Shinagawa, Tatsuya; Kuwata, Takaaki; Nakata, Josuke; Minegishi, Tsutomu; Takanabe, Kazuhiro; Domen, Kazunari

2016-01-01

A novel “photovoltaics (PV) + electrolyzer” concept is presented using a simple, small, and completely stand-alone non-biased device for solar-driven overall water splitting. Three or four spherical-shaped p-n junction silicon balls were successfully connected in series, named “SPHELAR.” SPHELAR possessed small projected areas of 0.20 (3PVs) and 0.26 cm2 (4PVs) and exhibited working voltages sufficient for water electrolysis. Impacts of the configuration on the PV module performance were carefully analyzed, revealing that a drastic increase in the photocurrent (≈20%) was attained by the effective utilization of a reflective sheet. Separate investigations on the electrocatalyst performance showed that non-noble metal based materials with reasonably small sizes (<0.80 cm2) exhibited substantial currents at the PV working voltage. By combining the observations of the PV characteristics, light management and electrocatalyst performance, solar-driven overall water splitting was readily achieved, reaching solar-to-hydrogen efficiencies of 7.4% (3PVs) and 6.4% (4PVs). PMID:27087266

A miniature solar device for overall water splitting consisting of series-connected spherical silicon solar cells

NASA Astrophysics Data System (ADS)

Kageshima, Yosuke; Shinagawa, Tatsuya; Kuwata, Takaaki; Nakata, Josuke; Minegishi, Tsutomu; Takanabe, Kazuhiro; Domen, Kazunari

2016-04-01

A novel “photovoltaics (PV) + electrolyzer” concept is presented using a simple, small, and completely stand-alone non-biased device for solar-driven overall water splitting. Three or four spherical-shaped p-n junction silicon balls were successfully connected in series, named “SPHELAR.” SPHELAR possessed small projected areas of 0.20 (3PVs) and 0.26 cm2 (4PVs) and exhibited working voltages sufficient for water electrolysis. Impacts of the configuration on the PV module performance were carefully analyzed, revealing that a drastic increase in the photocurrent (≈20%) was attained by the effective utilization of a reflective sheet. Separate investigations on the electrocatalyst performance showed that non-noble metal based materials with reasonably small sizes (<0.80 cm2) exhibited substantial currents at the PV working voltage. By combining the observations of the PV characteristics, light management and electrocatalyst performance, solar-driven overall water splitting was readily achieved, reaching solar-to-hydrogen efficiencies of 7.4% (3PVs) and 6.4% (4PVs).

Hydrogen generation via photoelectrochemical water splitting using chemically exfoliated MoS{sub 2} layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joshi, R. K., E-mail: r.joshi@unsw.edu.au, E-mail: alwarappan@cecri.res.in; Sahajwalla, V.; Shukla, S.

2016-01-15

Study on hydrogen generation has been of huge interest due to increasing demand for new energy sources. Photoelectrochemical reaction by catalysts was proposed as a promising technique for hydrogen generation. Herein, we report the hydrogen generation via photoelectrochecmial reaction using films of exfoliated 2-dimensional (2D) MoS{sub 2}, which acts as an efficient photocatalyst. The film of chemically exfoliated MoS{sub 2} layers was employed for water splitting, leading to hydrogen generation. The amount of hydrogen was qualitatively monitored by observing overpressure of a water container. The high photo-current generated by MoS{sub 2} film resulted in hydrogen evolution. Our work shows thatmore » 2D MoS{sub 2} is one of the promising candidates as a photocatalyst for light-induced hydrogen generation. High photoelectrocatalytic efficiency of the 2D MoS{sub 2} shows a new way toward hydrogen generation, which is one of the renewable energy sources. The efficient photoelectrocatalytic property of the 2D MoS{sub 2} is possibly due to availability of catalytically active edge sites together with minimal stacking that favors the electron transfer.« less

High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duan, Haohong; Li, Dongguo; Tang, Yan

2017-04-05

The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermostmore » atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.« less

High-Performance Rh 2 P Electrocatalyst for Efficient Water Splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duan, Haohong; Li, Dongguo; Tang, Yan

2017-04-05

Search for active, stable and cost-efficient electrocatalysts for hydrogen production via water splitting could make substantial impact to the energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high surface area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) compared to Rh/C and Pt/C catalysts. The atomic structure of the rhodium phosphide nanocubes was directly observed by annular dark-field scanning transmission electron microscopy (ADF-STEM),more » which revealed phosphorous-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorous plays crucial role in determining the robust catalyst properties.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Dongseok; Young, James L.; Lim, Haneol

Despite their excellent photophysical properties and record-high solar-to-hydrogen conversion efficiency, the high cost and limited stability of III-V compound semiconductors prohibit their practical application in solar-driven photoelectrochemical water splitting. Here in this paper we present a strategy for III-V photocatalysis that can circumvent these difficulties via printed assemblies of epitaxially grown compound semiconductors. A thin film stack of GaAs-based epitaxial materials is released from the growth wafer and printed onto a non-native transparent substrate to form an integrated photocatalytic electrode for solar hydrogen generation. The heterogeneously integrated electrode configuration together with specialized epitaxial design serve to decouple the material interfacesmore » for illumination and electrocatalysis. Subsequently, this allows independent control and optimization of light absorption, carrier transport, charge transfer, and material stability. Using this approach, we construct a series-connected wireless tandem system of GaAs photoelectrodes and demonstrate 13.1% solar-to-hydrogen conversion efficiency of unassisted-mode water splitting.« less

Split exponential track length estimator for Monte-Carlo simulations of small-animal radiation therapy

NASA Astrophysics Data System (ADS)

Smekens, F.; Létang, J. M.; Noblet, C.; Chiavassa, S.; Delpon, G.; Freud, N.; Rit, S.; Sarrut, D.

2014-12-01

We propose the split exponential track length estimator (seTLE), a new kerma-based method combining the exponential variant of the TLE and a splitting strategy to speed up Monte Carlo (MC) dose computation for low energy photon beams. The splitting strategy is applied to both the primary and the secondary emitted photons, triggered by either the MC events generator for primaries or the photon interactions generator for secondaries. Split photons are replaced by virtual particles for fast dose calculation using the exponential TLE. Virtual particles are propagated by ray-tracing in voxelized volumes and by conventional MC navigation elsewhere. Hence, the contribution of volumes such as collimators, treatment couch and holding devices can be taken into account in the dose calculation. We evaluated and analysed the seTLE method for two realistic small animal radiotherapy treatment plans. The effect of the kerma approximation, i.e. the complete deactivation of electron transport, was investigated. The efficiency of seTLE against splitting multiplicities was also studied. A benchmark with analog MC and TLE was carried out in terms of dose convergence and efficiency. The results showed that the deactivation of electrons impacts the dose at the water/bone interface in high dose regions. The maximum and mean dose differences normalized to the dose at the isocenter were, respectively of 14% and 2% . Optimal splitting multiplicities were found to be around 300. In all situations, discrepancies in integral dose were below 0.5% and 99.8% of the voxels fulfilled a 1%/0.3 mm gamma index criterion. Efficiency gains of seTLE varied from 3.2 × 105 to 7.7 × 105 compared to analog MC and from 13 to 15 compared to conventional TLE. In conclusion, seTLE provides results similar to the TLE while increasing the efficiency by a factor between 13 and 15, which makes it particularly well-suited to typical small animal radiation therapy applications.

Carbon Nitride-Aromatic Diimide-Graphene Nanohybrids: Metal-Free Photocatalysts for Solar-to-Hydrogen Peroxide Energy Conversion with 0.2% Efficiency.

PubMed

Kofuji, Yusuke; Isobe, Yuki; Shiraishi, Yasuhiro; Sakamoto, Hirokatsu; Tanaka, Shunsuke; Ichikawa, Satoshi; Hirai, Takayuki

2016-08-10

Solar-to-chemical energy conversion is a challenging subject for renewable energy storage. In the past 40 years, overall water splitting into H2 and O2 by semiconductor photocatalysis has been studied extensively; however, they need noble metals and extreme care to avoid explosion of the mixed gases. Here we report that generating hydrogen peroxide (H2O2) from water and O2 by organic semiconductor photocatalysts could provide a new basis for clean energy storage without metal and explosion risk. We found that carbon nitride-aromatic diimide-graphene nanohybrids prepared by simple hydrothermal-calcination procedure produce H2O2 from pure water and O2 under visible light (λ > 420 nm). Photoexcitation of the semiconducting carbon nitride-aromatic diimide moiety transfers their conduction band electrons to graphene and enhances charge separation. The valence band holes on the semiconducting moiety oxidize water, while the electrons on the graphene moiety promote selective two-electron reduction of O2. This metal-free system produces H2O2 with solar-to-chemical energy conversion efficiency 0.20%, comparable to the highest levels achieved by powdered water-splitting photocatalysts.

Solution deposited and modified iron oxide for enhanced solar water splitting

NASA Astrophysics Data System (ADS)

Abel, Anthony J.

Growing worldwide energy demand coupled with an increasing awareness of anthropogenic climate change has driven research into carbon-neutral and solar-derived energy sources. One attractive strategy is the storage of solar energy in the bonds of H2 formed by photoelectrochemical (PEC) water splitting. Hematite, an iron oxide, has been widely investigated as a candidate material for PEC water splitting due to its stability, non-toxicity, earth abundance and consequent low cost, and a theoretical 15% solar-to-hydrogen conversion efficiency. However, poor electrical properties and slow rates of the water oxidation reaction have limited its potential as an economical water splitting catalyst. Additionally, the most efficient hematite-based devices are fabricated via expensive, vacuum-phase techniques, limiting scalability to broad integration into the energy supply. In this thesis, I develop a new, solution-based deposition method for high quality, planar hematite thin films using successive ionic layer adsorption and reaction (SILAR). The constant geometry and tight control over layer thickness possible with SILAR makes these films ideal model systems to understand the two key steps of PEC water oxidation: charge separation and interfacial hole transfer. In Chapter 3, I report on facile annealing treatments to dope hematite with Ti and Sn, and I show that these impurity atoms at the hematite/electrolyte interface increase hole transfer efficiency from nearly 0 to above 60%. However, charge separation remains below 15% with these dopants incorporated via solid state diffusion, mainly due to low hole mobility. To overcome this associated small transport length, extremely thin hematite coatings were deposited on Sb:SnO2 monolayer inverse opal scaffolds. With this modified substrate, photocurrent increased proportionately to the surface area of the scaffold. While Chapter 3 discusses incorporation of dopants via solid state diffusion, Chapter 4 examines methods to incorporate Ti via modified SILAR solutions. With this method, hematite films with well-controlled, uniform doping profiles were successfully fabricated. An optimal Ti concentration of 4.2% in the film enabled a charge separation efficiency of >20%, and I show that holes generated within 3 nm of the depletion region are separated with unity efficiency. With the addition of an ultrathin FeOOH overlayer, hole transfer efficiency is increased to 100% as a result of an increased concentration of reactive holes at the hematite/electrolyte interface. These combined effects lead to photocurrents >0.85 mAcm-2 at 1.23 VRHE, which is competitive with champion planar films regardless of fabrication method. Importantly, the methods of fabrication and analysis described in this thesis are applicable to a wide range of materials for a variety of applications. The SILAR method can be applied to many compounds, provided their constituent atoms are soluble in liquid solvents. Additionally, the facile optical and electrochemical measurements used to analyze hematite in Chapters 3 and 4 can be readily adapted to other semiconductor materials with the aim of understanding their charge transport properties.

Water oxidation chemistry of photosystem II.

PubMed

Brudvig, Gary W

2008-03-27

Photosystem II (PSII) uses light energy to split water into protons, electrons and O2. In this reaction, nature has solved the difficult chemical problem of efficient four-electron oxidation of water to yield O2 without significant amounts of reactive intermediate species such as superoxide, hydrogen peroxide and hydroxyl radicals. In order to use nature's solution for the design of artificial catalysts that split water, it is important to understand the mechanism of the reaction. The recently published X-ray crystal structures of cyanobacterial PSII complexes provide information on the structure of the Mn and Ca ions, the redox-active tyrosine called YZ and the surrounding amino acids that comprise the O2-evolving complex (OEC). The emerging structure of the OEC provides constraints on the different hypothesized mechanisms for O2 evolution. The water oxidation mechanism of PSII is discussed in the light of biophysical and computational studies, inorganic chemistry and X-ray crystallographic information.

A rational approach towards enhancing solar water splitting: a case study of Au-RGO/N-RGO-TiO2.

PubMed

Bharad, Pradnya A; Sivaranjani, Kumarsrinivasan; Gopinath, Chinnakonda S

2015-07-07

A rational approach was employed to enhance the solar water splitting (SWS) efficiency by systematically combining various important factors that helps to increase the photocatalytic activity. The rational approach includes four important parameters, namely, charge generation through simulated sunlight absorption, charge separation and diffusion, charge utilization through redox reaction, and the electronic integration of all of the above three factors. The complexity of the TiO2 based catalyst and its SWS activity was increased systematically by adding reduced graphene oxide (RGO) or N-doped RGO and/or nanogold. Au-N-RGO-TiO2 shows the maximum apparent quantum yield (AQY) of 2.46% with a H2 yield (525 μmol g(-1) h(-1)) from aqueous methanol, and overall water splitting activity (22 μmol g(-1) h(-1); AQY = 0.1%) without any sacrificial agent under one sun conditions. This exercise helps to understand the factors which help to enhance the SWS activity. Activity enhancement was observed when there is synergy among the components, especially the simulated sunlight absorption (or one sun conditions), charge separation/conduction and charge utilization. Electronic integration among the components provides the synergy for efficient solar light harvesting. In our opinion, the above synergy helps to increase the overall utilization of charge carriers towards the higher activity.

When NiO@Ni Meets WS2 Nanosheet Array: A Highly Efficient and Ultrastable Electrocatalyst for Overall Water Splitting.

PubMed

Wang, Dewen; Li, Qun; Han, Ce; Xing, Zhicai; Yang, Xiurong

2018-01-24

The development of low-cost, high-efficiency, and stable bifunctional electrocatalysts toward the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of paramount importance for large-scale water splitting. Here, we develop a new strategy for the first design and synthesis of a NiO@Ni decorated WS 2 nanosheet array on carbon cloth (NiO@Ni/WS 2 /CC) composite. This composite serves as a unique three-dimensional (3D) synergistic electrocatalyst that not only combines the intrinsic properties of individual NiO@Ni and WS 2 , but also exhibits significantly improved HER and OER activities when compared to that of pure NiO@Ni and WS 2 . This electrocatalyst possesses Pt-like activity for HER and exhibits better OER performance than that for commercial RuO 2 , as well as demonstrating superior long-term durability in alkaline media. Furthermore, it enables an alkaline electrolyzer with a current density of 10 mA cm -2 at a cell voltage as 1.42 V, which is the lowest one among all reported values to date. The excellent performance is mainly attributed to the unique 3D configuration and multicomponent synergies among NiO, Ni, and WS 2 . Our findings provide a new idea to design advanced bifunctional catalysts for water splitting.

Dye-sensitized photoelectrochemical water oxidation through a buried junction.

PubMed

Xu, Pengtao; Huang, Tian; Huang, Jianbin; Yan, Yun; Mallouk, Thomas E

2018-06-18

Water oxidation has long been a challenge in artificial photosynthetic devices that convert solar energy into fuels. Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) provide a modular approach for integrating light-harvesting molecules with water-oxidation catalysts on metal-oxide electrodes. Despite recent progress in improving the efficiency of these devices by introducing good molecular water-oxidation catalysts, WS-DSPECs have poor stability, owing to the oxidation of molecular components at very positive electrode potentials. Here we demonstrate that a solid-state dye-sensitized solar cell (ss-DSSC) can be used as a buried junction for stable photoelectrochemical water splitting. A thin protecting layer of TiO 2 grown by atomic layer deposition (ALD) stabilizes the operation of the photoanode in aqueous solution, although as a solar cell there is a performance loss due to increased series resistance after the coating. With an electrodeposited iridium oxide layer, a photocurrent density of 1.43 mA cm -2 was observed in 0.1 M pH 6.7 phosphate solution at 1.23 V versus reversible hydrogen electrode, with good stability over 1 h. We measured an incident photon-to-current efficiency of 22% at 540 nm and a Faradaic efficiency of 43% for oxygen evolution. While the potential profile of the catalyst layer suggested otherwise, we confirmed the formation of a buried junction in the as-prepared photoelectrode. The buried junction design of ss-DSSs adds to our understanding of semiconductor-electrocatalyst junction behaviors in the presence of a poor semiconducting material.

Comparing photoelectrochemical water oxidation, recombination kinetics and charge trapping in the three polymorphs of TiO2.

PubMed

Moss, Benjamin; Lim, Kee Kean; Beltram, Alessandro; Moniz, Savio; Tang, Junwang; Fornasiero, Paolo; Barnes, Piers; Durrant, James; Kafizas, Andreas

2017-06-07

In this article we present the first comparative study of the transient decay dynamics of photo-generated charges for the three polymorphs of TiO 2 . To our knowledge, this is the first such study of the brookite phase of TiO 2 over timescales relevant to the kinetics of water splitting. We find that the behavior of brookite, both in the dynamics of relaxation of photo-generated charges and in energetic distribution, is similar to the anatase phase of TiO 2 . Moreover, links between the rate of recombination of charge carriers, their energetic distribution and the mode of transport are made in light of our findings and used to account for the differences in water splitting efficiency observed across the three polymorphs.

Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells

PubMed Central

Swierk, John R.; Méndez-Hernández, Dalvin D.; McCool, Nicholas S.; Liddell, Paul; Terazono, Yuichi; Pahk, Ian; Tomlin, John J.; Oster, Nolan V.; Moore, Thomas A.; Moore, Ana L.; Gust, Devens; Mallouk, Thomas E.

2015-01-01

Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO2 solar cell. We report the synthesis, spectral, and electrochemical properties of the sensitizers. Despite slow recombination of photoinjected electrons with oxidized porphyrins, photocurrents are low because of low injection yields and slow electron self-exchange between oxidized porphyrins. The free-base porphyrins are stable under conditions of water photoelectrolysis and in some cases photovoltages in excess of 1 V are observed. PMID:25583488

Photosynthetic water splitting by the Mn4Ca2+OX catalyst of photosystem II: its structure, robustness and mechanism.

PubMed

Barber, James

2017-01-01

The biological energy cycle of our planet is driven by photosynthesis whereby sunlight is absorbed by chlorophyll and other accessory pigments. The excitation energy is then efficiently transferred to a reaction centre where charge separation occurs in a few picoseconds. In the case of photosystem II (PSII), the energy of the charge transfer state is used to split water into oxygen and reducing equivalents. This is accomplished by the relatively low energy content of four photons of visible light. PSII is a large multi-subunit membrane protein complex embedded in the lipid environment of the thylakoid membranes of plants, algae and cyanobacteria. Four high energy electrons, together with four protons (4H+), are used to reduce plastoquinone (PQ), the terminal electron acceptor of PSII, to plastoquinol (PQH2). PQH2 passes its reducing equivalents to an electron transfer chain which feeds into photosystem I (PSI) where they gain additional reducing potential from a second light reaction which is necessary to drive CO2 reduction. The catalytic centre of PSII consists of a cluster of four Mn ions and a Ca2+ linked by oxo bonds. In addition, there are seven amino acid ligands. In this Article, I discuss the structure of this metal cluster, its stability and the probability that an acid-base (nucleophilic-electrophilic) mechanism catalyses the water splitting reaction on the surface of the metal-cluster. Evidence for this mechanism is presented from studies on water splitting catalysts consisting of organo-complexes of ruthenium and manganese and also by comparison with the enzymology of carbon monoxide dehydrogenase (CODH). Finally the relevance of our understanding of PSII is discussed in terms of artificial photosynthesis with emphasis on inorganic water splitting catalysts as oxygen generating photoelectrodes.

Targeted Synthesis of Unique Nickel Sulfide (NiS, NiS2) Microarchitectures and the Applications for the Enhanced Water Splitting System.

PubMed

Luo, Pan; Zhang, Huijuan; Liu, Li; Zhang, Yan; Deng, Ju; Xu, Chaohe; Hu, Ning; Wang, Yu

2017-01-25

Water splitting is one of the ideal technologies to meet the ever increasing demands of energy. Many materials have aroused great attention in this field. The family of nickel-based sulfides is one of the examples that possesses interesting properties in water-splitting fields. In this paper, a controllable and simple strategy to synthesize nickel sulfides was proposed. First, we fabricated NiS 2 hollow microspheres via a hydrothermal process. After a precise heat control in a specific atmosphere, NiS porous hollow microspheres were prepared. NiS 2 was applied in hydrogen evolution reaction (HER) and shows a marvelous performance both in acid medium (an overpotential of 174 mV to achieve a current density of 10 mA/cm 2 and the Tafel slope is only 63 mV/dec) and in alkaline medium (an overpotential of 148 mV to afford a current density of 10 mA/cm 2 and the Tafel slope is 79 mV/dec). NiS was used in oxygen evolution reaction (OER) showing a low overpotential of 320 mV to deliver a current density of 10 mA/cm 2 , which is meritorious. These results enlighten us to make an efficient water-splitting system, including NiS 2 as HER catalyst in a cathode and NiS as OER catalyst in an anode. The system shows high activity and good stabilization. Specifically, it displays a stable current density of 10 mA/cm 2 with the applying voltage of 1.58 V, which is a considerable electrolyzer for water splitting.

Design Guidelines for High-Performance Particle-Based Photoanodes for Water Splitting: Lanthanum Titanium Oxynitride as a Model.

PubMed

Landsmann, Steve; Maegli, Alexandra E; Trottmann, Matthias; Battaglia, Corsin; Weidenkaff, Anke; Pokrant, Simone

2015-10-26

Semiconductor powders are perfectly suited for the scalable fabrication of particle-based photoelectrodes, which can be used to split water using the sun as a renewable energy source. This systematic study is focused on variation of the electrode design using LaTiO2 N as a model system. We present the influence of particle morphology on charge separation and transport properties combined with post-treatment procedures, such as necking and size-dependent co-catalyst loading. Five rules are proposed to guide the design of high-performance particle-based photoanodes by adding or varying several process steps. We also specify how much efficiency improvement can be achieved using each of the steps. For example, implementation of a connectivity network and surface area enhancement leads to thirty times improvement in efficiency and co-catalyst loading achieves an improvement in efficiency by a factor of seven. Some of these guidelines can be adapted to non-particle-based photoelectrodes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A graded catalytic–protective layer for an efficient and stable water-splitting photocathode

DOE PAGES

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne; ...

2017-01-09

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

Formation mechanism of TiO2 nanotubes and their applications in photoelectrochemical water splitting and supercapacitors.

PubMed

Chen, Bo; Hou, Junbo; Lu, Kathy

2013-05-14

Structural observations of the transition of TiO2 nanopores into nanotubes by increasing the OH(-) concentration in the electrolyte challenge the validity of existing formation mechanisms of anodic TiO2 nanotubes. In this study, dehydration of titanium hydroxide in the cell wall is proposed as the mechanism that leads to the separation of neighboring nanotubes. Based on this understanding, bamboo-type TiO2 nanotubes with large surface area and excellent interconnectivity are achieved by cycling high and low applied potentials. After thermal treatment in a H2 atmosphere, the bamboo-type TiO2 nanotubes show large photoelectrochemical water splitting efficiency and supercapacitors performace.

Ultrathin planar hematite film for solar photoelectrochemical water splitting

DOE PAGES

Liu, Dong; Bierman, David M.; Lenert, Andrej; ...

2015-10-08

Hematite holds promise for photoelectrochemical (PEC) water splitting due to its stability, low-cost, abundance and appropriate bandgap. However, it suffers from a mismatch between the hole diffusion length and light penetration length. We have theoretically designed and characterized an ultrathin planar hematite/silver nanohole array/silver substrate photoanode. Due to the supported destructive interference and surface plasmon resonance, photons are efficiently absorbed in an ultrathin hematite film. In conclusion, compared with ultrathin hematite photoanodes with nanophotonic structures, this photoanode has comparable photon absorption but with intrinsically lower recombination losses due to its planar structure and promises to exceed the state-of-the-art photocurrent ofmore » hematite photoanodes.« less

Photocatalytic water splitting: Materials design and high-throughput screening of molecular compositions

NASA Astrophysics Data System (ADS)

Khnayzer, Rony S.

Due to the expected increases on energy demand in the near future, the development of new catalytic molecular compositions and materials capable of directly converting water, with the aid of solar photons, into hydrogen becomes obviated. Hydrogen is a combustible fuel and precious high-energy feedstock chemical. However, for the water-splitting reaction to proceed efficiently and economically enough for large-scale application, efficient light-absorbing sensitizers and water splitting catalysts are required. To study the kinetics of the water reduction reaction, we have used titania (TiO2) nanoparticles as a robust scaffold to photochemically grow platinum (Pt) nanoparticles from a unique surface-anchored molecular precursor Pt(dcbpy)Cl2 [dcbpy = 4,4'-dicarboxylic acid-2,2'-bipyridine]. The hybrid Pt/TiO 2 nanomaterials obtained were shown to be a superior water reduction catalyst (WRC) in aqueous suspensions when compared with the benchmark platinized TiO2. In addition, cobalt phosphate (CoPi) water oxidation catalyst (WOC) was photochemically assembled on the surface of TiO2, and its structure and mechanism of activity showed resemblance to the established electrochemically grown CoPi material. Both WRC and WOC described above possessed near unity Faradaic efficiency for hydrogen and oxygen production respectively, and were fully characterized by electron microscopy, x-ray absorption spectroscopy, electrochemistry and photochemistry. While there are established materials and molecules that are able to drive water splitting catalysis, some of these efficient semiconductors, including titanium dioxide (TiO2) and tungsten trioxide (WO3), are only able to absorb high-energy (ultraviolet or blue) photons. This high-energy light represents merely a fraction of the solar spectrum that strikes the earth and the energy content of those remaining photons is simply wasted. A strategy to mitigate this problem has been developed over the years in our laboratory. Briefly, photons of low energy are converted into higher energy light using a process termed photon upconversion. Using this technique, low energy photons supplied by the sun can be converted into light of appropriate energy to trigger electronic transitions in high energy absorbing photoactive materials without any chemical modification of the latter. We have shown, that this technology is capable of upconverting visible sunlight to sensitize wide-bandgap semiconductors such as WO3, subsequently extending the photoaction of these materials to cover a larger portion of the solar spectrum. Besides the engineering of different compositions that serve as either sensitizers or catalysts in these solar energy conversion schemes, we have designed an apparatus for parallel high-throughput screening of these photocatalytic compositions. This combinatorial approach to solar fuels photocatalysis has already led to unprecedented fundamental understanding of the generation of hydrogen gas from pure water. The activity of a series of new Ru(II) sensitizers along with Co(II) molecular WRCs were optimized under visible light excitation utilizing different experimental conditions. The multi-step mechanism of activity of selected compositions was further elucidated by pump-probe transient absorption spectroscopy.

Investigation of porosity and heterojunction effects of a mesoporous hematite electrode on photoelectrochemical water splitting.

PubMed

Liu, Jingling; Shahid, Muhammad; Ko, Young-Seon; Kim, Eunchul; Ahn, Tae Kyu; Park, Jong Hyeok; Kwon, Young-Uk

2013-06-28

In this paper, we report the porosity and heterojunction effects of hematite (α-Fe2O3) on the photoelectrochemical (PEC) water splitting properties. The worm-like mesoporous hematite thin films (MHFs) with a pore size of ~9 nm and a wall thickness of ~5 nm were successfully obtained through the self-assembly process. MHFs formed on FTO showed much better PEC properties than those of nonporous hematite thin films (NP-HF) owing to the suppression of charge recombination. The PEC data of MHFs under front and back illumination conditions indicated that the porous structure allows the diffusion of electrolyte deep inside the MHF increasing the number of holes to be utilized in the water oxidation reaction. A heterojunction structure was formed by introducing a thin layer of SnO2 (~15 nm in thickness) between the MHF and FTO for a dramatically enhanced PEC response, which is attributed to the efficient electron transfer. Our spectroscopic and electrochemical data show that the SnO2 layer functions as an efficient electron transmitter, but does not affect the recombination kinetics of MHFs.

Nickel-based anodic electrocatalysts for fuel cells and water splitting

NASA Astrophysics Data System (ADS)

Chen, Dayi

Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel-based catalysts, methanol oxidation suffers from high overpotential and catalyst poisoning by high concentration of substrates, so current nickel-based catalysts are more suitable to be used as oxygen evolution catalysts. A photoanode design that applies nickel oxides to a semiconductor that is incorporated with surface-plasmonic metal electrodes to do solar water oxidation with visible light is proposed.

An anti-photocorrosive photoanode based on a CdS/NixSy@NF heterostructure for visible-light-driven water splitting

NASA Astrophysics Data System (ADS)

Zhang, Dantong; Liu, Lulu; Zhang, Lei; Qi, Kun; Zhang, Haiyan; Cui, Xiaoqiang

2017-10-01

Photoelectrochemical (PEC) water splitting holds promise for both sustainable energy generation and energy storage. CdS, a sulphide semiconductor possessing a narrow band gap (2.4 eV) and high photocatalytic activity, has been widely used to build photoanodes for PEC water splitting; however, it also suffers from photocorrosion under irradiation. An innovative method is presented here to significantly improve the stability of CdS photoanodes by constructing a p-n junction comprising CdS/NixSy on nickel foam (NF) via a one-pot hydrothermal method. The n-type CdS is surrounded by p-type NixSy serving as a fast and effective hole receiver of excess holes from CdS. More importantly, the CdS/NixSy shows significantly improved PEC stability compared to the pure CdS electrode, with ≈70% of the initial photocurrent retained after 2000 s of irradiation (>420 nm). This work provides a new insight into the fabrication of other p-n junction self-assembled photoanodes to simultaneously enhance charge separation and transport for efficient and stable solar fuel production.

Constructing a novel hierarchical 3D flower-like nano/micro titanium phosphate with efficient hydrogen evolution from water splitting

NASA Astrophysics Data System (ADS)

Guo, Si-yao; Han, Song

2014-12-01

A novel nano/micro hierarchical structured titanium phosphate with unique 3D flower-like morphology has been prepared by a simple hydrothermal method without adding any surfactants. The shape of the titanium phosphate could be controlled by simply adjusting the concentration of phosphoric acid. The 3D flower-like titanium phosphate with diameter of 2-3 μm is characterized by the assembly of numerous porous and connected lamella structures. Interestingly, this novel hierarchical mesoporous 3D flower-like titanium exhibits enhanced hydrogen evolution from water splitting under xenon lamp irradiation in the presence of methanol as the sacrificial reagent, which is also the first example of 3D flower-like titanium phosphate with high photocatalytic activity for water splitting. Since the use of titanium phosphate as a photocatalyst has been mostly neglected up to now, this low-cost, simple procedure and large-scale yield of 3D nano/micro structure titanium phosphate could be expected to be applicable in the synthesis of controlled, reproducible and robust photocatalytic systems.

Extraction of nickel from NiFe-LDH into Ni2P@NiFe hydroxide as a bifunctional electrocatalyst for efficient overall water splitting† †Electronic supplementary information (ESI) available: Experimental and computational details and additional data. See DOI: 10.1039/c7sc04569g

PubMed Central

Zhang, Fang-Shuai; Wang, Jia-Wei; Luo, Jun; Liu, Rui-Rui

2017-01-01

The development of highly efficient, low-cost and stable electrocatalysts for overall water splitting is highly desirable for the storage of intermittent solar energy and wind energy sources. Herein, we show for the first time that nickel can be extracted from NiFe-layered double hydroxide (NiFe-LDH) to generate an Ni2P@FePOx heterostructure. The Ni2P@FePOx heterostructure was converted to an Ni2P@NiFe hydroxide heterostructure (P-NiFe) during water splitting, which displays high electrocatalytic performance for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1.0 M KOH solution, with an overpotential of 75 mV at 10 mA cm–2 for HER, and overpotentials of 205, 230 and 430 mV at 10, 100 and 1000 mA cm–2 for OER, respectively. Moreover, it could afford a stable current density of 10 mA cm–2 for overall water splitting at 1.51 V in 1.0 M KOH with long-term durability (100 h). This cell voltage is among the best reported values for bifunctional electrocatalysts. The results of theoretical calculations demonstrate that P-NiFe displays optimized adsorption energies for both HER and OER intermediates at the nickel active sites, thus dramatically enhancing its electrocatalytic activity. PMID:29675186

Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution

NASA Astrophysics Data System (ADS)

Park, Sunghak; Chang, Woo Je; Lee, Chan Woo; Park, Sangbaek; Ahn, Hyo-Yong; Nam, Ki Tae

2017-01-01

The solar-driven splitting of hydrohalic acids (HX) is an important and fast growing research direction for H2 production. In addition to the hydrogen, the resulting chemicals (X2/X3-) can be used to propagate a continuous process in a closed cycle and are themselves useful products. Here we present a strategy for photocatalytic hydrogen iodide (HI) splitting using methylammonium lead iodide (MAPbI3) in an effort to develop a cost-effective and easily scalable process. Considering that MAPbI3 is a water-soluble ionic compound, we exploit the dynamic equilibrium of the dissolution and precipitation of MAPbI3 in saturated aqueous solutions. The I- and H+ concentrations of the aqueous solution are determined to be the critical parameters for the stabilization of the tetragonal MAPbI3 phase. Stable and efficient H2 production under visible light irradiation was demonstrated. The solar HI splitting efficiency of MAPbI3 was 0.81% when using Pt as a cocatalyst.

Metal-free organic sensitizers for use in water-splitting dye-sensitized photoelectrochemical cells

DOE PAGES

Swierk, John R.; Méndez-Hernández, Dalvin D.; McCool, Nicholas S.; ...

2015-01-12

Solar fuel generation requires the efficient capture and conversion of visible light. In both natural and artificial systems, molecular sensitizers can be tuned to capture, convert, and transfer visible light energy. We demonstrate that a series of metal-free porphyrins can drive photoelectrochemical water splitting under broadband and red light (λ > 590 nm) illumination in a dye-sensitized TiO 2 solar cell. Here, we report the synthesis, spectral, and electrochemical properties of the sensitizers. Despite slow recombination of photoinjected electrons with oxidized porphyrins, photocurrents are low because of low injection yields and slow electron self-exchange between oxidized porphyrins. As a result,more » the free-base porphyrins are stable under conditions of water photoelectrolysis and in some cases photovoltages in excess of 1 V are observed.« less

Plasmonic Enhancement in BiVO4 Photonic Crystals for Efficient Water Splitting

PubMed Central

Zhang, Liwu; Lin, Chia-Yu; Valev, Ventsislav K; Reisner, Erwin; Steiner, Ullrich; Baumberg, Jeremy J

2014-01-01

Photo-electrochemical water splitting is a very promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the solar-to-H2 conversion efficiency is still very low due to rapid bulk recombination of charge carriers. Here, a photonic nano-architecture is developed to improve charge carrier generation and separation by manipulating and confining light absorption in a visible-light-active photoanode constructed from BiVO4 photonic crystal and plasmonic nanostructures. Synergistic effects of photonic crystal stop bands and plasmonic absorption are observed to operate in this photonic nanostructure. Within the scaffold of an inverse opal photonic crystal, the surface plasmon resonance is significantly enhanced by the photonic Bragg resonance. Nanophotonic photoanodes show AM 1.5 photocurrent densities of 3.1 ± 0.1 mA cm−2 at 1.23 V versus RHE, which is among the highest for oxide-based photoanodes and over 4 times higher than the unstructured planar photoanode. PMID:24916174

Unassisted photoelectrochemical water splitting exceeding 7% solar-to-hydrogen conversion efficiency using photon recycling

PubMed Central

Shi, Xinjian; Jeong, Hokyeong; Oh, Seung Jae; Ma, Ming; Zhang, Kan; Kwon, Jeong; Choi, In Taek; Choi, Il Yong; Kim, Hwan Kyu; Kim, Jong Kyu; Park, Jong Hyeok

2016-01-01

Various tandem cell configurations have been reported for highly efficient and spontaneous hydrogen production from photoelectrochemical solar water splitting. However, there is a contradiction between two main requirements of a front photoelectrode in a tandem cell configuration, namely, high transparency and high photocurrent density. Here we demonstrate a simple yet highly effective method to overcome this contradiction by incorporating a hybrid conductive distributed Bragg reflector on the back side of the transparent conducting substrate for the front photoelectrochemical electrode, which functions as both an optical filter and a conductive counter-electrode of the rear dye-sensitized solar cell. The hybrid conductive distributed Bragg reflectors were designed to be transparent to the long-wavelength part of the incident solar spectrum (λ>500 nm) for the rear solar cell, while reflecting the short-wavelength photons (λ<500 nm) which can then be absorbed by the front photoelectrochemical electrode for enhanced photocurrent generation. PMID:27324578

Plasmonic enhancement in BiVO4 photonic crystals for efficient water splitting.

PubMed

Zhang, Liwu; Lin, Chia-Yu; Valev, Ventsislav K; Reisner, Erwin; Steiner, Ullrich; Baumberg, Jeremy J

2014-10-15

Photo-electrochemical water splitting is a very promising and environmentally friendly route for the conversion of solar energy into hydrogen. However, the solar-to-H2 conversion efficiency is still very low due to rapid bulk recombination of charge carriers. Here, a photonic nano-architecture is developed to improve charge carrier generation and separation by manipulating and confining light absorption in a visible-light-active photoanode constructed from BiVO4 photonic crystal and plasmonic nanostructures. Synergistic effects of photonic crystal stop bands and plasmonic absorption are observed to operate in this photonic nanostructure. Within the scaffold of an inverse opal photonic crystal, the surface plasmon resonance is significantly enhanced by the photonic Bragg resonance. Nanophotonic photoanodes show AM 1.5 photocurrent densities of 3.1 ± 0.1 mA cm(-2) at 1.23 V versus RHE, which is among the highest for oxide-based photoanodes and over 4 times higher than the unstructured planar photoanode. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafine Ti4+ doped α-Fe2O3 nanorod array photoanodes with high charge separation efficiency for solar water splitting

NASA Astrophysics Data System (ADS)

Liu, Yilin; Liu, Jie; Luo, Wenjun; Wen, Xin; Liu, Xiaokang; Zou, Zhigang; Huang, Wei

2017-06-01

Hematite (α-Fe2O3) is a promising photoanode material for solar water splitting due to its suitable band gap, earth-abundance, excellent stability and non-toxicity. However, a short hole diffusion length limits its performance. A nanorod array structure can shorten hole transfer distance to photoelectrode/electrolyte interface and decrease recombination of photo-generated carriers. However, average diameters of all previously reported nanorods are over 50 nm, thus being too thick for holes to transfer to the interface. It is still a big challenge to prepare a Fe2O3 nanorod array photoelectrode with finer diameter. In this study, we prepare an ultrafine α-Fe2O3 nanorod array film with average diameter about 25 nm by calcining γ-FeOOH for the first time. The ultrafine nanorod array photoanode indicates much higher carrier separation efficiency and performance than a conventional nanorod array film.

Focusing the view on nature's water-splitting catalyst.

PubMed

Zein, Samir; Kulik, Leonid V; Yano, Junko; Kern, Jan; Pushkar, Yulia; Zouni, Athina; Yachandra, Vittal K; Lubitz, Wolfgang; Neese, Frank; Messinger, Johannes

2008-03-27

Nature invented a catalyst about 3Gyr ago, which splits water with high efficiency into molecular oxygen and hydrogen equivalents (protons and electrons). This reaction is energetically driven by sunlight and the active centre contains relatively cheap and abundant metals: manganese and calcium. This biological system therefore forms the paradigm for all man-made attempts for direct solar fuel production, and several studies are underway to determine the electronic and geometric structures of this catalyst. In this report we briefly summarize the problems and the current status of these efforts and propose a density functional theory-based strategy for obtaining a reliable high-resolution structure of this unique catalyst that includes both the inorganic core and the first ligand sphere.

Solar-to-Chemical Energy Conversion with Photoelectrochemical Tandem Cells.

PubMed

Sivula, Kevin

2013-01-01

Efficiently and inexpensively converting solar energy into chemical fuels is an important goal towards a sustainable energy economy. An integrated tandem cell approach could reasonably convert over 20% of the sun's energy directly into chemical fuels like H2 via water splitting. Many different systems have been investigated using various combinations of photovoltaic cells and photoelectrodes, but in order to be economically competitive with the production of H2 from fossil fuels, a practical water splitting tandem cell must optimize cost, longevity and performance. In this short review, the practical aspects of solar fuel production are considered from the perspective of a semiconductor-based tandem cell and the latest advances with a very promising technology - metal oxide photoelectrochemical tandem cells - are presented.

Focusing the view on nature's water-splitting catalyst

PubMed Central

Zein, Samir; Kulik, Leonid V; Yano, Junko; Kern, Jan; Pushkar, Yulia; Zouni, Athina; Yachandra, Vittal K; Lubitz, Wolfgang; Neese, Frank; Messinger, Johannes

2007-01-01

Nature invented a catalyst about 3 Gyr ago, which splits water with high efficiency into molecular oxygen and hydrogen equivalents (protons and electrons). This reaction is energetically driven by sunlight and the active centre contains relatively cheap and abundant metals: manganese and calcium. This biological system therefore forms the paradigm for all man-made attempts for direct solar fuel production, and several studies are underway to determine the electronic and geometric structures of this catalyst. In this report we briefly summarize the problems and the current status of these efforts and propose a density functional theory-based strategy for obtaining a reliable high-resolution structure of this unique catalyst that includes both the inorganic core and the first ligand sphere. PMID:17989003

Silicon Nitride for Direct Water-Splitting and Corrosion Mitigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Head, J.; Turner, J.A.

2006-01-01

Todays fossil fuels are becoming harder to obtain, creating pollution problems, and posing hazards to people’s health. One alternative to fossil fuels is hydrogen, capable of serving as a clean and efficient energy carrier. Certain semiconductors are able to harness the energy of photons and direct it into water electrolysis in a process known as photoelectrochemical water splitting. Triple junction devices integrate three semiconductors of different band gaps resulting in a monolithic material that absorbs over a broader spectrum. Amorphous silicon (a-Si) is one such material that, when stacked in tandem, possesses water-splitting capabilities. Even though a-Si is capable ofmore » splitting water, it is an unstable material in solution and therefore requires a coating to protect the surface from corrosion. A stable, transparent material that has the potential for corrosion protection is silicon nitride. In this study, silicon nitride thin films were grown using DC magnetron sputtering with varying amounts of argon and nitrogen added to the system. X-ray diffraction indicated amorphous silicon nitride films. Current as a function of potential was determined from cyclic voltammetry measurements. Mott-Schottky analysis showed n-type behavior with absorption and transmission measurements indicated variation in flatband potentials. Variation in band gap values ranging from 1.90 to 4.0 eV. Corrosion measurements reveal that the silicon nitride samples exhibit both p-type and n-type behavior. Photocurrent over a range of potentials was greater in samples that were submerged in acidic electrolyte. Silicon nitride shows good stability in acidic, neutral, and basic solutions, indicative of a good material for corrosion mitigation.« less

Recent Progress in Metal‐Organic Frameworks for Applications in Electrocatalytic and Photocatalytic Water Splitting

PubMed Central

Wang, Wei; Xu, Xiaomin; Zhou, Wei

2017-01-01

The development of clean and renewable energy materials as alternatives to fossil fuels is foreseen as a potential solution to the crucial problems of environmental pollution and energy shortages. Hydrogen is an ideal energy material for the future, and water splitting using solar/electrical energy is one way to generate hydrogen. Metal‐organic frameworks (MOFs) are a class of porous materials with unique properties that have received rapidly growing attention in recent years for applications in water splitting due to their remarkable design flexibility, ultra‐large surface‐to‐volume ratios and tunable pore channels. This review focuses on recent progress in the application of MOFs in electrocatalytic and photocatalytic water splitting for hydrogen generation, including both oxygen and hydrogen evolution. It starts with the fundamentals of electrocatalytic and photocatalytic water splitting and the related factors to determine the catalytic activity. The recent progress in the exploitation of MOFs for water splitting is then summarized, and strategies for designing MOF‐based catalysts for electrocatalytic and photocatalytic water splitting are presented. Finally, major challenges in the field of water splitting are highlighted, and some perspectives of MOF‐based catalysts for water splitting are proposed. PMID:28435777

Fast, accurate photon beam accelerator modeling using BEAMnrc: A systematic investigation of efficiency enhancing methods and cross-section data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fragoso, Margarida; Kawrakow, Iwan; Faddegon, Bruce A.

In this work, an investigation of efficiency enhancing methods and cross-section data in the BEAMnrc Monte Carlo (MC) code system is presented. Additionally, BEAMnrc was compared with VMC++, another special-purpose MC code system that has recently been enhanced for the simulation of the entire treatment head. BEAMnrc and VMC++ were used to simulate a 6 MV photon beam from a Siemens Primus linear accelerator (linac) and phase space (PHSP) files were generated at 100 cm source-to-surface distance for the 10x10 and 40x40 cm{sup 2} field sizes. The BEAMnrc parameters/techniques under investigation were grouped by (i) photon and bremsstrahlung cross sections,more » (ii) approximate efficiency improving techniques (AEITs), (iii) variance reduction techniques (VRTs), and (iv) a VRT (bremsstrahlung photon splitting) in combination with an AEIT (charged particle range rejection). The BEAMnrc PHSP file obtained without the efficiency enhancing techniques under study or, when not possible, with their default values (e.g., EXACT algorithm for the boundary crossing algorithm) and with the default cross-section data (PEGS4 and Bethe-Heitler) was used as the ''base line'' for accuracy verification of the PHSP files generated from the different groups described previously. Subsequently, a selection of the PHSP files was used as input for DOSXYZnrc-based water phantom dose calculations, which were verified against measurements. The performance of the different VRTs and AEITs available in BEAMnrc and of VMC++ was specified by the relative efficiency, i.e., by the efficiency of the MC simulation relative to that of the BEAMnrc base-line calculation. The highest relative efficiencies were {approx}935 ({approx}111 min on a single 2.6 GHz processor) and {approx}200 ({approx}45 min on a single processor) for the 10x10 field size with 50 million histories and 40x40 cm{sup 2} field size with 100 million histories, respectively, using the VRT directional bremsstrahlung splitting (DBS) with no electron splitting. When DBS was used with electron splitting and combined with augmented charged particle range rejection, a technique recently introduced in BEAMnrc, relative efficiencies were {approx}420 ({approx}253 min on a single processor) and {approx}175 ({approx}58 min on a single processor) for the 10x10 and 40x40 cm{sup 2} field sizes, respectively. Calculations of the Siemens Primus treatment head with VMC++ produced relative efficiencies of {approx}1400 ({approx}6 min on a single processor) and {approx}60 ({approx}4 min on a single processor) for the 10x10 and 40x40 cm{sup 2} field sizes, respectively. BEAMnrc PHSP calculations with DBS alone or DBS in combination with charged particle range rejection were more efficient than the other efficiency enhancing techniques used. Using VMC++, accurate simulations of the entire linac treatment head were performed within minutes on a single processor. Noteworthy differences ({+-}1%-3%) in the mean energy, planar fluence, and angular and spectral distributions were observed with the NIST bremsstrahlung cross sections compared with those of Bethe-Heitler (BEAMnrc default bremsstrahlung cross section). However, MC calculated dose distributions in water phantoms (using combinations of VRTs/AEITs and cross-section data) agreed within 2% of measurements. Furthermore, MC calculated dose distributions in a simulated water/air/water phantom, using NIST cross sections, were within 2% agreement with the BEAMnrc Bethe-Heitler default case.« less

Materials and systems for unassisted photoelectrochemical solar fuels production (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lee, Jae Sung

2016-10-01

About 400 semiconductor solids are known to have photocatalytic activity for water splitting. Yet there is no single material that could satisfy all the requirements for desired photocatalysts: i) suitable band gap energy (1.7 eV< Eg < 2.3 eV) for high efficiency, ii) proper band position for reduction and/or oxidation of water, iii) long-term stability in aqueous solutions, iv) low cost, v) high crystallinity, and vi) high conductivity. Hence, in the selection of photocatalytic materials, we better start from intrinsically stable materials made of earth-abundant elements. The band bap energy is also the primary consideration to absorb ample amount of solar energy of wide wavelength spectrum. It sets the limit of theoretically maximum efficiency and it could also be extended by band engineering techniques. Upon selection of the candidate materials, we can also modify the materials for full utilization their potentials. The main path of efficiency loss in PEC water splitting process is recombination of photoelectrons and holes. We discuss the material designs including i) p-n heterojunction photoanodes for effective electron-hole separation, ii) electron highway to facilitate interparticle electron transfer, iii) metal or anion doping to improve conductivity of the semiconductor and to extend the range of light absorption, iv) one-dimensional nanomaterials to secure a short hole diffusion distance and vectoral electron transfer, and v) loading co-catalysts for facile charge separation. High efficiency has been demonstrated for all these examples due to efficient electron-hole separation. Finally, total systems for unassisted solar fuel production are demonstrated.

Semiconductor nanostructures for artificial photosynthesis

NASA Astrophysics Data System (ADS)

Yang, Peidong

2012-02-01

Nanowires, with their unique capability to bridge the nanoscopic and macroscopic worlds, have already been demonstrated as important materials for different energy conversion. One emerging and exciting direction is their application for solar to fuel conversion. The generation of fuels by the direct conversion of solar energy in a fully integrated system is an attractive goal, but no such system has been demonstrated that shows the required efficiency, is sufficiently durable, or can be manufactured at reasonable cost. One of the most critical issues in solar water splitting is the development of a suitable photoanode with high efficiency and long-term durability in an aqueous environment. Semiconductor nanowires represent an important class of nanostructure building block for direct solar-to-fuel application because of their high surface area, tunable bandgap and efficient charge transport and collection. Nanowires can be readily designed and synthesized to deterministically incorporate heterojunctions with improved light absorption, charge separation and vectorial transport. Meanwhile, it is also possible to selectively decorate different oxidation or reduction catalysts onto specific segments of the nanowires to mimic the compartmentalized reactions in natural photosynthesis. In this talk, I will highlight several recent examples in this lab using semiconductor nanowires and their heterostructures for the purpose of direct solar water splitting.

The Efficiency of Split Panel Designs in an Analysis of Variance Model

PubMed Central

Wang, Wei-Guo; Liu, Hai-Jun

2016-01-01

We consider split panel design efficiency in analysis of variance models, that is, the determination of the cross-sections series optimal proportion in all samples, to minimize parametric best linear unbiased estimators of linear combination variances. An orthogonal matrix is constructed to obtain manageable expression of variances. On this basis, we derive a theorem for analyzing split panel design efficiency irrespective of interest and budget parameters. Additionally, relative estimator efficiency based on the split panel to an estimator based on a pure panel or a pure cross-section is present. The analysis shows that the gains from split panel can be quite substantial. We further consider the efficiency of split panel design, given a budget, and transform it to a constrained nonlinear integer programming. Specifically, an efficient algorithm is designed to solve the constrained nonlinear integer programming. Moreover, we combine one at time designs and factorial designs to illustrate the algorithm’s efficiency with an empirical example concerning monthly consumer expenditure on food in 1985, in the Netherlands, and the efficient ranges of the algorithm parameters are given to ensure a good solution. PMID:27163447

76 FR 72872 - Rule Concerning Disclosures Regarding Energy Consumption and Water Use of Certain Home Appliances...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-28

... standards impose regional efficiency standards for split air conditioners, package air conditioners, and gas.... Specifically, DOE will require nonweatherized gas furnaces to comply by May 1, 2013; and weatherized gas... Dakota, Ohio, Oregon, Pennsylvania, Rhode Island, South Dakota, Utah, Vermont, Washington, West Virginia...

BiVO4/WO3/SnO2 Double-Heterojunction Photoanode with Enhanced Charge Separation and Visible-Transparency for Bias-Free Solar Water-Splitting with a Perovskite Solar Cell.

PubMed

Baek, Ji Hyun; Kim, Byeong Jo; Han, Gill Sang; Hwang, Sung Won; Kim, Dong Rip; Cho, In Sun; Jung, Hyun Suk

2017-01-18

Coupling dissimilar oxides in heterostructures allows the engineering of interfacial, optical, charge separation/transport and transfer properties of photoanodes for photoelectrochemical (PEC) water splitting. Here, we demonstrate a double-heterojunction concept based on a BiVO 4 /WO 3 /SnO 2 triple-layer planar heterojunction (TPH) photoanode, which shows simultaneous improvements in the charge transport (∼93% at 1.23 V vs RHE) and transmittance at longer wavelengths (>500 nm). The TPH photoanode was prepared by a facile solution method: a porous SnO 2 film was first deposited on a fluorine-doped tin oxide (FTO)/glass substrate followed by WO 3 deposition, leading to the formation of a double layer of dense WO 3 and a WO 3 /SnO 2 mixture at the bottom. Subsequently, a BiVO 4 nanoparticle film was deposited by spin coating. Importantly, the WO 3 /(WO 3 +SnO 2 ) composite bottom layer forms a disordered heterojunction, enabling intimate contact, lower interfacial resistance, and efficient charge transport/transfer. In addition, the top BiVO 4 /WO 3 heterojunction layer improves light absorption and charge separation. The resultant TPH photoanode shows greatly improved internal quantum efficiency (∼80%) and PEC water oxidation performance (∼3.1 mA/cm 2 at 1.23 V vs RHE) compared to the previously reported BiVO 4 /WO 3 photoanodes. The PEC performance was further improved by a reactive-ion etching treatment and CoO x electrocatalyst deposition. Finally, we demonstrated a bias-free and stable solar water-splitting by constructing a tandem PEC device with a perovskite solar cell (STH ∼3.5%).

Electronic and Morphological Dual Modulation of Cobalt Carbonate Hydroxides by Mn Doping toward Highly Efficient and Stable Bifunctional Electrocatalysts for Overall Water Splitting.

PubMed

Tang, Tang; Jiang, Wen-Jie; Niu, Shuai; Liu, Ning; Luo, Hao; Chen, Yu-Yun; Jin, Shi-Feng; Gao, Feng; Wan, Li-Jun; Hu, Jin-Song

2017-06-21

Developing bifunctional efficient and durable non-noble electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is highly desirable and challenging for overall water splitting. Herein, Co-Mn carbonate hydroxide (CoMnCH) nanosheet arrays with controllable morphology and composition were developed on nickel foam (NF) as such a bifunctional electrocatalyst. It is discovered that Mn doping in CoCH can simultaneously modulate the nanosheet morphology to significantly increase the electrochemical active surface area for exposing more accessible active sites and tune the electronic structure of Co center to effectively boost its intrinsic activity. As a result, the optimized Co 1 Mn 1 CH/NF electrode exhibits unprecedented OER activity with an ultralow overpotential of 294 mV at 30 mA cm -2 , compared with all reported metal carbonate hydroxides. Benefited from 3D open nanosheet array topographic structure with tight contact between nanosheets and NF, it is able to deliver a high and stable current density of 1000 mA cm -2 at only an overpotential of 462 mV with no interference from high-flux oxygen evolution. Despite no reports about effective HER on metal carbonate hydroxides yet, the small overpotential of 180 mV at 10 mA cm -2 for HER can be also achieved on Co 1 Mn 1 CH/NF by the dual modulation of Mn doping. This offers a two-electrode electrolyzer using bifunctional Co 1 Mn 1 CH/NF as both anode and cathode to perform stable overall water splitting with a cell voltage of only 1.68 V at 10 mA cm -2 . These findings may open up opportunities to explore other multimetal carbonate hydroxides as practical bifunctional electrocatalysts for scale-up water electrolysis.

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE PAGES

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.; ...

2016-12-12

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Oriented epitaxial TiO2 nanowires for water splitting

NASA Astrophysics Data System (ADS)

Hou, Wenting; Cortez, Pablo; Wuhrer, Richard; Macartney, Sam; Bozhilov, Krassimir N.; Liu, Rong; Sheppard, Leigh R.; Kisailus, David

2017-06-01

Highly oriented epitaxial rutile titanium dioxide (TiO2) nanowire arrays have been hydrothermally grown on polycrystalline TiO2 templates with their orientation dependent on the underlying TiO2 grain. Both the diameter and areal density of the nanowires were tuned by controlling the precursor concentration, and the template surface energy and roughness. Nanowire tip sharpness was influenced by precursor solubility and diffusivity. A new secondary ion mass spectrometer technique has been developed to install additional nucleation sites in single crystal TiO2 templates and the effect on nanowire growth was probed. Using the acquired TiO2 nanowire synthesis knowhow, an assortment of nanowire arrays were installed upon the surface of undoped TiO2 photo-electrodes and assessed for their photo-electrochemical water splitting performance. The key result obtained was that the presence of short and dispersed nanowire arrays significantly improved the photocurrent when the illumination intensity was increased from 100 to 200 mW cm-2. This is attributed to the alignment of the homoepitaxially grown nanowires to the [001] direction, which provides the fastest charge transport in TiO2 and an improved pathway for photo-holes to find water molecules and undertake oxidation. This result lays a foundation for achieving efficient water splitting under conditions of concentrated solar illumination.

Plasmon enhanced water splitting mediated by hybrid bimetallic Au-Ag core-shell nanostructures.

PubMed

Erwin, William R; Coppola, Andrew; Zarick, Holly F; Arora, Poorva; Miller, Kevin J; Bardhan, Rizia

2014-11-07

In this work, we employed wet chemically synthesized bimetallic Au-Ag core-shell nanostructures (Au-AgNSs) to enhance the photocurrent density of mesoporous TiO2 for water splitting and we compared the results with monometallic Au nanoparticles (AuNPs). While Au-AgNSs incorporated photoanodes give rise to 14× enhancement in incident photon to charge carrier efficiency, AuNPs embedded photoanodes result in 6× enhancement. By varying nanoparticle concentration in the photoanodes, we observed ∼245× less Au-AgNSs are required relative to AuNPs to generate similar photocurrent enhancement for solar fuel conversion. Power-dependent measurements of Au-AgNSs and AuNPs showed a first order dependence to incident light intensity, relative to half-order dependence for TiO2 only photoanodes. This indicated that plasmonic nanostructures enhance charge carriers formed on the surface of the TiO2 which effectively participate in photochemical reactions. Our experiments and simulations suggest the enhanced near-field, far-field, and multipolar resonances of Au-AgNSs facilitating broadband absorption of solar radiation collectively gives rise to their superior performance in water splitting.

A new preparation of a bifunctional crystalline heterogeneous copper electrocatalyst by electrodeposition using a Robson-type macrocyclic dinuclear copper complex for efficient hydrogen and oxygen evolution from water.

PubMed

Majumder, Samit; Abdel Haleem, Ashraf; Nagaraju, Perumandla; Naruta, Yoshinori

2017-07-18

The development of low-cost, stable bifunctional electrocatalysts, which operate in the same electrolyte with a low overpotential for water splitting, including the oxygen evolution reaction and the hydrogen evolution reaction, remains an attractive prospect and a great challenge. In this study, a water soluble Robson-type macrocyclic dicopper(ii) complex has been used for the first time as a catalyst precursor for the generation of a copper-based bifunctional heterogeneous catalyst film, which can be used for both HER and OER at a near neutral pH. In sodium borate buffer at pH 9.20, this complex decomposed to give a Cu(OH) 2 /Cu 2 O-based thin film on FTO that catalyzes both hydrogen production and water oxidation. The morphology, nature and composition of the thin film were fully characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron, and energy dispersive X-ray spectroscopies. The catalyst film showed high stability during the course of electrolysis in either the cathodic or the anodic direction for more than 4 h. Faradaic efficiencies of ∼92% for HER and ∼96% for OER were achieved. The switch between the two half-reactions of catalytic water splitting was fully reversible in nature.

Studies of thermochemical water-splitting cycles

NASA Technical Reports Server (NTRS)

Remick, R. J.; Foh, S. E.

1980-01-01

Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

Electrochemically hydrogenated TiO2 nanotubes with improved photoelectrochemical water splitting performance

PubMed Central

2013-01-01

One-dimensional anodic titanium oxide (ATO) nanotube arrays hold great potential as photoanode for photoelectrochemical (PEC) water splitting. In this work, we report a facile and eco-friendly electrochemical hydrogenation method to modify the electronic and PEC properties of ATO nanotube films. The hydrogenated ATO (ATO-H) electrodes present a significantly improved photocurrent of 0.65 mA/cm2 in comparison with that of pristine ATO nanotubes (0.29 mA/cm2) recorded under air mass 1.5 global illumination. The incident photon-to-current efficiency measurement suggests that the enhanced photocurrent of ATO-H nanotubes is mainly ascribed to the improved photoactivity in the UV region. We propose that the electrochemical hydrogenation induced surface oxygen vacancies contribute to the substantially enhanced electrical conductivity and photoactivity. PMID:24047205

Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanwald, Kai E.; Berto, Tobias F.; Jentys, Andreas

Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents formore » H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for SEM and AAS measurements and Dr. Udishnu Sanyal for TEM imaging. Christine Schwarz is acknowledged for technical assistance in NMR experiments.« less

Cu2O Photocathode for Low Bias Photoelectrochemical Water Splitting Enabled by NiFe-Layered Double Hydroxide Co-Catalyst

PubMed Central

Qi, Huan; Wolfe, Jonathan; Fichou, Denis; Chen, Zhong

2016-01-01

Layered double hydroxides (LDHs) are bimetallic hydroxides that currently attract considerable attention as co-catalysts in photoelectrochemical (PEC) systems in view of water splitting under solar light. A wide spectrum of LDHs can be easily prepared on demand by tuning their chemical composition and structural morphology. We describe here the electrochemical growth of NiFe-LDH overlayers on Cu2O electrodes and study their PEC behavior. By using the modified Cu2O/NiFe-LDH electrodes we observe a remarkable seven-fold increase of the photocurrent intensity under an applied voltage as low as −0.2 V vs Ag/AgCl. The origin of such a pronounced effect is the improved electron transfer towards the electrolyte brought by the NiFe-LDH overlayer due to an appropriate energy level alignment. Long-term photostability tests reveal that Cu2O/NiFe-LDH photocathodes show no photocurrent loss after 40 hours of operation under light at −0.2 V vs Ag/AgCl low bias condition. These improved performances make Cu2O/NiFe-LDH a suitable photocathode material for low voltage H2 production. Indeed, after 8 hours of H2 production under −0.2 V vs Ag/AgCl the PEC cell delivers a 78% faradaic efficiency. This unprecedented use of Cu2O/NiFe-LDH as an efficient photocathode opens new perspectives in view of low biasd or self-biased PEC water splitting under sunlight illumination. PMID:27487918

Earth-Abundant Oxygen Evolution Catalysts Coupled onto ZnO Nanowire Arrays for Efficient Photoelectrochemical Water Cleavage

PubMed Central

Jiang, Chaoran; Moniz, Savio J A; Khraisheh, Majeda; Tang, Junwang

2014-01-01

ZnO has long been considered as a model UV-driven photoanode for photoelectrochemical water splitting, but its performance has been limited by fast charge-carrier recombination, extremely poor stability in aqueous solution, and slow kinetics of water oxidation. These issues were addressed by applying a strategy of optimization and passivation of hydrothermally grown 1D ZnO nanowire arrays. The length and diameter of bare ZnO nanowires were optimized by varying the growth time and precursor concentration to achieve optimal photoelectrochemical performance. The addition of earth-abundant cobalt phosphate (Co-Pi) and nickel borate (Ni-B) oxygen evolution catalysts onto ZnO nanowires resulted in substantial cathodic shifts in onset potential to as low as about 0.3 V versus the reversible hydrogen electrode (RHE) for Ni-B/ZnO, for which a maximum photocurrent density of 1.1 mA cm−2 at 0.9 V (vs. RHE) with applied bias photon-to-current efficiency of 0.4 % and an unprecedented near-unity incident photon-to-current efficiency at 370 nm. In addition the potential required for saturated photocurrent was dramatically reduced from 1.6 to 0.9 V versus RHE. Furthermore, the stability of these ZnO nanowires was significantly enhanced by using Ni-B compared to Co-Pi due to its superior chemical robustness, and it thus has additional functionality as a stable protecting layer on the ZnO surface. These remarkable enhancements in both photocatalytic activity and stability directly address the current severe limitations in the use of ZnO-based photoelectrodes for water-splitting applications, and can be applied to other photoanodes for efficient solar-driven fuel synthesis. PMID:25156820

Toward Eco-Friendly and Highly Efficient Solar Water Splitting Using In2S3/Anatase/Rutile TiO2 Dual-Staggered-Heterojunction Nanodendrite Array Photoanode.

PubMed

Yang, Jih-Sheng; Wu, Jih-Jen

2018-01-31

The TiO 2 -based heterojunction nanodendrite (ND) array composed of anatase nanoparticles (ANPs) on the surface of the rutile ND (RND) array is selected as the model photoanode to demonstrate the strategies toward eco-friendly and efficient solar water splitting using neutral electrolyte and seawater. Compared with the performances in alkaline electrolyte, a non-negligible potential drop across the electrolyte as well as impeded charge injection and charge separation is monitored in the ANP/RND array photoanode with neutral electrolyte, which are, respectively, ascribed to the series resistance of neutral electrolyte, the fundamentally pH-dependent water oxidation mechanism on TiO 2 surface, as well as the less band bending at the interface of TiO 2 and neutral electrolyte. Accordingly, a TiO 2 -based dual-staggered heterojunction ND array photoanode is further designed in this work to overcome the issue of less band bending with the neutral electrolyte. The improvement of charge separation efficiency is realized by the deposition of a transparent In 2 S 3 layer on the ANP/RND array photoanode for constructing additional staggered heterojunction. Under illumination of AM 1.5G (100 mW cm -2 ), the improved photocurrent densities acquired both in neutral electrolyte and seawater at 1.23 V vs reversible hydrogen electrode (RHE), which approach the theoretical value for rutile TiO 2 , are demonstrated in the dual-staggered-heterojunction ND array photoanode. Faradaic efficiencies of ∼95 and ∼32% for solar water oxidation in neutral electrolyte and solar seawater oxidation for 2 h are acquired at 1.23 V vs RHE, respectively.

Spectrum splitting metrics and effect of filter characteristics on photovoltaic system performance.

PubMed

Russo, Juan M; Zhang, Deming; Gordon, Michael; Vorndran, Shelby; Wu, Yuechen; Kostuk, Raymond K

2014-03-10

During the past few years there has been a significant interest in spectrum splitting systems to increase the overall efficiency of photovoltaic solar energy systems. However, methods for comparing the performance of spectrum splitting systems and the effects of optical spectral filter design on system performance are not well developed. This paper addresses these two areas. The system conversion efficiency is examined in detail and the role of optical spectral filters with respect to the efficiency is developed. A new metric termed the Improvement over Best Bandgap is defined which expresses the efficiency gain of the spectrum splitting system with respect to a similar system that contains the highest constituent single bandgap photovoltaic cell. This parameter indicates the benefit of using the more complex spectrum splitting system with respect to a single bandgap photovoltaic system. Metrics are also provided to assess the performance of experimental spectral filters in different spectrum splitting configurations. The paper concludes by using the methodology to evaluate spectrum splitting systems with different filter configurations and indicates the overall efficiency improvement that is possible with ideal and experimental designs.

Electrospun strontium titanata nanofibers incorporated with nickel oxide nanoparticles for improved photocatalytic activities

NASA Astrophysics Data System (ADS)

Alharbi, Abdulaziz; Alarifi, Ibrahim M.; Khan, Waseem S.; Asmatulu, Ramazan

2015-03-01

The inexpensive sources of fossil fuels in the world are limited, and will deplete soon because of the huge demand on the energy and growing economies worldwide. Thus, many research activities have been focused on the non-fossil fuel based energy sources, and this will continue next few decades. Water splitting using photocatalysts is one of the major alternative energy technologies to produce hydrogen directly from water using photon energy of the sun. Numerous solid photocatalysts have been used by researchers for water splitting. In the present study, nickel oxide and strontium titanata were chosen as photocatalysts for water splitting. Poly (vinyl pyrrolidone) (PVP) was incorporated with nickel oxide [Ni2O3] (co-catalyst), while poly (vinyl acetate) (PVAc) was mixed with titanium (IV) isopropoxide [C12H28O4Ti] and strontium nitrate [Sr(NO3)2]. Then, two solutions were electrospun using coaxial electrospinning technique to generate nanoscale fibers incorporated with NiOx nanoparticles. The fibers were then heat treated at elevated temperatures for 2hr in order to transform the strontium titanata and nickel oxide into crystalline form for a better photocatalytic efficiency. The morphology of fibers was characterized via scanning electron microscopy (SEM), while the surface hydrophobicity was determined using water contact angle goniometer. The UV-vis spectrophotometer was also used to determine the band gap energy values of the nanofibers. This study may open up new possibilities to convert water into fuel directly using the novel photocatalysts.

Innovative solar thermochemical water splitting.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hogan, Roy E. Jr.; Siegel, Nathan P.; Evans, Lindsey R.

2008-02-01

Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximitymore » and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.« less

Particulate photocatalysts for overall water splitting

NASA Astrophysics Data System (ADS)

Chen, Shanshan; Takata, Tsuyoshi; Domen, Kazunari

2017-10-01

The conversion of solar energy to chemical energy is a promising way of generating renewable energy. Hydrogen production by means of water splitting over semiconductor photocatalysts is a simple, cost-effective approach to large-scale solar hydrogen synthesis. Since the discovery of the Honda-Fujishima effect, considerable progress has been made in this field, and numerous photocatalytic materials and water-splitting systems have been developed. In this Review, we summarize existing water-splitting systems based on particulate photocatalysts, focusing on the main components: light-harvesting semiconductors and co-catalysts. The essential design principles of the materials employed for overall water-splitting systems based on one-step and two-step photoexcitation are also discussed, concentrating on three elementary processes: photoabsorption, charge transfer and surface catalytic reactions. Finally, we outline challenges and potential advances associated with solar water splitting by particulate photocatalysts for future commercial applications.

Unraveling the hydrodynamics of split root water uptake experiments using CT scanned root architectures and three dimensional flow simulations

PubMed Central

Koebernick, Nicolai; Huber, Katrin; Kerkhofs, Elien; Vanderborght, Jan; Javaux, Mathieu; Vereecken, Harry; Vetterlein, Doris

2015-01-01

Split root experiments have the potential to disentangle water transport in roots and soil, enabling the investigation of the water uptake pattern of a root system. Interpretation of the experimental data assumes that water flow between the split soil compartments does not occur. Another approach to investigate root water uptake is by numerical simulations combining soil and root water flow depending on the parameterization and description of the root system. Our aim is to demonstrate the synergisms that emerge from combining split root experiments with simulations. We show how growing root architectures derived from temporally repeated X-ray CT scanning can be implemented in numerical soil-plant models. Faba beans were grown with and without split layers and exposed to a single drought period during which plant and soil water status were measured. Root architectures were reconstructed from CT scans and used in the model R-SWMS (root-soil water movement and solute transport) to simulate water potentials in soil and roots in 3D as well as water uptake by growing roots in different depths. CT scans revealed that root development was considerably lower with split layers compared to without. This coincided with a reduction of transpiration, stomatal conductance and shoot growth. Simulated predawn water potentials were lower in the presence of split layers. Simulations showed that this was related to an increased resistance to vertical water flow in the soil by the split layers. Comparison between measured and simulated soil water potentials proved that the split layers were not perfectly isolating and that redistribution of water from the lower, wetter compartments to the drier upper compartments took place, thus water losses were not equal to the root water uptake from those compartments. Still, the layers increased the resistance to vertical flow which resulted in lower simulated collar water potentials that led to reduced stomatal conductance and growth. PMID:26074935

CoM(M=Fe,Cu,Ni)-embedded nitrogen-enriched porous carbon framework for efficient oxygen and hydrogen evolution reactions

NASA Astrophysics Data System (ADS)

Feng, Xiaogeng; Bo, Xiangjie; Guo, Liping

2018-06-01

Rational synthesis and development of earth-abundant materials with efficient electrocatalytic activity and stability for water splitting is a critical but challenging step for sustainable energy application. Herein, a family of bimetal (CoFe, CoCu, CoNi) embedded nitrogen-doped carbon frameworks is developed through a facile and simple thermal conversion strategy of metal-doped zeolitic imidazolate frameworks. Thanks to collaborative superiorities of abundant M-N-C species, modulation action of secondary metal, cobalt-based electroactive phases, template effect of MOFs and unique porous structure, bimetal embedded nitrogen-doped carbon frameworks materials manifest good oxygen and hydrogen evolution catalytic activity. Especially, after modulating the species and molar ratio of metal sources, optimal Co0.75Fe0.25 nitrogen-doped carbon framework catalyst just requires a low overpotential of 303 mV to achieve 10 mA cm-2 with a low Tafel slope (39.49 mV dec-1) for oxygen evolution reaction, which even surpasses that of commercial RuO2. In addition, the optimal catalyst can function as an efficient bifunctional electrocatalyst for overall water splitting with satisfying activity and stability. This development offers an attractive direction for the rational design and fabrication of porous carbon materials for electrochemical energy applications.

A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

NASA Technical Reports Server (NTRS)

Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

1980-01-01

The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

Covalent Surface Modification of Gallium Arsenide Photocathodes for Water Splitting in Highly Acidic Electrolyte.

PubMed

Garner, Logan E; Steirer, K Xerxes; Young, James L; Anderson, Nicholas C; Miller, Elisa M; Tinkham, Jonathan S; Deutsch, Todd G; Sellinger, Alan; Turner, John A; Neale, Nathan R

2017-02-22

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2 ) illumination resulting from the covalently bound surface dipole. Though X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the tunneling splitting in a cyclic water trimer

NASA Astrophysics Data System (ADS)

Mandziuk, Margaret

2016-09-01

We propose an alternative explanation of the "bifurcation" splittings observed for the water trimer in the VRT experiments of Saykally's group [Chem. Rev. 103 (2003) 2533]. In our interpretation, the splittings originate from the quantum delocalization of hydrogen bonded protons in the mean field potential between two oxygen neighbors. The pattern and the order of our calculated splittings is in the range of experimentally observed values. Consequently, quantum delocalization of protons should be considered seriously as the origin of experimentally observed fine splittings. The presented model can be extended to a water pentamer and, hopefully, advance our understanding of liquid water.

Band engineered epitaxial 3D GaN-InGaN core-shell rod arrays as an advanced photoanode for visible-light-driven water splitting.

PubMed

Caccamo, Lorenzo; Hartmann, Jana; Fàbrega, Cristian; Estradé, Sonia; Lilienkamp, Gerhard; Prades, Joan Daniel; Hoffmann, Martin W G; Ledig, Johannes; Wagner, Alexander; Wang, Xue; Lopez-Conesa, Lluis; Peiró, Francesca; Rebled, José Manuel; Wehmann, Hergo-Heinrich; Daum, Winfried; Shen, Hao; Waag, Andreas

2014-02-26

3D single-crystalline, well-aligned GaN-InGaN rod arrays are fabricated by selective area growth (SAG) metal-organic vapor phase epitaxy (MOVPE) for visible-light water splitting. Epitaxial InGaN layer grows successfully on 3D GaN rods to minimize defects within the GaN-InGaN heterojunctions. The indium concentration (In ∼ 0.30 ± 0.04) is rather homogeneous in InGaN shells along the radial and longitudinal directions. The growing strategy allows us to tune the band gap of the InGaN layer in order to match the visible absorption with the solar spectrum as well as to align the semiconductor bands close to the water redox potentials to achieve high efficiency. The relation between structure, surface, and photoelectrochemical property of GaN-InGaN is explored by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Auger electron spectroscopy (AES), current-voltage, and open circuit potential (OCP) measurements. The epitaxial GaN-InGaN interface, pseudomorphic InGaN thin films, homogeneous and suitable indium concentration and defined surface orientation are properties demanded for systematic study and efficient photoanodes based on III-nitride heterojunctions.

Composition and Band Gap Tailoring of Crystalline (GaN)1- x(ZnO) x Solid Solution Nanowires for Enhanced Photoelectrochemical Performance.

PubMed

Li, Jing; Liu, Baodan; Wu, Aimin; Yang, Bing; Yang, Wenjin; Liu, Fei; Zhang, Xinglai; An, Vladimir; Jiang, Xin

2018-05-07

Photoelectrochemical water splitting has emerged as an effective artificial photosynthesis technology to generate clean energy of H 2 from sunlight. The core issue in this reaction system is to develop a highly efficient photoanode with a large fraction of solar light absorption and greater active surface area. In this work, we take advantage of energy band engineering to synthesize (GaN) 1- x (ZnO) x solid solution nanowires with ZnO contents ranging from 10.3% to 47.6% and corresponding band gap tailoring from 3.08 to 2.77 eV on the basis of the Au-assisted VLS mechanism. The morphology of nanowires directly grown on the conductive substrate facilitates the charge transfer and simultaneously improves the surface reaction sites. As a result, a photocurrent approximately 10 times larger than that for a conventional powder-based photoanode is obtained, which indicates the potential of (GaN) 1- x (ZnO) x nanowires in the preparation of superior photoanodes for enhanced water splitting. It is anticipated that the water-splitting capability of (GaN) 1- x (ZnO) x nanowire can be further increased through alignment control for enhanced visible light absorption and reduction of charge transfer resistance.

Core-Shell ZIF-8@ZIF-67-Derived CoP Nanoparticle-Embedded N-Doped Carbon Nanotube Hollow Polyhedron for Efficient Overall Water Splitting.

PubMed

Pan, Yuan; Sun, Kaian; Liu, Shoujie; Cao, Xing; Wu, Konglin; Cheong, Weng-Chon; Chen, Zheng; Wang, Yu; Li, Yang; Liu, Yunqi; Wang, Dingsheng; Peng, Qing; Chen, Chen; Li, Yadong

2018-02-21

The construction of highly active and stable non-noble-metal electrocatalysts for hydrogen and oxygen evolution reactions is a major challenge for overall water splitting. Herein, we report a novel hybrid nanostructure with CoP nanoparticles (NPs) embedded in a N-doped carbon nanotube hollow polyhedron (NCNHP) through a pyrolysis-oxidation-phosphidation strategy derived from core-shell ZIF-8@ZIF-67. Benefiting from the synergistic effects between highly active CoP NPs and NCNHP, the CoP/NCNHP hybrid exhibited outstanding bifunctional electrocatalytic performances. When the CoP/NCNHP was employed as both the anode and cathode for overall water splitting, a potential as low as 1.64 V was needed to achieve the current density of 10 mA·cm -2 , and it still exhibited superior activity after continuously working for 36 h with nearly negligible decay in potential. Density functional theory calculations indicated that the electron transfer from NCNHP to CoP could increase the electronic states of the Co d-orbital around the Fermi level, which could increase the binding strength with H and therefore improve the electrocatalytic performance. The strong stability is attributed to high oxidation resistance of the CoP surface protected by the NCNHP.

Silicon/Carbon Nanotube Photocathode for Splitting Water

NASA Technical Reports Server (NTRS)

Amashukeli, Xenia; Manohara, Harish; Greer, Harold F.; Hall, Lee J.; Gray, Harry B.; Subbert, Bryan

2013-01-01

A proof-of-concept device is being developed for hydrogen gas production based on water-splitting redox reactions facilitated by cobalt tetra-aryl porphyrins (Co[TArP]) catalysts stacked on carbon nanotubes (CNTs) that are grown on n-doped silicon substrates. The operational principle of the proposed device is based on conversion of photoelectron energy from sunlight into chemical energy, which at a later point, can be turned into electrical and mechanical power. The proposed device will consist of a degenerately n-doped silicon substrate with Si posts covering the surface of a 4-in. (approximately equal to 10cm) wafer. The substrate will absorb radiation, and electrons will move radially out of Si to CNT. Si posts are designed such that the diameters are small enough to allow considerable numbers of electrons to transport across to the CNT layer. CNTs will be grown on top of Si using conformal catalyst (Fe/Ni) deposition over a thin alumina barrier layer. Both metallic and semiconducting CNT will be used in this investigation, thus allowing for additional charge generation from CNT in the IR region. Si post top surfaces will be masked from catalyst deposition so as to prevent CNT growth on the top surface. A typical unit cell will then consist of a Si post covered with CNT, providing enhanced surface area for the catalyst. The device will then be dipped into a solution of Co[TArP] to enable coating of CNT with Co(P). The Si/CNT/Co [TArP] assembly then will provide electrons for water splitting and hydrogen gas production. A potential of 1.23 V is needed to split water, and near ideal band gap is approximately 1.4 eV. The combination of doped Si/CNT/Co [TArP] will enable this redox reaction to be more efficient.

Insights into highly improved solar-driven photocatalytic oxygen evolution over integrated Ag3PO4/MoS2 heterostructures

NASA Astrophysics Data System (ADS)

Cui, Xingkai; Yang, Xiaofei; Xian, Xiaozhai; Tian, Lin; Tang, Hua; Liu, Qinqin

2018-04-01

Oxygen evolution has been considered as the rate-determining step in photocatalytic water splitting due to its sluggish four-electron half-reaction rate, the development of oxygen-evolving photocatalysts with well-defined morphologies and superior interfacial contact is highly important for achieving high-performance solar water splitting. Herein, we report the fabrication of Ag3PO4/MoS2 nanocomposites and, for the first time, their use in photocatalytic water splitting into oxygen under LED light illumination. Ag3PO4 nanoparticles were found to be anchored evenly on the surface of MoS2 nanosheets, confirming an efficient hybridization of two semiconductor materials. A maximum oxygen-generating rate of 201.6 mol L-1 g-1 h-1 was determined when 200 mg MoS2 nanosheets were incorporated into Ag3PO4 nanoparticles, which is around 5 times higher than that of bulk Ag3PO4. Obvious enhancements in light-harvesting property, as well as electron-hole separation and charge transportation are revealed by the combination of different characterizations. ESR analysis verified that more active oxygen-containing radicals generate over illuminated Ag3PO4/MoS2 composite photocatalysts rather than irradiated Ag3PO4. The improvement in oxygen evolution performance of Ag3PO4/MoS2 composite photocatalysts is ascribed to wide spectra response in the visible-light region, more efficient charge separation and enhanced oxidation capacity in the valence band (VB). This study provides new insights into the design and development of novel composite photocatalytic materials for solar-to-fuel conversion.

Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

NASA Astrophysics Data System (ADS)

Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

2015-11-01

Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of -20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of -0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production.

Interfacial engineering of metal-insulator-semiconductor junctions for efficient and stable photoelectrochemical water oxidation

PubMed Central

Digdaya, Ibadillah A.; Adhyaksa, Gede W. P.; Trześniewski, Bartek J.; Garnett, Erik C.; Smith, Wilson A.

2017-01-01

Solar-assisted water splitting can potentially provide an efficient route for large-scale renewable energy conversion and storage. It is essential for such a system to provide a sufficiently high photocurrent and photovoltage to drive the water oxidation reaction. Here we demonstrate a photoanode that is capable of achieving a high photovoltage by engineering the interfacial energetics of metal–insulator–semiconductor junctions. We evaluate the importance of using two metals to decouple the functionalities for a Schottky contact and a highly efficient catalyst. We also illustrate the improvement of the photovoltage upon incidental oxidation of the metallic surface layer in KOH solution. Additionally, we analyse the role of the thin insulating layer to the pinning and depinning of Fermi level that is responsible to the resulting photovoltage. Finally, we report the advantage of using dual metal overlayers as a simple protection route for highly efficient metal–insulator–semiconductor photoanodes by showing over 200 h of operational stability. PMID:28660883

Promoting Charge Separation and Injection by Optimizing the Interfaces of GaN:ZnO Photoanode for Efficient Solar Water Oxidation.

PubMed

Wang, Zhiliang; Zong, Xu; Gao, Yuying; Han, Jingfeng; Xu, Zhiqiang; Li, Zheng; Ding, Chunmei; Wang, Shengyang; Li, Can

2017-09-13

Photoelectrochemical water splitting provides an attractive way to store solar energy in molecular hydrogen as a kind of sustainable fuel. To achieve high solar conversion efficiency, the most stringent criteria are effective charge separation and injection in electrodes. Herein, efficient photoelectrochemical water oxidation is realized by optimizing charge separation and surface charge transfer of GaN:ZnO photoanode. The charge separation can be greatly improved through modified moisture-assisted nitridation and HCl acid treatment, by which the interfaces in GaN:ZnO solid solution particles are optimized and recombination centers existing at the interfaces are depressed in GaN:ZnO photoanode. Moreover, a multimetal phosphide of NiCoFeP was employed as water oxidation cocatalyst to improve the charge injection at the photoanode/electrolyte interface. Consequently, it significantly decreases the overpotential and brings the photocurrent to a benchmark of 3.9 mA cm -2 at 1.23 V vs RHE and a solar conversion efficiency over 1% was obtained.

Acid and base recovery from brine solution using PVP intermediate-based bipolar membrane through water splitting technology

NASA Astrophysics Data System (ADS)

Venugopal, Krishnaveni; Murugappan, Minnoli; Dharmalingam, Sangeetha

2017-07-01

Potable water has become a scarce resource in many countries. In fact, the world is not running out of water, but rather, the relatively fixed quantity is becoming too contaminated for many applications. Hence, the present work was designed to evaluate the desalination efficiency of resin and glass fiber-reinforced Polysulfone polymer-based monopolar and bipolar (BPM) ion exchange membranes (with polyvinyl pyrrolidone as the intermediate layer) on a real sample brine solution for 8 h duration. The prepared ion exchange membranes (IEMs) were characterized using FTIR, SEM, TGA, water absorption, and contact angle measurements. The BPM efficiency, electrical conductivity, salinity, sodium, and chloride ion concentration were evaluated for both prepared and commercial-based IEM systems. The current efficiency and energy consumption values obtained during BPMED process were found to be 45 % and 0.41 Wh for RPSu-PVP-based IEM system and 38 % and 1.60 Wh for PSDVB-based IEM system, respectively.

Free-standing ternary NiWP film for efficient water oxidation reaction

NASA Astrophysics Data System (ADS)

Yang, Yunpeng; Zhou, Kuo; Ma, Lili; Liang, Yanqin; Yang, Xianjin; Cui, Zhenduo; Zhu, Shengli; Li, Zhaoyang

2018-03-01

High-efficient catalysts for oxygen evolution reaction (OER) is of great concern in improving energy efficiency for water splitting. Here we report a high-performance OER electrocatalyst of nickel-tungsten-phosphorus (NiWP) film prepared by template method. This free-standing ternary electrocatalyst exhibits a remarkable electrocatalytic activity of OER in alkaline medium due to the synergetic effect among these elements and the good electrical conductivity. The reported NiWP composite catalyst has an overpotential of as low as 0.4 V (vs. RHE) at 30 mA cm-2, better than that of the commercial RuO2 catalyst. Moreover, a small charge transfer resistance of 4.06 Ω and a Tafel slope of 68 mV dec-1 demonstrate the outstanding catalytic activity.

Water Splitting Using Porous Silicon Photo-electrodes for Hydrogen Production

NASA Astrophysics Data System (ADS)

Ali, M.; Starkov, V. V.; Gosteva, E. A.; Druzhinin, A. V.; Sattar, S.

2017-11-01

This paper presents the efficiency study results of using gradient-porous silicon structures with different morphology, as photo-anodes for photo-electrochemical dissociation of water. The results of a study of the physicochemical properties of gradient-porous silicon structures show the relatively low cost and simplicity of the technological process, as well as the possibility of forming structures with predefined properties, allow the creation of effective devices for artificial photosynthesis based on porous silicon for subsequent use in hydrogen energy.

Surface engineering of graphitic carbon nitride polymers with cocatalysts for photocatalytic overall water splitting

PubMed Central

Zhang, Guigang; Lan, Zhi-An

2017-01-01

Graphitic carbon nitride based polymers, being metal-free, accessible, environmentally benign and sustainable, have been widely investigated for artificial photosynthesis in recent years for the photocatalytic splitting of water to produce hydrogen fuel. However, the photocatalytic stoichiometric splitting of pure water into H2 and O2 with a molecular ratio of 2 : 1 is far from easy, and is usually hindered by the huge activation energy barrier and sluggish surface redox reaction kinetics. Herein, we provide a concise overview of cocatalyst modified graphitic carbon nitride based photocatalysts, with our main focus on the modulation of the water splitting redox reaction kinetics. We believe that a timely and concise review on this promising but challenging research topic will certainly be beneficial for general readers and researchers in order to better understand the property–activity relationship towards overall water splitting, which could also trigger the development of new organic architectures for photocatalytic overall water splitting through the rational control of surface chemistry. PMID:28959425

Atomic-Scale Origin of Long-Term Stability and High Performance of p-GaN Nanowire Arrays for Photocatalytic Overall Pure Water Splitting.

PubMed

Kibria, Md Golam; Qiao, Ruimin; Yang, Wanli; Boukahil, Idris; Kong, Xianghua; Chowdhury, Faqrul Alam; Trudeau, Michel L; Ji, Wei; Guo, Hong; Himpsel, F J; Vayssieres, Lionel; Mi, Zetian

2016-10-01

The atomic-scale origin of the unusually high performance and long-term stability of wurtzite p-GaN oriented nanowire arrays is revealed. Nitrogen termination of both the polar (0001¯) top face and the nonpolar (101¯0) side faces of the nanowires is essential for long-term stability and high efficiency. Such a distinct atomic configuration ensures not only stability against (photo) oxidation in air and in water/electrolyte but, as importantly, also provides the necessary overall reverse crystal polarization needed for efficient hole extraction in p-GaN. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Band structure engineering of semiconductors for enhanced photoelectrochemical water splitting: The case of TiO2

NASA Astrophysics Data System (ADS)

Yin, Wan-Jian; Tang, Houwen; Wei, Su-Huai; Al-Jassim, Mowafak M.; Turner, John; Yan, Yanfa

2010-07-01

Here, we propose general strategies for the rational design of semiconductors to simultaneously meet all of the requirements for a high-efficiency, solar-driven photoelectrochemical (PEC) water-splitting device. As a case study, we apply our strategies for engineering the popular semiconductor, anatase TiO2 . Previous attempts to modify known semiconductors such as TiO2 have often focused on a particular individual criterion such as band gap, neglecting the possible detrimental consequence to other important criteria. Density-functional theory calculations reveal that with appropriate donor-acceptor coincorporation alloys with anatase TiO2 hold great potential to satisfy all of the criteria for a viable PEC device. We predict that (Mo, 2N) and (W, 2N) are the best donor-acceptor combinations in the low-alloy concentration regime whereas (Nb, N) and (Ta, N) are the best choice of donor-acceptor pairs in the high-alloy concentration regime.

Possible influence of the Kuramoto length in a photo-catalytic water splitting reaction revealed by Poisson-Nernst-Planck equations involving ionization in a weak electrolyte

NASA Astrophysics Data System (ADS)

Suzuki, Yohichi; Seki, Kazuhiko

2018-03-01

We studied ion concentration profiles and the charge density gradient caused by electrode reactions in weak electrolytes by using the Poisson-Nernst-Planck equations without assuming charge neutrality. In weak electrolytes, only a small fraction of molecules is ionized in bulk. Ion concentration profiles depend on not only ion transport but also the ionization of molecules. We considered the ionization of molecules and ion association in weak electrolytes and obtained analytical expressions for ion densities, electrostatic potential profiles, and ion currents. We found the case that the total ion density gradient was given by the Kuramoto length which characterized the distance over which an ion diffuses before association. The charge density gradient is characterized by the Debye length for 1:1 weak electrolytes. We discuss the role of these length scales for efficient water splitting reactions using photo-electrocatalytic electrodes.

Computational Screening of 2D Materials for Photocatalysis.

PubMed

Singh, Arunima K; Mathew, Kiran; Zhuang, Houlong L; Hennig, Richard G

2015-03-19

Two-dimensional (2D) materials exhibit a range of extraordinary electronic, optical, and mechanical properties different from their bulk counterparts with potential applications for 2D materials emerging in energy storage and conversion technologies. In this Perspective, we summarize the recent developments in the field of solar water splitting using 2D materials and review a computational screening approach to rapidly and efficiently discover more 2D materials that possess properties suitable for solar water splitting. Computational tools based on density-functional theory can predict the intrinsic properties of potential photocatalyst such as their electronic properties, optical absorbance, and solubility in aqueous solutions. Computational tools enable the exploration of possible routes to enhance the photocatalytic activity of 2D materials by use of mechanical strain, bias potential, doping, and pH. We discuss future research directions and needed method developments for the computational design and optimization of 2D materials for photocatalysis.

Nanostructured TaON/Ta3N5 as a highly efficient type-II heterojunction photoanode for photoelectrochemical water splitting.

PubMed

Pei, Lang; Wang, Hongxu; Wang, Xiaohui; Xu, Zhe; Yan, Shicheng; Zou, Zhigang

2018-06-20

Enhancing the charge separation by a semiconductor heterojunction is greatly promising and challenging for photoelectrochemical (PEC) water splitting. Here, we report for the first time the design and fabrication of a TaON/Ta3N5 heterojunction photoanode, in which the electrode Ta3N5 is the primary light absorber and TaON acts as an electron conductor. By combining the merits of the substantial light harvesting of Ta3N5 with the excellent charge transport capability of TaON, the TaON/Ta3N5 heterojunction photoanode, without any co-catalysts, shows a 350 mV negative shift of photocurrent onset potential to 0.65 V versus the reversible hydrogen electrode (RHE) compared to that of the Ta3N5 photoanode. The design and fabrication scheme can be readily extended to other (oxy)nitride semiconductors for heterojunction construction.

Recent Progress in Energy-Driven Water Splitting.

PubMed

Tee, Si Yin; Win, Khin Yin; Teo, Wee Siang; Koh, Leng-Duei; Liu, Shuhua; Teng, Choon Peng; Han, Ming-Yong

2017-05-01

Hydrogen is readily obtained from renewable and non-renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non-renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost-effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic-integrated solar-driven water electrolysis.

Recent Progress in Energy‐Driven Water Splitting

PubMed Central

Tee, Si Yin; Win, Khin Yin; Teo, Wee Siang; Koh, Leng‐Duei; Liu, Shuhua; Teng, Choon Peng

2017-01-01

Hydrogen is readily obtained from renewable and non‐renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non‐renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost‐effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic‐integrated solar‐driven water electrolysis. PMID:28546906

Substituent effects on photosensitized splitting of thymine cyclobutane dimer by an attached indole.

PubMed

Tang, Wenjian; Zhou, Hongmei; Wang, Jing; Pan, Chunxiao; Shi, Jingbo; Song, Qinhua

2012-12-21

In chromophore-containing cyclobutane pyrimidine dimer (CPD) model systems, solvent effects on the splitting efficiency may depend on the length of the linker, the molecular conformation, and the oxidation potential of the donor. To further explore the relationship between chromophore structure and splitting efficiency, we prepared a series of substituted indole-T< >T model compounds 2 a-2 g and measured their splitting quantum yields in various solvents. Two reverse solvent effects were observed: an increase in splitting efficiency in solvents of lower polarity for models 2 a-2 d with an electron-donating group (EDG), and vice versa for models 2 e-2 g with an electron-withdrawing group (EWG). According to the Hammett equation, the negative value of the slope of the Hammett plot indicates that the indole moiety during the T< >T-splitting reaction loses negative charge, and the larger negative value implies that the repair reaction is more sensitive to substituent effects in low-polarity solvents. The EDGs of the models 2 a-2 d can delocalize the charge-separated state, and low-polarity solvents make it more stable, which leads to higher splitting efficiency in low-polarity solvents. Conversely, the EWGs of models 2 e-2 g favor destabilization of the charge-separated state, and high-polarity solvents decrease the destabilization and hence lead to more efficient splitting in high-polarity solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermal growth of two dimensional hierarchical MoS2 nanospheres on one dimensional CdS nanorods for high performance and stable visible photocatalytic H2 evolution

NASA Astrophysics Data System (ADS)

Chava, Rama Krishna; Do, Jeong Yeon; Kang, Misook

2018-03-01

The visible photocatalytic H2 production from water splitting considered as a clean and renewable energy source could solve the problem of greenhouse gas emission from fossil fuels. Despite tremendous efforts, the development of cost effective, highly efficient and more stable visible photocatalysts for splitting of water remains a great challenge. Here, we report the heteronanostructures consisting of hierarchical MoS2 nanospheres grown on 1D CdS nanorods referred to as CdS-MoS2 HNSs as a high performance visible photocatalyst for H2 evolution. The as-synthesized CdS-MoS2 HNSs exhibited ∼11 fold increment of H2 evolution rate when compared to pure CdS nanorods. This remarkable enhanced hydrogen evolution performance can be assigned to the positive synergetic effect from heteronanostructures formed between the CdS and MoS2 components which assist as an electron sink and source for abundant active edge sites and in turn increases the charge separation. This study presents a low-cost visible photocatalyst for solar energy conversion to achieve efficient H2.

BiVO{sub 4} photoanodes for water splitting with high injection efficiency, deposited by reactive magnetron co-sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Haibo; Institute for Solar Fuels, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin; Freudenberg, Norman

2016-04-15

Photoactive bismuth vanadate (BiVO{sub 4}) thin films were deposited by reactive co-magnetron sputtering from metallic Bi and V targets. The effects of the V-to-Bi ratio, molybdenum doping and post-annealing on the crystallographic and photoelectrochemical (PEC) properties of the BiVO{sub 4} films were investigated. Phase-pure monoclinic BiVO{sub 4} films, which are more photoactive than the tetragonal BiVO{sub 4} phase, were obtained under slightly vanadium-rich conditions. After annealing of the Mo-doped BiVO{sub 4} films, the photocurrent increased 2.6 times compared to undoped films. After optimization of the BiVO{sub 4} film thickness, the photocurrent densities (without a catalyst or a blocking layer ormore » a hole scavenger) exceeded 1.2 mA/cm{sup 2} at a potential of 1.23 V{sub RHE} under solar AM1.5 irradiation. The surprisingly high injection efficiency of holes into the electrolyte is attributed to the highly porous film morphology. This co-magnetron sputtering preparation route for photoactive BiVO{sub 4} films opens new possibilities for the fabrication of large-scale devices for water splitting.« less

Highly Enhanced Photoelectrochemical Water Oxidation Efficiency Based on Triadic Quantum Dot/Layered Double Hydroxide/BiVO 4 Photoanodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Yanqun; Wang, Ruirui; Yang, Ye

2016-08-03

The water oxidation half-reaction is considered to be a bottleneck for achieving highly efficient solar-driven water splitting due to its multiproton-coupled four-electron process and sluggish kinetics. Herein, a triadic photoanode consisting of dual-sized CdTe quantum dots (QDs), Co-based layered double hydroxide (LDH) nanosheets, and BiVO4 particles, that is, QD@LDH@BiVO4, was designed. Two sets of consecutive Type-II band alignments were constructed to improve photogenerated electron-hole separation in the triadic structure. The efficient charge separation resulted in a 2-fold enhancement of the photocurrent of the QD@LDH@BiVO4 photoanode. A significantly enhanced oxidation efficiency reaching above 90% in the low bias region (i.e., Emore » < 0.8 V vs RHE) could be critical in determining the overall performance of a complete photoelectrochemical cell. The faradaic efficiency for water oxidation was almost 90%. The conduction band energy of QDs is -1.0 V more negative than that of LDH, favorable for the electron injection to LDH and enabling a more efficient hole separation. The enhanced photon-to-current conversion efficiency and improved water oxidation efficiency of the triadic structure may result from the non-negligible contribution of hot electrons or holes generated in QDs. Such a band-matching and multidimensional triadic architecture could be a promising strategy for achieving high-efficiency photoanodes by sufficiently utilizing and maximizing the functionalities of QDs.« less

First-Principles Study of the Band Diagrams and Schottky-Type Barrier Heights of Aqueous Ta3N5 Interfaces.

PubMed

Watanabe, Eriko; Ushiyama, Hiroshi; Yamashita, Koichi

2017-03-22

The photo(electro)chemical production of hydrogen by water splitting is an efficient and sustainable method for the utilization of solar energy. To improve photo(electro)catalytic activity, a Schottky-type barrier is typically useful to separate excited charge carriers in semiconductor electrodes. Here, we focused on studying the band diagrams and the Schottky-type barrier heights of Ta 3 N 5 , which is one of the most promising materials as a photoanode for water splitting. The band alignments of the undoped and n-type Ta 3 N 5 with adsorbents in a vacuum were examined to determine how impurities and adsorbents affect the band positions and Fermi energies. The band edge positions as well as the density of surface states clearly depended on the density of O N impurities in the bulk and surface regions. Finally, the band diagrams of the n-type Ta 3 N 5 /water interfaces were calculated with an improved interfacial model to include the effect of electrode potential with explicit water molecules. We observed partial Fermi level pinning in our calculations at the Ta 3 N 5 /water interface, which affects the driving force for charge separation.

Some Aspects of PDC Electrolysis

NASA Astrophysics Data System (ADS)

Poláčik, Ján; Pospíšil, Jiří

2016-10-01

In this paper, aspects of pulsed direct current (PDC) water splitting are described. Electrolysis is a simple and well-known method to produce hydrogen. The efficiency is relatively low in normal conditions using conventional DC. PDC in electrolysis brings about many advantages. It increases efficiency of hydrogen production, and performance of the electrolyser may be smoothly controlled without compromising efficiency of the process. In our approach, ultra-short pulses are applied. This method enhances efficiency of electrical energy in the process of decomposition of water into hydrogen and oxygen. Efficiency depends on frequency, shape and width of the electrical pulses. Experiments proved that efficiency was increased by 2 to 8 per cent. One of the prospects of PDC electrolysis producing hydrogen is in increase of efficiency of energy storage efficiency in the hydrogen. There are strong efforts to make the electrical grid more efficient and balanced in terms of production by installing electricity storage units. Using hydrogen as a fuel decreases air pollution and amount of carbon dioxide emissions in the air. In addition to energy storage, hydrogen is also important in transportation and chemical industry.

Efficient photosensitized splitting of the thymine dimer/oxetane unit on its modifying beta-cyclodextrin by a binding electron donor.

PubMed

Tang, Wen-Jian; Song, Qin-Hua; Wang, Hong-Bo; Yu, Jing-Yu; Guo, Qing-Xiang

2006-07-07

Two modified beta-cyclodextrins (beta-CDs) with a thymine dimer and a thymine oxetane adduct respectively, TD-CD and Ox-CD, have been prepared, and utilized to bind an electron-rich chromophore, indole or N,N-dimethylaniline (DMA), to form a supramolecular complex. We have examined the photosensitized splitting of the dimer/oxetane unit in TD-CD/Ox-CD by indole or DMA via an electron-transfer pathway, and observed high splitting efficiencies of the dimer/oxetane unit. On the basis of measurements of fluorescence spectra and splitting quantum yields, it is suggested that the splitting reaction occurs in a supramolecular complex by an inclusion interaction between the modified beta-CDs and DMA or indole. The back electron transfer, which leads low splitting efficiencies for the covalently-linked chromophore-dimer/oxetane compounds, is suppressed in the non-covalently-bound complex, and the mechanism has been discussed.

Porous Structured Ni–Fe–P Nanocubes Derived from a Prussian Blue Analogue as an Electrocatalyst for Efficient Overall Water Splitting

DOE PAGES

Xuan, Cuijuan; Wang, Jie; Xia, Weiwei; ...

2017-07-18

Exploring nonprecious metal electrocatalysts to replace the noble metal-based catalysts for full water electrocatalysis is still an ongoing challenge. In this work, porous structured ternary nickel–iron–phosphide (Ni–Fe–P) nanocubes were synthesized through one-step phosphidation of a Ni–Fe-based Prussian blue analogue. The Ni–Fe–P nanocubes exhibit a rough and loose porous structure on their surface under suitable phosphating temperature, which is favorable for the mass transfer and oxygen diffusion during the electrocatalysis process. As a result, Ni–Fe–P obtained at 350 °C with poorer crystallinity offers more unsaturated atoms as active sites to expedite the absorption of reactants. Additionally, the introduction of nickel improvedmore » the electronic structure and then reduced the charge-transfer resistance, which would result in a faster electron transport and an enhancement of the intrinsic electrocatalytic activities. Benefiting from the unique porous nanocubes and the chemical composition, the Ni–Fe–P nanocubes exhibit excellent hydrogen evolution reaction and oxygen evolution reaction activities in alkaline medium, with low overpotentials of 182 and 271 mV for delivering a current density of 10 mA cm–2, respectively. Moreover, the Ni–Fe–P nanocubes show outstanding stability for sustained water splitting in the two-electrode alkaline electrolyzer. Furthermore, this work not only provides a facile approach for designing bifunctional electrocatalysts but also further extends the application of metal–organic frameworks in overall water splitting.« less

Single-layer ZnMN2 (M = Si, Ge, Sn) zinc nitrides as promising photocatalysts.

PubMed

Bai, Yujie; Luo, Gaixia; Meng, Lijuan; Zhang, Qinfang; Xu, Ning; Zhang, Haiyang; Wu, Xiuqiang; Kong, Fanjie; Wang, Baolin

2018-05-30

Searching for two-dimensional semiconductor materials that are suitable for visible-light photocatalytic water splitting provides a sustainable solution to deal with the future energy crisis and environmental problems. Herein, based on first-principles calculations, single-layer ZnMN2 (M = Si, Ge, Sn) zinc nitrides are proposed as efficient photocatalysts for water splitting. Stability analyses show that the single-layer ZnMN2 zinc nitrides exhibit energetic and dynamical stability. The electronic properties reveal that all of the single-layer ZnMN2 zinc nitrides are semiconductors. Interestingly, single-layer ZnSnN2 is a direct band gap semiconductor with a desirable band gap (1.74 eV), and the optical adsorption spectrum confirms its optical absorption in the visible light region. The hydrogen evolution reaction (HER) calculations show that the catalytic activity for single-layer ZnMN2 (M = Ge, Sn) is better than that of single-layer ZnSiN2. Furthermore, the band gaps and band edge positions for the single-layer ZnMN2 zinc nitrides can be effectively tuned by biaxial strain. Especially, single-layer ZnGeN2 can be effectively tuned to match better with the redox potentials of water and enhance the light absorption in the visible light region at a tensile strain of 5%, which is confirmed by the corresponding optical absorption spectrum. Our results provide guidance for experimental synthesis efforts and future searches for single-layer materials suitable for photocatalytic water splitting.

Porous Structured Ni–Fe–P Nanocubes Derived from a Prussian Blue Analogue as an Electrocatalyst for Efficient Overall Water Splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xuan, Cuijuan; Wang, Jie; Xia, Weiwei

Exploring nonprecious metal electrocatalysts to replace the noble metal-based catalysts for full water electrocatalysis is still an ongoing challenge. In this work, porous structured ternary nickel–iron–phosphide (Ni–Fe–P) nanocubes were synthesized through one-step phosphidation of a Ni–Fe-based Prussian blue analogue. The Ni–Fe–P nanocubes exhibit a rough and loose porous structure on their surface under suitable phosphating temperature, which is favorable for the mass transfer and oxygen diffusion during the electrocatalysis process. As a result, Ni–Fe–P obtained at 350 °C with poorer crystallinity offers more unsaturated atoms as active sites to expedite the absorption of reactants. Additionally, the introduction of nickel improvedmore » the electronic structure and then reduced the charge-transfer resistance, which would result in a faster electron transport and an enhancement of the intrinsic electrocatalytic activities. Benefiting from the unique porous nanocubes and the chemical composition, the Ni–Fe–P nanocubes exhibit excellent hydrogen evolution reaction and oxygen evolution reaction activities in alkaline medium, with low overpotentials of 182 and 271 mV for delivering a current density of 10 mA cm–2, respectively. Moreover, the Ni–Fe–P nanocubes show outstanding stability for sustained water splitting in the two-electrode alkaline electrolyzer. Furthermore, this work not only provides a facile approach for designing bifunctional electrocatalysts but also further extends the application of metal–organic frameworks in overall water splitting.« less

Efficient water reduction with gallium phosphide nanowires

PubMed Central

Standing, Anthony; Assali, Simone; Gao, Lu; Verheijen, Marcel A.; van Dam, Dick; Cui, Yingchao; Notten, Peter H. L.; Haverkort, Jos E. M.; Bakkers, Erik P. A. M.

2015-01-01

Photoelectrochemical hydrogen production from solar energy and water offers a clean and sustainable fuel option for the future. Planar III/V material systems have shown the highest efficiencies, but are expensive. By moving to the nanowire regime the demand on material quantity is reduced, and new materials can be uncovered, such as wurtzite gallium phosphide, featuring a direct bandgap. This is one of the few materials combining large solar light absorption and (close to) ideal band-edge positions for full water splitting. Here we report the photoelectrochemical reduction of water, on a p-type wurtzite gallium phosphide nanowire photocathode. By modifying geometry to reduce electrical resistance and enhance optical absorption, and modifying the surface with a multistep platinum deposition, high current densities and open circuit potentials were achieved. Our results demonstrate the capabilities of this material, even when used in such low quantities, as in nanowires. PMID:26183949

BiVO4 Photoanode with Exposed (040) Facets for Enhanced Photoelectrochemical Performance

NASA Astrophysics Data System (ADS)

Xia, Ligang; Li, Jinhua; Bai, Jing; Li, Linsen; Chen, Shuai; Zhou, Baoxue

2018-03-01

A BiVO4 photoanode with exposed (040) facets was prepared to enhance its photoelectrochemical performance. The exposure of the (040) crystal planes of the BiVO4 film was induced by adding NaCl to the precursor solution. The as-prepared BiVO4 photoanode exhibits higher solar-light absorption and charge-separation efficiency compared to those of an anode prepared without adding NaCl. To our knowledge, the photocurrent density (1.26 mA cm-2 at 1.23 V vs. RHE) of as-prepared BiVO4 photoanode is the highest according to the reports for bare BiVO4 films under simulated AM1.5G solar light, and the incident photon-to-current conversion efficiency is above 35% at 400 nm. The photoelectrochemical (PEC) water-splitting performance was also dramatically improved with a hydrogen evolution rate of 9.11 μmol cm-2 h-1, which is five times compared with the BiVO4 photoanode prepared without NaCl (1.82 μmol cm-2 h-1). Intensity-modulated photocurrent spectroscopy and transient photocurrent measurements show a higher charge-carrier-transfer rate for this photoanode. These results demonstrate a promising approach for the development of high-performance BiVO4 photoanodes which can be used for efficient PEC water splitting and degradation of organic pollutants. [Figure not available: see fulltext.

Corruption of accuracy and efficiency of Markov chain Monte Carlo simulation by inaccurate numerical implementation of conceptual hydrologic models

NASA Astrophysics Data System (ADS)

Schoups, G.; Vrugt, J. A.; Fenicia, F.; van de Giesen, N. C.

2010-10-01

Conceptual rainfall-runoff models have traditionally been applied without paying much attention to numerical errors induced by temporal integration of water balance dynamics. Reliance on first-order, explicit, fixed-step integration methods leads to computationally cheap simulation models that are easy to implement. Computational speed is especially desirable for estimating parameter and predictive uncertainty using Markov chain Monte Carlo (MCMC) methods. Confirming earlier work of Kavetski et al. (2003), we show here that the computational speed of first-order, explicit, fixed-step integration methods comes at a cost: for a case study with a spatially lumped conceptual rainfall-runoff model, it introduces artificial bimodality in the marginal posterior parameter distributions, which is not present in numerically accurate implementations of the same model. The resulting effects on MCMC simulation include (1) inconsistent estimates of posterior parameter and predictive distributions, (2) poor performance and slow convergence of the MCMC algorithm, and (3) unreliable convergence diagnosis using the Gelman-Rubin statistic. We studied several alternative numerical implementations to remedy these problems, including various adaptive-step finite difference schemes and an operator splitting method. Our results show that adaptive-step, second-order methods, based on either explicit finite differencing or operator splitting with analytical integration, provide the best alternative for accurate and efficient MCMC simulation. Fixed-step or adaptive-step implicit methods may also be used for increased accuracy, but they cannot match the efficiency of adaptive-step explicit finite differencing or operator splitting. Of the latter two, explicit finite differencing is more generally applicable and is preferred if the individual hydrologic flux laws cannot be integrated analytically, as the splitting method then loses its advantage.

Mechanisms of mineral membrane fouling growth modulated by pulsed modes of current during electrodialysis: evidences of water splitting implications in the appearance of the amorphous phases of magnesium hydroxide and calcium carbonate.

PubMed

Cifuentes-Araya, Nicolás; Astudillo-Castro, Carolina; Bazinet, Laurent

2014-07-15

Experiments revealed the fouling nature evolutions along different electrodialysis (ED) trials, and how it disappears when current pulsation acts repetitively on the interfaces of ion-exchange membranes (IEMs). Fouling was totally controlled on the diluate side of cation-exchange membrane (CEM) by the repetitive pulsation frequency of the higher on-duty ratios applied. They created steady water splitting proton-barriers that neutralized OH(-) leakage through the membrane, decreasing the interfacial pH, and fouling of the concentrate side. The anion-exchange membrane (AEM) on the diluate side was similarly protected, but it was fouled once water splitting OH(-) generation became either intense enough or excessively weak. Interestingly, amorphous magnesium hydroxide (AMH) stemmed on the CEM-diluate side from brucite under intense water splitting OH(-) generation, and/or strong OH(-) leakage electromigration through the membrane. Water dissociation and overlimiting current regimes triggered drastic water molecule removal from crystal lattices through an accelerated cascade water splitting reaction. Also, amorphous calcium carbonate (ACC) appeared on CEM under intense water splitting reaction, and disappeared once intense OH(-) leakage was allowed by the water splitting proton-barrier dissipation. Our findings have implications for membrane fouling control, as well as for the understanding of the growth behavior of CaCO3 and Mg(OH)2 species on electromembrane interfaces. Copyright © 2014 Elsevier Inc. All rights reserved.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

PubMed

Zhang, Peili; Li, Lin; Nordlund, Dennis; Chen, Hong; Fan, Lizhou; Zhang, Biaobiao; Sheng, Xia; Daniel, Quentin; Sun, Licheng

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2 . The core-shell NiFeCu electrode exhibits pH-dependent oxygen evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.

Todd G. Deutsch | NREL

Science.gov Websites

page. Research Interests Solar energy conversion to hydrogen fuel via PEC water splitting III-V ://orcid.org/0000-0001-6577-1226 Dr. Deutsch has been studying photoelectrochemical (PEC) water splitting since semiconductor water-splitting systems under the joint guidance of Dr. Turner and Prof. Carl A. Koval in the

Photocatalytic hydrogen production of the CdS/TiO2-WO3 ternary hybrid under visible light irradiation.

PubMed

Chen, Yi-Lin; Lo, Shang-Lien; Chang, Hsiang-Ling; Yeh, Hsiao-Mei; Sun, Liping; Oiu, Chunsheng

2016-01-01

An attractive and effective method for converting solar energy into clean and renewable hydrogen energy is photocatalytic water splitting over semiconductors. The study aimed at utilizing organic sacrificial agents in water, modeled by formic acid, in combination with visible light driven photocatalysts to produce hydrogen with high efficiencies. The photocatalytic hydrogen production of cadmium sulfide (CdS)/titanate nanotubes (TNTs) binary hybrid with specific CdS content was investigated. After visible light irradiation for 3 h, the hydrogen production rate of 25 wt% CdS/TNT achieved 179.35 μmol·h(-1). Thanks to the two-step process, CdS/TNTs-WO3 ternary hybrid can better promote the efficiency of water splitting compared with CdS/TNTs binary hybrid. The hydrogen production of 25 wt% CdS/TNTs-WO3 achieved 212.68 μmol·h(-1), under the same condition. Coating of platinum metal onto the WO3 could further promote the reaction. Results showed that 0.2 g 0.1 wt% Pt/WO3 + 0.2 g 25 wt% CdS/TNTs had the best hydrogen production rate of 428.43 μmol·h(-1). The resultant materials were well characterized by high-resolution transmission electron microscope, X-ray diffraction, scanning electron microscopy, and UV-Vis spectra.

Photocatalytic water splitting—The untamed dream: A review of recent advances

DOE PAGES

Jafari, Tahereh; Moharreri, Ehsan; Amin, Alireza Shirazi; ...

2016-07-09

Here, photocatalytic water splitting using sunlight is a promising technology capable of providing high energy yield without pollutant byproducts. Herein, we review various aspects of this technology including chemical reactions, physiochemical conditions and photocatalyst types such as metal oxides, sulfides, nitrides, nanocomposites, and doped materials followed by recent advances in computational modeling of photoactive materials. As the best-known catalyst for photocatalytic hydrogen and oxygen evolution, TiO 2 is discussed in a separate section, along with its challenges such as the wide band gap, large overpotential for hydrogen evolution, and rapid recombination of produced electron-hole pairs. Various approaches are addressed tomore » overcome these shortcomings, such as doping with different elements, heterojunction catalysts, noble metal deposition, and surface modification. Development of a photocatalytic corrosion resistant, visible light absorbing, defect-tuned material with small particle size is the key to complete the sunlight to hydrogen cycle efficiently. Computational studies have opened new avenues to understand and predict the electronic density of states and band structure of advanced materials and could pave the way for the rational design of efficient photocatalysts for water splitting. Future directions are focused on developing innovative junction architectures, novel synthesis methods and optimizing the existing active materials to enhance charge transfer, visible light absorption, reducing the gas evolution overpotential and maintaining chemical and physical stability« less

Comparison of holographic lens and filter systems for lateral spectrum splitting

NASA Astrophysics Data System (ADS)

Vorndran, Shelby; Chrysler, Benjamin; Kostuk, Raymond K.

2016-09-01

Spectrum splitting is an approach to increasing the conversion efficiency of a photovoltaic (PV) system. Several methods can be used to perform this function which requires efficient spatial separation of different spectral bands of the incident solar radiation. In this paper several of holographic methods for implementing spectrum splitting are reviewed along with the benefits and disadvantages associated with each approach. The review indicates that a volume holographic lens has many advantages for spectrum splitting in terms of both power conversion efficiency and energy yield. A specific design for a volume holographic spectrum splitting lens is discussed for use with high bandgap InGaP and low bandgap silicon PV cells. The holographic lenses are modeled using rigorous coupled wave analysis, and the optical efficiency is evaluated using non-sequential raytracing. A proof-of-concept off-axis holographic lens is also recorded in dichromated gelatin film and the spectral diffraction efficiency of the hologram is measured with multiple laser sources across the diffracted spectral band. The experimental volume holographic lens (VHL) characteristics are compared to an ideal spectrum splitting filter in terms of power conversion efficiency and energy yield in environments with high direct normal incidence (DNI) illumination and high levels of diffuse illumination. The results show that the experimental VHL can achieve 62.5% of the ideal filter power conversion efficiency, 64.8% of the ideal filter DNI environment energy yield, and 57.7% of the ideal diffuse environment energy yield performance.

HYBRID SULFUR PROCESS REFERENCE DESIGN AND COST ANALYSIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorensek, M.; Summers, W.; Boltrunis, C.

2009-05-12

This report documents a detailed study to determine the expected efficiency and product costs for producing hydrogen via water-splitting using energy from an advanced nuclear reactor. It was determined that the overall efficiency from nuclear heat to hydrogen is high, and the cost of hydrogen is competitive under a high energy cost scenario. It would require over 40% more nuclear energy to generate an equivalent amount of hydrogen using conventional water-cooled nuclear reactors combined with water electrolysis compared to the proposed plant design described herein. There is a great deal of interest worldwide in reducing dependence on fossil fuels, whilemore » also minimizing the impact of the energy sector on global climate change. One potential opportunity to contribute to this effort is to replace the use of fossil fuels for hydrogen production by the use of water-splitting powered by nuclear energy. Hydrogen production is required for fertilizer (e.g. ammonia) production, oil refining, synfuels production, and other important industrial applications. It is typically produced by reacting natural gas, naphtha or coal with steam, which consumes significant amounts of energy and produces carbon dioxide as a byproduct. In the future, hydrogen could also be used as a transportation fuel, replacing petroleum. New processes are being developed that would permit hydrogen to be produced from water using only heat or a combination of heat and electricity produced by advanced, high temperature nuclear reactors. The U.S. Department of Energy (DOE) is developing these processes under a program known as the Nuclear Hydrogen Initiative (NHI). The Republic of South Africa (RSA) also is interested in developing advanced high temperature nuclear reactors and related chemical processes that could produce hydrogen fuel via water-splitting. This report focuses on the analysis of a nuclear hydrogen production system that combines the Pebble Bed Modular Reactor (PBMR), under development by PBMR (Pty.) Ltd. in the RSA, with the Hybrid Sulfur (HyS) Process, under development by the Savannah River National Laboratory (SRNL) in the US as part of the NHI. This work was performed by SRNL, Westinghouse Electric Company, Shaw, PBMR (Pty) Ltd., and Technology Insights under a Technical Consulting Agreement (TCA). Westinghouse Electric, serving as the lead for the PBMR process heat application team, established a cost-shared TCA with SRNL to prepare an updated HyS thermochemical water-splitting process flowsheet, a nuclear hydrogen plant preconceptual design and a cost estimate, including the cost of hydrogen production. SRNL was funded by DOE under the NHI program, and the Westinghouse team was self-funded. The results of this work are presented in this Final Report. Appendices have been attached to provide a detailed source of information in order to document the work under the TCA contract.« less

Nanosized TiO[subscript 2] for Photocatalytic Water Splitting Studied by Oxygen Sensor and Data Logger

ERIC Educational Resources Information Center

Zhang, Ruinan; Liu, Song; Yuan, Hongyan; Xiao, Dan; Choi, Martin M. F.

2012-01-01

Photocatalytic water splitting by semiconductor photocatalysts has attracted considerable attention in the past few decades. In this experiment, nanosized titanium dioxide (nano-TiO[subscript 2]) particles are used to photocatalytically split water, which is then monitored by an oxygen sensor. Sacrificial reagents such as organics (EDTA) and metal…

Supported black phosphorus nanosheets as hydrogen-evolving photocatalyst achieving 5.4% energy conversion efficiency at 353 K.

PubMed

Tian, Bin; Tian, Bining; Smith, Bethany; Scott, M C; Hua, Ruinian; Lei, Qin; Tian, Yue

2018-04-11

Solar-driven water splitting using powdered catalysts is considered as the most economical means for hydrogen generation. However, four-electron-driven oxidation half-reaction showing slow kinetics, accompanying with insufficient light absorption and rapid carrier combination in photocatalysts leads to low solar-to-hydrogen energy conversion efficiency. Here, we report amorphous cobalt phosphide (Co-P)-supported black phosphorus nanosheets employed as photocatalysts can simultaneously address these issues. The nanosheets exhibit robust hydrogen evolution from pure water (pH = 6.8) without bias and hole scavengers, achieving an apparent quantum efficiency of 42.55% at 430 nm and energy conversion efficiency of over 5.4% at 353 K. This photocatalytic activity is attributed to extremely efficient utilization of solar energy (~75% of solar energy) by black phosphorus nanosheets and high-carrier separation efficiency by amorphous Co-P. The hybrid material design realizes efficient solar-to-chemical energy conversion in suspension, demonstrating the potential of black phosphorus-based materials as catalysts for solar hydrogen production.

Principles and implementations of electrolysis systems for water splitting

DOE PAGES

Xiang, Chengxiang; Papadantonakis, Kimberly M.; Lewis, Nathan S.

2016-02-12

Efforts to develop renewable sources of carbon-neutral fuels have brought a renewed focus to research and development of sunlight-driven water-splitting systems. Electrolysis of water to produce H 2 and O 2 gases is the foundation of such systems, is conceptually and practically simple, and has been practiced both in the laboratory and industrially for many decades. In this Focus article, the fundamentals of water splitting and practices which distinguish commercial water-electrolysis systems from simple laboratory-scale demonstrations are described.

Blending Cr 2O 3 into a NiO-Ni electrocatalyst for sustained water splitting

DOE PAGES

Gong, Ming; Zhou, Wu; Kenney, Michael James; ...

2015-08-24

The rising H 2 economy demands active and durable electrocatalysts based on low-cost, earth-abundant materials for water electrolysis/photolysis. Here we report nanoscale Ni metal cores over-coated by a Cr 2O 3-blended NiO layer synthesized on metallic foam substrates. The Ni@NiO/Cr 2O 3 triphase material exhibits superior activity and stability similar to Pt for the hydrogen-evolution reaction in basic solutions. The chemically stable Cr 2O 3 is crucial for preventing oxidation of the Ni core, maintaining abundant NiO/Ni interfaces as catalytically active sites in the heterostructure and thus imparting high stability to the hydrogen-evolution catalyst. The highly active and stable electrocatalystmore » enables an alkaline electrolyzer operating at 20 mA cm –2 at a voltage lower than 1.5 V, lasting longer than 3 weeks without decay. Thus, the non-precious metal catalysts afford a high efficiency of about 15 % for light-driven water splitting using GaAs solar cells.« less

Solar High Temperature Water-Splitting Cycle with Quantum Boost

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, Robin; Davenport, Roger; Talbot, Jan

A sulfur family chemical cycle having ammonia as the working fluid and reagent was developed as a cost-effective and efficient hydrogen production technology based on a solar thermochemical water-splitting cycle. The sulfur ammonia (SA) cycle is a renewable and sustainable process that is unique in that it is an all-fluid cycle (i.e., with no solids handling). It uses a moderate temperature solar plant with the solar receiver operating at 800°C. All electricity needed is generated internally from recovered heat. The plant would operate continuously with low cost storage and it is a good potential solar thermochemical hydrogen production cycle formore » reaching the DOE cost goals. Two approaches were considered for the hydrogen production step of the SA cycle: (1) photocatalytic, and (2) electrolytic oxidation of ammonium sulfite to ammonium sulfate in aqueous solutions. Also, two sub-cycles were evaluated for the oxygen evolution side of the SA cycle: (1) zinc sulfate/zinc oxide, and (2) potassium sulfate/potassium pyrosulfate. The laboratory testing and optimization of all the process steps for each version of the SA cycle were proven in the laboratory or have been fully demonstrated by others, but further optimization is still possible and needed. The solar configuration evolved to a 50 MW(thermal) central receiver system with a North heliostat field, a cavity receiver, and NaCl molten salt storage to allow continuous operation. The H2A economic model was used to optimize and trade-off SA cycle configurations. Parametric studies of chemical plant performance have indicated process efficiencies of ~20%. Although the current process efficiency is technically acceptable, an increased efficiency is needed if the DOE cost targets are to be reached. There are two interrelated areas in which there is the potential for significant efficiency improvements: electrolysis cell voltage and excessive water vaporization. Methods to significantly reduce water evaporation are proposed for future activities. Electrolysis membranes that permit higher temperatures and lower voltages are attainable. The oxygen half cycle will need further development and improvement.« less

Cold sprayed WO3 and TiO2 electrodes for photoelectrochemical water and methanol oxidation in renewable energy applications.

PubMed

Haisch, Christoph; Schneider, Jenny; Fleisch, Manuel; Gutzmann, Henning; Klassen, Thomas; Bahnemann, Detlef W

2017-10-03

Films prepared by cold spray have potential applications as photoanodes in electrochemical water splitting and waste water purification. In the present study cold sprayed photoelectrodes produced with WO 3 (active under visible light illumination) and TiO 2 (active under UV illumination) on titanium metal substrates were investigated as photoanodes for the oxidation of water and methanol, respectively. Methanol was chosen as organic model pollutant in acidic electrolytes. Main advantages of the cold sprayed photoelectrodes are the improved metal-semiconductor junctions and the superior mechanical stability. Additionally, the cold spray method can be utilized as a large-scale electrode fabrication technique for photoelectrochemical applications. Incident photon to current efficiencies reveal that cold sprayed TiO 2 /WO 3 photoanodes exhibit the best photoelectrochemical properties with regard to the water and methanol oxidation reactions in comparison with the benchmark photocatalyst Aeroxide TiO 2 P25 due to more efficient harvesting of the total solar light irradiation related to their smaller band gap energies.

Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes.

PubMed

Berardi, Serena; Francàs, Laia; Neudeck, Sven; Maji, Somnath; Benet-Buchholz, Jordi; Meyer, Franc; Llobet, Antoni

2015-11-01

Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities

PubMed Central

Lu, Xunyu; Zhao, Chuan

2015-01-01

Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500 mA cm−2) at low applied potentials. Here we show that an efficient oxygen electrode can be developed by electrodepositing amorphous mesoporous nickel–iron composite nanosheets directly onto macroporous nickel foam substrates. The as-prepared oxygen electrode exhibits high catalytic activity towards water oxidation in alkaline solutions, which only requires an overpotential of 200 mV to initiate the reaction, and is capable of delivering current densities of 500 and 1,000 mA cm−2 at overpotentials of 240 and 270 mV, respectively. The electrode also shows prolonged stability against bulk water electrolysis at large current. Collectively, the as-prepared three-dimensional structured electrode is the most efficient oxygen evolution electrode in alkaline electrolytes reported to the best of our knowledge, and can potentially be applied for industrial scale water electrolysis. PMID:25776015

CuO-Functionalized Silicon Photoanodes for Photoelectrochemical Water Splitting Devices.

PubMed

Shi, Yuanyuan; Gimbert-Suriñach, Carolina; Han, Tingting; Berardi, Serena; Lanza, Mario; Llobet, Antoni

2016-01-13

One main difficulty for the technological development of photoelectrochemical (PEC) water splitting (WS) devices is the fabrication of active, stable and cost-effective photoelectrodes that ensure high performance. Here, we report the development of a CuO/Silicon based photoanode, which shows an onset potential for the water oxidation of 0.53 V vs SCE at pH 9, that is, an overpotential of 75 mV, and high stability above 10 h. These values account for a photovoltage of 420 mV due to the absorbed photons by silicon, as proven by comparing with analogous CuO/FTO electrodes that are not photoactive. The photoanodes have been fabricated by sputtering a thin film of Cu(0) on commercially available n-type Si wafers, followed by a photoelectrochemical treatment in basic pH conditions. The resulting CuO/Cu layer acts as (1) protective layer to avoid the corrosion of nSi, (2) p-type hole conducting layer for efficient charge separation and transportation, and (3) electrocatalyst to reduce the overpotential of the water oxidation reaction. The low cost, low toxicity, and good performance of CuO-based coatings can be an attractive solution to functionalize unstable materials for solar energy conversion.

Dye-sensitized photocatalyst for effective water splitting catalyst

NASA Astrophysics Data System (ADS)

Watanabe, Motonori

2017-12-01

Renewable hydrogen production is a sustainable method for the development of next-generation energy technologies. Utilising solar energy and photocatalysts to split water is an ideal method to produce hydrogen. In this review, the fundamental principles and recent progress of hydrogen production by artificial photosynthesis are reviewed, focusing on hydrogen production from photocatalytic water splitting using organic-inorganic composite-based photocatalysts.

Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

PubMed

Zhang, Chundong; Jun, Ki-Won; Ha, Kyoung-Su; Lee, Yun-Jo; Kang, Seok Chang

2014-07-15

Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

Instruments for Characterizing Carbon and Sulfur-Resistant Core-Shell Redox Catalysts for Combined Hydrocarbon Reforming and Water-Splitting

DTIC Science & Technology

2015-11-22

SECURITY CLASSIFICATION OF: This project aims to investigate a novel core-shell redox catalyst for combined methane partial oxidation and water...Properly designed redox catalyst are shown to be highly effective for syngas production (from methane ) and water-splitting. The resulting syngas has a...27709-2211 redox catalyst, methane partial oxidation, water-splitting REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR

Electrocatalytic and photocatalytic hydrogen evolution integrated with organic oxidation.

PubMed

You, Bo; Han, Guanqun; Sun, Yujie

2018-06-08

Renewable energy-driven hydrogen production from electrocatalytic and photocatalytic water splitting has been widely recognized as a promising approach to utilize green energy resources and hence reduces our dependence on legacy fossil fuels as well as alleviates net carbon dioxide emissions. The realization of large-scale water splitting, however, is mainly impeded by its slow kinetics, particularly because of its sluggish anodic half reaction, the oxygen evolution reaction (OER), whose product O2 is ironically not of high value. In fact, the co-production of H2 and O2 in conventional water electrolysis may result in the formation of explosive H2/O2 gas mixtures due to gas crossover and reactive oxygen species (ROS); both pose safety concerns and shorten the lifetimes of water splitting cells. With these considerations in mind, replacing the OER with thermodynamically more favorable organic oxidation reactions is much more preferred, which will not only substantially reduce the voltage input for H2 evolution from water and avoid the generation of H2/O2 gas mixtures and ROS, but also possibly lead to the co-production of value-added organic products on the anode. Indeed, such an innovative strategy for H2 production integrated with valuable organic oxidation has attracted increasing attention in both electrocatalysis and photocatalysis. This feature article showcases the most recent examples along this endeavor. As exemplified in the main text, the oxidative transformation of a variety of organic substrates, including alcohols, ammonia, urea, hydrazine, and biomass-derived intermediate chemicals, can be integrated with energy-efficient H2 evolution. We specifically highlight the importance of oxidative biomass valorization coupled with H2 production, as biomass is the only green carbon source whose scale is comparable to fossil fuels. Finally, the remaining challenges and future opportunities are also discussed.

(Fe0.2Ni0.8)0.96S tubular spheres supported on Ni foam as an efficient bifunctional electrocatalyst for overall water splitting.

PubMed

Xu, Peiman; Li, Jingwei; Luo, Jiaxian; Wei, Licheng; Zhang, Dawei; Zhou, Dan; Xu, Weiming; Yuan, Dingsheng

2018-06-21

Earth-abundant and efficient bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly significant for renewable energy systems. However, the performance of existing electrocatalysts is usually restricted by the low electroic conductivity and the limited amount of exposed active sites. In this work, (Fe 0.2 Ni 0.8 ) 0.96 S tubular spheres supported on Ni foam have been prepared by a sulfuration of FeNi layered double hydroxide spheres grown on Ni foam. Benefiting from the unique tubular sphere architecture, the rich inner defects and the enhanced electron interactions between Fe, Ni and S, this electrocatalyst shows low overpotential of 48 mV for HER at 10 mA cm -2 in 1.0 mol L -1 KOH solution, which is one of the lowest value of non-previous electrocatalyts for HER in alkaline electrolyte. Furthermore, assembled this versatile electrode as an alkaline electrolyzer for overall water splitting, a current density of 10 mA cm -2 is achieved at a low cell voltage of 1.56 V, and reach up to 30 mA cm -2 only at an operating cell voltage of 1.65 V.

Metallic Ni3S2 Films Grown by Atomic Layer Deposition as an Efficient and Stable Electrocatalyst for Overall Water Splitting.

PubMed

Ho, Thi Anh; Bae, Changdeuck; Nam, Hochul; Kim, Eunsoo; Lee, Seung Yong; Park, Jong Hyeok; Shin, Hyunjung

2018-04-18

We describe the direct preparation of crystalline Ni 3 S 2 thin films via atomic layer deposition (ALD) techniques at temperatures as low as 250 °C without postthermal treatments. A new ALD chemistry is proposed using bis(1-dimethylamino-2-methyl-2-butoxy) nickel(II) [Ni(dmamb) 2 ] and H 2 S as precursors. Homogeneous and conformal depositions of Ni 3 S 2 films were achieved on 4 in. wafers (both metal and oxide substrates, including Au and SiO 2 ). The resulting crystalline Ni 3 S 2 layers exhibited highly efficient and stable performance as electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solutions, with a low overpotential of 300 mV and a high turnover frequency for HER and an overpotential of 400 mV for OER (at a current density of 10 mA/cm 2 ). Using our Ni 3 S 2 films as both the cathode and the anode, two-electrode full-cell electrolyzers were constructed, which showed stable operation for 100 h at a current density of 10 mA/cm 2 . The proposed ALD electrocatalysts on planar surfaces exhibited the best performance among Ni 3 S 2 materials for overall water splitting recorded to date.

Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production.

PubMed

Li, Lianwei; Cai, Zhengxu; Wu, Qinghe; Lo, Wai-Yip; Zhang, Na; Chen, Lin X; Yu, Luping

2016-06-22

Developing highly efficient photocatalyts for water splitting is one of the grand challenges in solar energy conversion. Here, we report the rational design and synthesis of porous conjugated polymer (PCP) that photocatalytically generates hydrogen from water splitting. The design mimics natural photosynthetics systems with conjugated polymer component to harvest photons and the transition metal part to facilitate catalytic activities. A series of PCPs have been synthesized with different light harvesting chromophores and transition metal binding bipyridyl (bpy) sites. The photocatalytic activity of these bpy-containing PCPs can be greatly enhanced due to the improved light absorption, better wettability, local ordering structure, and the improved charge separation process. The PCP made of strong and fully conjugated donor chromophore DBD (M4) shows the highest hydrogen production rate at ∼33 μmol/h. The results indicate that copolymerization between a strong electron donor and weak electron acceptor into the same polymer chain is a useful strategy for developing efficient photocatalysts. This study also reveals that the residual palladium in the PCP networks plays a key role for the catalytic performance. The hydrogen generation activity of PCP photocatalyst can be further enhanced to 164 μmol/h with an apparent quantum yield of 1.8% at 350 nm by loading 2 wt % of extra platinum cocatalyst.

Fabrication and improved photoelectrochemical properties of a transferred GaN-based thin film with InGaN/GaN layers.

PubMed

Cao, Dezhong; Xiao, Hongdi; Gao, Qingxue; Yang, Xiaokun; Luan, Caina; Mao, Hongzhi; Liu, Jianqiang; Liu, Xiangdong

2017-08-17

Herein, a lift-off mesoporous GaN-based thin film, which consisted of a strong phase-separated InGaN/GaN layer and an n-GaN layer, was fabricated via an electrochemical etching method in a hydrofluoric acid (HF) solution for the first time and then transferred onto quartz or n-Si substrates, acting as photoanodes during photoelectrochemical (PEC) water splitting in a 1 M NaCl aqueous solution. Compared to the as-grown GaN-based film, the transferred GaN-based thin films possess higher and blue-shifted light emission, presumably resulting from an increase in the surface area and stress relaxation in the InGaN/GaN layer embedded on the mesoporous n-GaN. The properties such as (i) high photoconversion efficiency, (ii) low turn-on voltage (-0.79 V versus Ag/AgCl), and (iii) outstanding stability enable the transferred films to have excellent PEC water splitting ability. Furthermore, as compared to the film transferred onto the quartz substrate, the film transferred onto the n-Si substrate exhibits higher photoconversion efficiency (2.99% at -0.10 V) due to holes (h + ) in the mesoporous n-GaN layer that originate from the n-Si substrate.

Recycling of rare earth particle by mini-hydrocyclones.

PubMed

Yu, Jian-Feng; Fu, Jian; Cheng, Hao; Cui, Zhengwei

2017-03-01

Mini-hydrocyclones were applied to separate the fine rare earth particles from the suspensions. The effects of the flow rate, split ratio, and feed concentration on the total separation efficiency and grade separation efficiency were studied. The combined effects of the flow rate (1200-1600L/h), split ratio (20-60%) and concentration (0.6-1.0wt%) on the total separation efficiency in mini-hydrocyclones were investigated using a response surface methodology. The optimum operating parameters for a total separation efficiency of 92.5% were: feed flow rate=1406L/h, split ratio=20%, and feed concentration=1wt%. Copyright © 2016 Elsevier Ltd. All rights reserved.

One-Dimensional Metal-Oxide Nanostructures for Solar Photocatalytic Water-Splitting

NASA Astrophysics Data System (ADS)

Wang, Fengyun; Song, Longfei; Zhang, Hongchao; Luo, Linqu; Wang, Dong; Tang, Jie

2017-08-01

Because of their unique physical and chemical properties, one-dimensional (1-D) metal-oxide nanostructures have been extensively applied in the areas of gas sensors, electrochromic devices, nanogenerators, and so on. Solar water-splitting has attracted extensive research interest because hydrogen generated from solar-driven water splitting is a clean, sustainable, and abundant energy source that not only solves the energy crisis, but also protects the environment. In this comprehensive review, the main synthesis methods, properties, and especially prominent applications in solar water splitting of 1-D metal-oxides, including titanium dioxide (TiO2), zinc oxide (ZnO), tungsten trioxide (WO3), iron oxide (Fe2O3), and copper oxide (CuO) are fully discussed.

Z-schematic water splitting by the synergistic effect of a type-II heterostructure and a highly efficient oxygen evolution catalyst

NASA Astrophysics Data System (ADS)

Li, Xiaoyun; Hu, Haihua; Xu, Lingbo; Cui, Can; Qian, Degui; Li, Shuang; Zhu, Wenzhe; Wang, Peng; Lin, Ping; Pan, Jiaqi; Li, Chaorong

2018-05-01

Artificial Z-scheme system inspired by the natural photosynthesis in green plants has attracted extensive attention owing to its advantages such as simultaneously wide range light absorption, highly efficient charge separation and strong redox ability. In this paper, we report the synthesis of a novel all-solid-state direct Z-scheme photocatalyst of Ag3PO4/CeO2/TiO2 by depositing Ag3PO4 nanoparticles (NPs) on CeO2/TiO2 hierarchical branched nanowires (BNWs), where the CeO2/TiO2 BNWs act as a novel substrate for the well dispersed nano-size Ag3PO4. The Ag3PO4/CeO2/TiO2 photocatalyst exhibits excellent ability of photocatalytic oxygen evolution from pure water splitting. It is suggested that the Z-scheme charge transfer route between CeO2/TiO2 and Ag3PO4 improves the redox ability. On the other hand, the cascade energy level alignment in CeO2/TiO2 BNWs expedites the spatial charge separation, and hence suppresses photocatalytic backward reaction. However, it is difficult to realize a perfect excitation balance in Ag3PO4/CeO2/TiO2 and the composite still surfers photo-corrosion in photocatalysis reaction. Nevertheless, our results provide an innovative strategy of constructing a Z-scheme system from a type-II heterostructure and a highly efficient oxygen evolution catalyst.

Tunable Resonance Coupling in Single Si Nanoparticle-Monolayer WS2 Structures.

PubMed

Lepeshov, Sergey; Wang, Mingsong; Krasnok, Alex; Kotov, Oleg; Zhang, Tianyi; Liu, He; Jiang, Taizhi; Korgel, Brian; Terrones, Mauricio; Zheng, Yuebing; Alú, Andrea

2018-05-16

Two-dimensional semiconducting transition metal dichalcogenides (TMDCs) are extremely attractive materials for optoelectronic applications in the visible and near-infrared range. Coupling these materials to optical nanocavities enables advanced quantum optics and nanophotonic devices. Here, we address the issue of resonance coupling in hybrid exciton-polariton structures based on single Si nanoparticles (NPs) coupled to monolayer (1L)-WS 2 . We predict a strong coupling regime with a Rabi splitting energy exceeding 110 meV for a Si NP covered by 1L-WS 2 at the magnetic optical Mie resonance because of the symmetry of the mode. Further, we achieve a large enhancement in the Rabi splitting energy up to 208 meV by changing the surrounding dielectric material from air to water. The prediction is based on the experimental estimation of TMDC dipole moment variation obtained from the measured photoluminescence spectra of 1L-WS 2 in different solvents. An ability of such a system to tune the resonance coupling is realized experimentally for optically resonant spherical Si NPs placed on 1L-WS 2 . The Rabi splitting energy obtained for this scenario increases from 49.6 to 86.6 meV after replacing air by water. Our findings pave the way to develop high-efficiency optoelectronic, nanophotonic, and quantum optical devices.

Understanding charge transfer dynamics in QDs-TiO2 nanorod array photoanodes for solar fuel generation

NASA Astrophysics Data System (ADS)

Li, Jiangtian; McClure, Joshua P.; Fu, Richard; Jiang, Rongzhong; Chu, Deryn

2018-01-01

Harvesting light to drive water splitting for hydrogen generation is an attractive approach to satisfy the urgent energy demands. The design and fabrication of photoelectrode materials that are able to harvest sunlight is an important scientific undertaking. In this study, a two-quantum-dot (QD) layer is developed to decorate one-dimensional TiO2 nanorod arrays, which are subsequently utilized as photoanodes to harvest the wide-spectrum sunlight for water splitting. The QD-coated TiO2 nanorod arrays extend the light absorption range from the UV into the visible region yielding increased solar-to-hydrogen efficiencies. Transient photocurrent decay measurements demonstrate that the multi-layer CdSe-CdS QDs deposited onto the TiO2 nanorod arrays result in a stepwise band alignment that not only improves the hole extraction but also facilitates electron injection from the QDs to TiO2 rods. Moreover, the multi-heterojunction photoanode introduces interfacial states that act as recombination centers to trap the photogenerated electrons.

Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting

NASA Astrophysics Data System (ADS)

Selvaraj, Seenivasan; Moon, Hee; Kim, Do-Heyoung

2018-01-01

Photo-electrochemical water splitting with hematite photo-anodes under solar irradiation has attracted considerable attention as regards the production of renewable hydrogen energy. However, many challenges remain unresolved, as the full contribution of the catalytic over-layers has not been fully realized. Herein, we incorporate uniform spinel nickel-ferrite over-layers in hematite photo-anodes to obtain an improved understanding of the associated intrinsic changes. We achieve a 1.5-mA/cm2 photo-current density at 1.23 VRHE (RHE: reversible hydrogen electrode) under one-sun illumination conditions, along with a negative shift of 200 mV in the onset potential, for NiFe2O4-coated Sn-doped hematite photo-anodes. Fundamental electrochemical analyses clearly show that the shift in the onset potential is predominantly due to the enhanced photo-voltage development inside the hematite, rather than being purely caused by the interfacial kinetics. These insights reveal a new direction for fundamental research on photo-anodes towards fabrication of more efficient photo-anode systems.

High-efficiency p-n junction oxide photoelectrodes for photoelectrochemical water splitting.

PubMed

Liu, Zhifeng; Yan, Lu

2016-11-16

Development of all oxide p-n junctions makes a significant advancement in photoelectrode catalysis functional materials. In this article, we report the preparation of TiO 2 nanorod (NR)/Cu 2 O photoanodes via a simple hydrothermal method followed by an electrochemical deposition process. This facile synthesis route can simultaneously achieve uniform TiO 2 NR/Cu 2 O composite nanostructures and obtain varied amounts of Cu 2 O by controlling the deposition time. The photocurrent density of TiO 2 NR/Cu 2 O heterojunction photoanodes enhanced the photocatalytic activity with a photocurrent density of 5.25 mA cm -2 at 1.23 V versus RHE compared to pristine TiO 2 NR photoanodes under the same conditions. It is demonstrated that the presence of Cu 2 O has played an important role in expanding the spectral response region and reducing the photogenerated charge recombination rate. More importantly, the results provide new insights into the performance of all oxide p-n junctions as photoanodes for PEC water splitting.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

NASA Astrophysics Data System (ADS)

Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.; Walczak, Karl A.; Favaro, Marco; Beeman, Jeffrey W.; Hess, Lucas H.; Wang, Cheng; Zhu, Chenhui; Gul, Sheraz; Yano, Junko; Kisielowski, Christian; Schwartzberg, Adam; Sharp, Ian D.

2017-03-01

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Recent advances in visible-light-responsive photocatalysts for hydrogen production and solar energy conversion--from semiconducting TiO2 to MOF/PCP photocatalysts.

PubMed

Horiuchi, Yu; Toyao, Takashi; Takeuchi, Masato; Matsuoka, Masaya; Anpo, Masakazu

2013-08-28

The present perspective describes recent advances in visible-light-responsive photocatalysts intended to develop novel and efficient solar energy conversion technologies, including water splitting and photofuel cells. Water splitting is recognized as one of the most promising techniques to convert solar energy as a clean and abundant energy resource into chemical energy in the form of hydrogen. In recent years, increasing concern is directed to not only the development of new photocatalytic materials but also the importance of technologies to produce hydrogen and oxygen separately. Photofuel cells can convert solar energy into electrical energy by decomposing bio-related compounds and livestock waste as fuels. The advances of photocatalysts enabling these solar energy conversion technologies have been going on since the discovery of semiconducting titanium dioxide materials and have extended to organic-inorganic hybrid materials, such as metal-organic frameworks and porous coordination polymers (MOF/PCP).

Graphene-based heterojunction photocatalysts

NASA Astrophysics Data System (ADS)

Li, Xin; Shen, Rongchen; Ma, Song; Chen, Xiaobo; Xie, Jun

2018-02-01

Due to their unique physicochemical, optical and electrical properties, 2D semimetallic or semiconducting graphene has been extensively utilized to construct highly efficient heterojunction photocatalysts for driving a variety of redox reactions under proper light irradiation. In this review, we carefully addressed the fundamental mechanism of heterogeneous photocatalysis, fundamental properties and advantages of graphene in photocatalysis, and classification and comparison of graphene-based heterojunction photocatalysts. Subsequently, we thoroughly highlighted and discussed various graphene-based heterojunction photocatalysts, including Schottky junctions, Type-II heterojunctions, Z-scheme heterojunctions, Van der Waals heterostructures, in plane heterojunctions and multicomponent heterojunctions. Several important photocatalytic applications, such as photocatalytic water splitting (H2 evolution and overall water splitting), degradation of pollutants, carbon dioxide reduction and bacteria disinfection, are also summarized. Through reviewing the important advances on this topic, it may inspire some new ideas for exploiting highly effective graphene-based heterojunction photocatalysts for a number of applications in photocatlysis and other fields, such as photovoltaic, (photo)electrocatalysis, lithium battery, fuel cell, supercapacitor and adsorption separation.

A Janus cobalt-based catalytic material for electro-splitting of water

NASA Astrophysics Data System (ADS)

Cobo, Saioa; Heidkamp, Jonathan; Jacques, Pierre-André; Fize, Jennifer; Fourmond, Vincent; Guetaz, Laure; Jousselme, Bruno; Ivanova, Valentina; Dau, Holger; Palacin, Serge; Fontecave, Marc; Artero, Vincent

2012-09-01

The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable and efficient systems for the conversion and storage of renewable energy sources. The production of hydrogen through water splitting seems a promising and appealing solution. We found that a robust nanoparticulate electrocatalytic material, H2-CoCat, can be electrochemically prepared from cobalt salts in a phosphate buffer. This material consists of metallic cobalt coated with a cobalt-oxo/hydroxo-phosphate layer in contact with the electrolyte and mediates H2 evolution from neutral aqueous buffer at modest overpotentials. Remarkably, it can be converted on anodic equilibration into the previously described amorphous cobalt oxide film (O2-CoCat or CoPi) catalysing O2 evolution. The switch between the two catalytic forms is fully reversible and corresponds to a local interconversion between two morphologies and compositions at the surface of the electrode. After deposition, the noble-metal-free coating thus functions as a robust, bifunctional and switchable catalyst.

Cobalt Covalent Doping in MoS2 to Induce Bifunctionality of Overall Water Splitting.

PubMed

Xiong, Qizhong; Wang, Yun; Liu, Peng-Fei; Zheng, Li-Rong; Wang, Guozhong; Yang, Hua-Gui; Wong, Po-Keung; Zhang, Haimin; Zhao, Huijun

2018-05-28

The layer-structured MoS 2 is a typical hydrogen evolution reaction (HER) electrocatalyst but it possesses poor activity for the oxygen evolution reaction (OER). In this work, a cobalt covalent doping approach capable of inducing HER and OER bifunctionality into MoS 2 for efficient overall water splitting is reported. The results demonstrate that covalently doping cobalt into MoS 2 can lead to dramatically enhanced HER activity while simultaneously inducing remarkable OER activity. The catalyst with optimal cobalt doping density can readily achieve HER and OER onset potentials of -0.02 and 1.45 V (vs reversible hydrogen electrode (RHE)) in 1.0 m KOH. Importantly, it can deliver high current densities of 10, 100, and 200 mA cm -2 at low HER and OER overpotentials of 48, 132, 165 mV and 260, 350, 390 mV, respectively. The reported catalyst activation approach can be adapted for bifunctionalization of other transition metal dichalcogenides. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel nanoparticles-embedded N-doped carbon nanotubes as a biocompatible electrocatalyst in a water splitting-biosynthetic hybrid system for CO2 conversion.

PubMed

Li, Zhongjian; Li, Gang; Chen, Xinlu; Xia, Zheng; Yao, Jiani; Yang, Bin; Lei, Lecheng; Hou, Yang

2018-05-29

CO2 reduction has drawn increasing attention due to the concern of global warming. Water splitting-biosynthetic hybrid systems are novel and efficient approaches for CO2 conversion. Intimate coupling of electrocatalysts and biosynthesis requires the catalysts possess both high catalytic performance and excellent biocompatibility, which is a bottleneck of developing such catalysts. Here, a novel Ni nanoparticles-embedded N-doped carbon nanotubes (Ni@N-C) complex was synthesized as a hydrogen evolution reaction electrocatalyst and was coupled with a hydrogen-oxidizing autotroph, Cupriavidus necator H16, to convert CO2 to poly-β-hydroxybutyrate. In the Ni@N-C, the Ni nanoparticles were encapsulated in N-C nanotubes, which prevented bacteria from direct contact with Ni and inhibited Ni2+ leaching. As a result, Ni@N-C exhibited excellent biocompatibility and stability. This work demonstrates electrocatalysts and biosynthesis can be intimately coupled via rational catalyst design. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoelectrodes based upon Mo:BiVO4 inverse opals for photoelectrochemical water splitting.

PubMed

Zhou, Min; Bao, Jian; Xu, Yang; Zhang, Jiajia; Xie, Junfeng; Guan, Meili; Wang, Chengliang; Wen, Liaoyong; Lei, Yong; Xie, Yi

2014-07-22

BiVO4 has been regarded as a promising material for photoelectrochemical water splitting, but it suffers from a major challenge on charge collection and utilization. In order to meet this challenge, we design a nanoengineered three-dimensional (3D) ordered macro-mesoporous architecture (a kind of inverse opal) of Mo:BiVO4 through a controllable colloidal crystal template method with the help of a sandwich solution infiltration method and adjustable post-heating time. Within expectation, a superior photocurrent density is achieved in return for this design. This enhancement originates primarily from effective charge collection and utilization according to the analysis of electrochemical impedance spectroscopy and so on. All the results highlight the great significance of the 3D ordered macro-mesoporous architecture as a promising photoelectrode model for the application in solar conversion. The cooperating amplification effects of nanoengineering from composition regulation and morphology innovation are helpful for creating more purpose-designed photoelectrodes with highly efficient performance.

Thermodynamic analysis of alternate energy carriers, hydrogen and chemical heat pipes

NASA Technical Reports Server (NTRS)

Cox, K. E.; Carty, R. H.; Conger, W. L.; Soliman, M. A.; Funk, J. E.

1976-01-01

The paper discusses the production concept and efficiency of two new energy transmission and storage media intended to overcome the disadvantages of electricity as an overall energy carrier. These media are hydrogen produced by water-splitting and the chemical heat pipe. Hydrogen can be transported or stored, and burned as energy is needed, forming only water and thus obviating pollution problems. The chemical heat pipe envisions a system in which heat is stored as the heat of reaction in chemical species. The thermodynamic analysis of these two methods is discussed in terms of first-law and second-law efficiency. It is concluded that chemical heat pipes offer large advantages over thermochemical hydrogen generation schemes on a first-law efficiency basis except for the degradation of thermal energy in temperature thus providing a source of low-temperature (800 K) heat for process heat applications. On a second-law efficiency basis, hydrogen schemes are superior in that the amount of available work is greater as compared to chemical heat pipes.

Enhancing Mo:BiVO 4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon-Induced Energy Transfer [Rational Nanopositioning for BiVO 4 Solar Water Splitting by Plasmon-induced Energy Transfer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jung Kyu; Shi, Xinjian; Jeong, Myung Jin

Here, plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon–induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum–doped bismuth vanadium oxide (Mo:BiVO 4), regarded as one of the bestmore » metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO 4 photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO 4. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time–correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO 4 at 1.23 V versus RHE by ≈2.2–fold (2.83 mA cm –2).« less

Enhancing Mo:BiVO 4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon-Induced Energy Transfer [Rational Nanopositioning for BiVO 4 Solar Water Splitting by Plasmon-induced Energy Transfer

DOE PAGES

Kim, Jung Kyu; Shi, Xinjian; Jeong, Myung Jin; ...

2017-10-04

Here, plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon–induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum–doped bismuth vanadium oxide (Mo:BiVO 4), regarded as one of the bestmore » metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO 4 photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO 4. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time–correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO 4 at 1.23 V versus RHE by ≈2.2–fold (2.83 mA cm –2).« less

Novel microwave-assisted synthesis of porous g-C3N4/SnO2 nanocomposite for solar water-splitting

NASA Astrophysics Data System (ADS)

Seza, A.; Soleimani, F.; Naseri, N.; Soltaninejad, M.; Montazeri, S. M.; Sadrnezhaad, S. K.; Mohammadi, M. R.; Moghadam, H. Asgari; Forouzandeh, M.; Amin, M. H.

2018-05-01

Highly porous nanocomposites of graphitic-carbon nitride and tin oxide (g-C3N4/SnO2) were prepared through simple pyrolysis of urea molecules under microwave irradiation. The initial amount of tin was varied in order to investigate the effect of SnO2 content on preparation and properties of the composites. The synthesized nanocomposites were well-characterized by XRD, FE-SEM, HR-TEM, BET, FTIR, XPS, DRS, and PL. A homogeneous distribution of SnO2 nanoparticles with the size of less than 10 nm on the porous C3N4 sheets could be obtained, suggesting that in-situ synthesis of SnO2 nanoparticles was responsible for the formation of g-C3N4. The process likely occurred by the aid of the large amounts of OH groups formed on the surfaces of SnO2 nanoparticles during the polycondensation reactions of tin derivatives which could facilitate the pyrolysis of urea to carbon nitride. The porous nanocomposite prepared with initial tin amount of 0.175 g had high specific surface area of 195 m2 g-1 which showed high efficiency photoelectrochemical water-splitting ability. A maximum photocurrent density of 33 μA cm-2 was achieved at an applied potential of 0.5 V when testing this nanocomposite as photo-anode in water-splitting reactions under simulated visible light irradiation, introducing it as a promising visible light photoactive material.

Photoelectrochemical water splitting with mesoporous hematite prepared by a solution-based colloidal approach.

PubMed

Sivula, Kevin; Zboril, Radek; Le Formal, Florian; Robert, Rosa; Weidenkaff, Anke; Tucek, Jiri; Frydrych, Jiri; Grätzel, Michael

2010-06-02

Sustainable hydrogen production through photoelectrochemical water splitting using hematite (alpha-Fe(2)O(3)) is a promising approach for the chemical storage of solar energy, but is complicated by the material's nonoptimal optoelectronic properties. Nanostructuring approaches have been shown to increase the performance of hematite, but the ideal nanostructure giving high efficiencies for all absorbed light wavelengths remains elusive. Here, we report for the first time mesoporous hematite photoelectodes prepared by a solution-based colloidal method which yield water-splitting photocurrents of 0.56 mA cm(-2) under standard conditions (AM 1.5G 100 mW cm(-2), 1.23 V vs reversible hydrogen electrode, RHE) and over 1.0 mA cm(-2) before the dark current onset (1.55 V vs RHE). The sintering temperature is found to increase the average particle size, and have a drastic effect on the photoactivity. X-ray photoelectron spectroscopy and magnetic measurements using a SQUID magnetometer link this effect to the diffusion and incorporation of dopant atoms from the transparent conducting substrate. In addition, examining the optical properties of the films reveals a considerable change in the absorption coefficient and onset properties, critical aspects for hematite as a solar energy converter, as a function of the sintering temperature. A detailed investigation into hematite's crystal structure using powder X-ray diffraction with Rietveld refinement to account for these effects correlates an increase in a C(3v)-type crystal lattice distortion to the improved optical properties.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Peili; Li, Lin; Nordlund, Dennis

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation

DOE PAGES

Zhang, Peili; Li, Lin; Nordlund, Dennis; ...

2018-01-26

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less

An Earth-Abundant Catalyst-Based Seawater Photoelectrolysis System with 17.9% Solar-to-Hydrogen Efficiency.

PubMed

Hsu, Shao-Hui; Miao, Jianwei; Zhang, Liping; Gao, Jiajian; Wang, Hongming; Tao, Huabing; Hung, Sung-Fu; Vasileff, Anthony; Qiao, Shi Zhang; Liu, Bin

2018-05-01

The implementation of water splitting systems, powered by sustainable energy resources, appears to be an attractive strategy for producing high-purity H 2 in the absence of the release of carbon dioxide (CO 2 ). However, the high cost, impractical operating conditions, and unsatisfactory efficiency and stability of conventional methods restrain their large-scale development. Seawater covers 70% of the Earth's surface and is one of the most abundant natural resources on the planet. New research is looking into the possibility of using seawater to produce hydrogen through electrolysis and will provide remarkable insight into sustainable H 2 production, if successful. Here, guided by density functional theory (DFT) calculations to predict the selectivity of gas-evolving catalysts, a seawater-splitting device equipped with affordable state-of-the-art electrocatalysts composed of earth-abundant elements (Fe, Co, Ni, and Mo) is demonstrated. This device shows excellent durability and specific selectivity toward the oxygen evolution reaction in seawater with near 100% Faradaic efficiency for the production of H 2 and O 2 . Powered by a single commercial III-V triple-junction photovoltaic cell, the integrated system achieves spontaneous and efficient generation of high-purity H 2 and O 2 from seawater at neutral pH with a remarkable 17.9% solar-to-hydrogen efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of inorganic substances on water splitting in ion-exchange membranes; II. Optimal contents of inorganic substances in preparing bipolar membranes.

PubMed

Kang, Moon-Sung; Choi, Yong-Jin; Moon, Seung-Hyeon

2004-05-15

An approach to enhancing the water-splitting performance of bipolar membranes (BPMs) is introducing an inorganic substance at the bipolar (BP) junction. In this study, the immobilization of inorganic matters (i.e., iron hydroxides and silicon compounds) at the BP junction and the optimum concentration have been investigated. To immobilize these inorganic matters, novel methods (i.e., electrodeposition of the iron hydroxide and processing of the sol-gel to introduce silicon groups at the BP junction) were suggested. At optimal concentrations, the immobilized inorganic matters significantly enhanced the water-splitting fluxes, indicating that they provide alternative paths for water dissociation, but on the other hand possibly reduce the polarization of water molecules between the sulfonic acid and quaternary ammonium groups at high contents. Consequently, the amount of inorganic substances introduced should be optimized to obtain the maximum water splitting in the BPM.

Performance evaluation of pumping systems used in commercial-scale, split-pond aquaculture

USDA-ARS?s Scientific Manuscript database

Split-pond aquaculture systems have been adopted widely by United States catfish farmers as a way to improve production performance. The split-pond consists of a fish-culture basin that is connected to a waste-treatment lagoon by two water conveyance structures. Water is circulated between the two b...

Improving Efficiency of Passive RFID Tag Anti-Collision Protocol Using Dynamic Frame Adjustment and Optimal Splitting.

PubMed

Memon, Muhammad Qasim; He, Jingsha; Yasir, Mirza Ammar; Memon, Aasma

2018-04-12

Radio frequency identification is a wireless communication technology, which enables data gathering and identifies recognition from any tagged object. The number of collisions produced during wireless communication would lead to a variety of problems including unwanted number of iterations and reader-induced idle slots, computational complexity in terms of estimation as well as recognition of the number of tags. In this work, dynamic frame adjustment and optimal splitting are employed together in the proposed algorithm. In the dynamic frame adjustment method, the length of frames is based on the quantity of tags to yield optimal efficiency. The optimal splitting method is conceived with smaller duration of idle slots using an optimal value for splitting level M o p t , where (M > 2), to vary slot sizes to get the minimal identification time for the idle slots. The application of the proposed algorithm offers the advantages of not going for the cumbersome estimation of the quantity of tags incurred and the size (number) of tags has no effect on its performance efficiency. Our experiment results show that using the proposed algorithm, the efficiency curve remains constant as the number of tags varies from 50 to 450, resulting in an overall theoretical gain in the efficiency of 0.032 compared to system efficiency of 0.441 and thus outperforming both dynamic binary tree slotted ALOHA (DBTSA) and binary splitting protocols.

Solar photocatalytic water oxidation over Ag3PO4/g-C3N4 composite materials mediated by metallic Ag and graphene

NASA Astrophysics Data System (ADS)

Cui, Xingkai; Tian, Lin; Xian, Xiaozhai; Tang, Hua; Yang, Xiaofei

2018-02-01

Solar-driven water splitting over semiconductor-based photocatalysts provides direct conversion of solar energy to chemical energy, in which electron-hole separation and charge transport are critical for enhancing the photocatalytic activity of semiconducting materials. Moreover, the search for active photocatalysts that efficiently oxidize water remains a challenging task. Here, we demonstrate that a series of Ag3PO4/Ag/graphene/graphitic carbon nitride (g-C3N4) heterostructured materials can drive photocatalytic water oxidation efficiently under LED illumination. The water oxidation behavior of as-prepared composite photocatalysts in relation to the added amount of g-C3N4 and the roles of electron mediators was investigated in detail. Based on the illuminated Z-scheme photocatalytic mechanism, the photogenerated electrons and holes can be separated effectively and the electron-hole recombination of bulk material is suppressed. The reduced metallic Ag nanoparticles were found to function as the center for the accumulation of electrons from Ag3PO4 and holes from g-C3N4. By exploiting the proper addition of g-C3N4 into the composite, photocatalytic oxygen evolution performance over the heterostructured materials could be suitably tuned, which resulted in highly efficient water oxidation.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

Composition of legume soaking water and emulsifying properties in gluten-free bread.

PubMed

Huang, San; Liu, Yuling; Zhang, Weihan; Dale, Kylie J; Liu, Silu; Zhu, Jingnan; Serventi, Luca

2018-04-01

Soaking of legumes results in the loss of macronutrients, micronutrients and phytochemicals. Fibre, protein and phytochemicals found in legumes exert emulsifying activity that may improve the structure and texture of gluten-free bread. The legume soaking water of haricot beans, garbanzo chickpeas, whole green lentils, split yellow peas and yellow soybeans were tested in this study for functional properties and use as food ingredients. Composition, physicochemical properties and effect on the quality of gluten-free bread were determined for each legume soaking water. Haricot beans and split yellow peas released the highest amount of solids in the legume soaking water: 1.89 and 2.38 g/100 g, respectively. Insoluble fibre was the main constituent of haricot beans legume soaking water, while water-soluble carbohydrates and protein were the major fraction of split yellow peas. High quantities of phenolics (∼400 µg/g) and saponins (∼3 mg/g) were found in the legume soaking water of haricot beans, whole green lentils and split yellow peas. High emulsifying activity (46 and 50%) was found for the legume soaking water of garbanzo chickpeas and split yellow peas, probably due to their protein content and high ratio of water-soluble carbohydrates to dry matter. Such activity resulted in softer texture of the gluten-free bread. A homogeneous structure of crumb pores was found for split yellow peas, opposing that of whole green lentils. A balance between the contents of yeast nutrients and antinutrients was the likely basis of the different appearances.

Holographic lens spectrum splitting photovoltaic system for increased diffuse collection and annual energy yield

NASA Astrophysics Data System (ADS)

Vorndran, Shelby D.; Wu, Yuechen; Ayala, Silvana; Kostuk, Raymond K.

2015-09-01

Concentrating and spectrum splitting photovoltaic (PV) modules have a limited acceptance angle and thus suffer from optical loss under off-axis illumination. This loss manifests itself as a substantial reduction in energy yield in locations where a significant portion of insulation is diffuse. In this work, a spectrum splitting PV system is designed to efficiently collect and convert light in a range of illumination conditions. The system uses a holographic lens to concentrate shortwavelength light onto a smaller, more expensive indium gallium phosphide (InGaP) PV cell. The high efficiency PV cell near the axis is surrounded with silicon (Si), a less expensive material that collects a broader portion of the solar spectrum. Under direct illumination, the device achieves increased conversion efficiency from spectrum splitting. Under diffuse illumination, the device collects light with efficiency comparable to a flat-panel Si module. Design of the holographic lens is discussed. Optical efficiency and power output of the module under a range of illumination conditions from direct to diffuse are simulated with non-sequential raytracing software. Using direct and diffuse Typical Metrological Year (TMY3) irradiance measurements, annual energy yield of the module is calculated for several installation sites. Energy yield of the spectrum splitting module is compared to that of a full flat-panel Si reference module.

Hydrogen Production from Nuclear Energy via High Temperature Electrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

James E. O'Brien; Carl M. Stoots; J. Stephen Herring

2006-04-01

This paper presents the technical case for high-temperature nuclear hydrogen production. A general thermodynamic analysis of hydrogen production based on high-temperature thermal water splitting processes is presented. Specific details of hydrogen production based on high-temperature electrolysis are also provided, including results of recent experiments performed at the Idaho National Laboratory. Based on these results, high-temperature electrolysis appears to be a promising technology for efficient large-scale hydrogen production.

Reduced TiO2-Graphene Oxide Heterostructure As Broad Spectrum-Driven Efficient Water-Splitting Photocatalysts.

PubMed

Li, Lihua; Yu, Lili; Lin, Zhaoyong; Yang, Guowei

2016-04-06

The reduced TiO2-graphene oxide heterostructure as an alternative broad spectrum-driven efficient water splitting photocatalyst has become a really interesting topic, however, its syntheses has many flaws, e.g., tedious experimental steps, time-consuming, small scale production, and requirement of various additives, for example, hydrazine hydrate is widely used as reductant to the reduction of graphene oxide, which is high toxicity and easy to cause the second pollution. For these issues, herein, we reported the synthesis of the reduced TiO2-graphene oxide heterostructure by a facile chemical reduction agent-free one-step laser ablation in liquid (LAL) method, which achieves extended optical response range from ultraviolet to visible and composites TiO(2-x) (reduced TiO2) nanoparticle and graphene oxide for promoting charge conducting. 30.64% Ti(3+) content in the reduced TiO2 nanoparticles induces the electronic reconstruction of TiO2, which results in 0.87 eV decrease of the band gap for the visible light absorption. TiO(2-x)-graphene oxide heterostructure achieved drastically increased photocatalytic H2 production rate, up to 23 times with respect to the blank experiment. Furthermore, a maximum H2 production rate was measured to be 16 mmol/h/g using Pt as a cocatalyst under the simulated sunlight irradiation (AM 1.5G, 135 mW/cm(2)), the quantum efficiencies were measured to be 5.15% for wavelength λ = 365 ± 10 nm and 1.84% for λ = 405 ± 10 nm, and overall solar energy conversion efficiency was measured to be 14.3%. These findings provided new insights into the broad applicability of this methodology for accessing fascinate photocatalysts.

Mechano-chemical pathways to H2O and CO2 splitting

NASA Astrophysics Data System (ADS)

Vedadi, Mohammad H.; Haas, Stephan

2011-10-01

The shock-induced collapse of CO2-filled nanobubbles is investigated using molecular dynamics simulations based on a reactive force field. The energetic nanojet and high-pressure water hammer shock formed during and after collapse of the nanobubble trigger mechano-chemical H2O-CO2 reactions, some of which lead to splitting of water and formation of O2 molecules. The dominant pathways through which splitting of water molecules occur are identified.

Plasmon inducing effects for enhanced photoelectrochemical water splitting: X-ray absorption approach to electronic structures.

PubMed

Chen, Hao Ming; Chen, Chih Kai; Chen, Chih-Jung; Cheng, Liang-Chien; Wu, Pin Chieh; Cheng, Bo Han; Ho, You Zhe; Tseng, Ming Lun; Hsu, Ying-Ya; Chan, Ting-Shan; Lee, Jyh-Fu; Liu, Ru-Shi; Tsai, Din Ping

2012-08-28

Artificial photosynthesis using semiconductors has been investigated for more than three decades for the purpose of transferring solar energy into chemical fuels. Numerous studies have revealed that the introduction of plasmonic materials into photochemical reaction can substantially enhance the photo response to the solar splitting of water. Until recently, few systematic studies have provided clear evidence concerning how plasmon excitation and which factor dominates the solar splitting of water in photovoltaic devices. This work demonstrates the effects of plasmons upon an Au nanostructure-ZnO nanorods array as a photoanode. Several strategies have been successfully adopted to reveal the mutually independent contributions of various plasmonic effects under solar irradiation. These have clarified that the coupling of hot electrons that are formed by plasmons and the electromagnetic field can effectively increase the probability of a photochemical reaction in the splitting of water. These findings support a new approach to investigating localized plasmon-induced effects and charge separation in photoelectrochemical processes, and solar water splitting was used herein as platform to explore mechanisms of enhancement of surface plasmon resonance.

Bandgap engineering and charge separation in two-dimensional GaS-based van der Waals heterostructures for photocatalytic water splitting

NASA Astrophysics Data System (ADS)

Wang, Biao; Kuang, Anlong; Luo, Xukai; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong

2018-05-01

Two-dimensional (2D) gallium sulfide (GaS), hexagonal boron nitride (h-BN) and graphitic carbon nitride (g-C3N4) have been fabricated and expected to be promising photocatalysts under ultraviolet irradiation. Here, we employ hybrid density functional calculations to explore the potential of the 2D GaS-based heterojunctions GaS/h-BN (g-C3N4) for the design of efficient water redox photocatalysts. Both heterostructures can be formed via van der Waals (vdW) interaction and are direct bandgap semiconductors, whose bandgaps are reduced comparing with isolated GaS, h-BN or g-C3N4 monolayers and whose bandedges straddle water redox potentials. Furthermore, the optical absorption of GaS/h-BN (g-C3N4) heterostructures is observably enhanced in the ultraviolet-visible (UV-vis) light range. The electron-hole pairs in GaS/h-BN (g-C3N4) heterostructures are completely separated from different layers. In addition, the in-plane biaxial strain can effectively modulate the electronic properties of GaS/h-BN (g-C3N4) heterostructures. Thus the GaS/h-BN (g-C3N4) heterostructures are anticipated to be promising candidates for photocatalytic water splitting to produce hydrogen.

Level Alignment as Descriptor for Semiconductor/Catalyst Systems in Water Splitting: The Case of Hematite/Cobalt Hexacyanoferrate Photoanodes.

PubMed

Hegner, Franziska Simone; Cardenas-Morcoso, Drialys; Giménez, Sixto; López, Núria; Galan-Mascaros, Jose Ramon

2017-11-23

The realization of artificial photosynthesis may depend on the efficient integration of photoactive semiconductors and catalysts to promote photoelectrochemical water splitting. Many efforts are currently devoted to the processing of multicomponent anodes and cathodes in the search for appropriate synergy between light absorbers and active catalysts. No single material appears to combine both features. Many experimental parameters are key to achieve the needed synergy between both systems, without clear protocols for success. Herein, we show how computational chemistry can shed some light on this cumbersome problem. DFT calculations are useful to predict adequate energy-level alignment for thermodynamically favored hole transfer. As proof of concept, we experimentally confirmed the limited performance enhancement in hematite photoanodes decorated with cobalt hexacyanoferrate as a competent water-oxidation catalyst. Computational methods describe the misalignment of their energy levels, which is the origin of this mismatch. Photoelectrochemical studies indicate that the catalyst exclusively shifts the hematite surface state to lower potentials, which therefore reduces the onset for water oxidation. Although kinetics will still depend on interface architecture, our simple theoretical approach may identify and predict plausible semiconductor/catalyst combinations, which will speed up experimental work towards promising photoelectrocatalytic systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Active GaN-Stabilized Ta3 N5 Thin-Film Photoanode for Solar Water Oxidation.

PubMed

Zhong, Miao; Hisatomi, Takashi; Sasaki, Yutaka; Suzuki, Sayaka; Teshima, Katsuya; Nakabayashi, Mamiko; Shibata, Naoya; Nishiyama, Hiroshi; Katayama, Masao; Yamada, Taro; Domen, Kazunari

2017-04-18

Ta 3 N 5 is a very promising photocatalyst for solar water splitting because of its wide spectrum solar energy utilization up to 600 nm and suitable energy band position straddling the water splitting redox reactions. However, its development has long been impeded by poor compatibility with electrolytes. Herein, we demonstrate a simple sputtering-nitridation process to fabricate high-performance Ta 3 N 5 film photoanodes owing to successful synthesis of the vital TaO δ precursors. An effective GaN coating strategy is developed to remarkably stabilize Ta 3 N 5 by forming a crystalline nitride-on-nitride structure with an improved nitride/electrolyte interface. A stable, high photocurrent density of 8 mA cm -2 was obtained with a CoPi/GaN/Ta 3 N 5 photoanode at 1.2 V RHE under simulated sunlight, with O 2 and H 2 generated at a Faraday efficiency of unity over 12 h. Our vapor-phase deposition method can be used to fabricate high-performance (oxy)nitrides for practical photoelectrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Light-Driven Water Splitting by a Covalently Linked Ruthenium-Based Chromophore–Catalyst Assembly

DOE PAGES

Sherman, Benjamin D.; Xie, Yan; Sheridan, Matthew V.; ...

2016-12-09

The preparation and characterization of new Ru(II) polypyridyl-based chromophore–catalyst assemblies, [(4,4'-PO 3H 2-bpy) 2Ru(4-Mebpy-4'-epic)Ru(bda)(pic)] 2+ (1, bpy = 2,2'-bipyridine; 4-Mebpy-4'-epic = 4-(4-methylbipyridin-4'-yl-ethyl)-pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate; pic = 4-picoline), and [(bpy) 2Ru(4-Mebpy-4'-epic)Ru(bda)(pic)] 2+ (1') are described, as is the application of 1 in a dye-sensitized photoelectrosynthesis cell (DSPEC) for solar water splitting. Furthermore, on SnO 2/TiO 2 core–shell electrodes in a DSPEC configuration with a Pt cathode, the chromophore–catalyst assembly undergoes light-driven water oxidation at pH 5.7 in a 0.1 M acetate buffer, 0.5 M in NaClO 4. We observed photocurrents of ~0.85 mA cm –2, with illumination by a 100more » mW cm –2 white light source, after 30 s under a 0.1 V vs Ag/AgCl applied bias with a faradaic efficiency for O 2 production of 74% measured over a 5 min illumination period.« less

Light-Driven Water Splitting by a Covalently Linked Ruthenium-Based Chromophore–Catalyst Assembly

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sherman, Benjamin D.; Xie, Yan; Sheridan, Matthew V.

The preparation and characterization of new Ru(II) polypyridyl-based chromophore–catalyst assemblies, [(4,4'-PO 3H 2-bpy) 2Ru(4-Mebpy-4'-epic)Ru(bda)(pic)] 2+ (1, bpy = 2,2'-bipyridine; 4-Mebpy-4'-epic = 4-(4-methylbipyridin-4'-yl-ethyl)-pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate; pic = 4-picoline), and [(bpy) 2Ru(4-Mebpy-4'-epic)Ru(bda)(pic)] 2+ (1') are described, as is the application of 1 in a dye-sensitized photoelectrosynthesis cell (DSPEC) for solar water splitting. Furthermore, on SnO 2/TiO 2 core–shell electrodes in a DSPEC configuration with a Pt cathode, the chromophore–catalyst assembly undergoes light-driven water oxidation at pH 5.7 in a 0.1 M acetate buffer, 0.5 M in NaClO 4. We observed photocurrents of ~0.85 mA cm –2, with illumination by a 100more » mW cm –2 white light source, after 30 s under a 0.1 V vs Ag/AgCl applied bias with a faradaic efficiency for O 2 production of 74% measured over a 5 min illumination period.« less

Origin of the improved photocatalytic activity of Cu incorporated TiO2 for hydrogen generation from water

NASA Astrophysics Data System (ADS)

Hu, Qianqian; Huang, Jiquan; Li, Guojing; Jiang, Yabin; Lan, Hai; Guo, Wang; Cao, Yongge

2016-09-01

Cu incorporated TiO2 has been regarded as a low-cost photocatalyst with excellent photocatalytic performance for water splitting. Here we try to exploit the origin of its high reactivity by fabricating a series of Cu incorporated TiO2 films with the same Cu content under different atmosphere. Based on the comprehensive structure and surface characterizations, it is found that CuO is unstable and will be reduced to Cu2O or even to metallic Cu under light irradiation during the photocatalytic reaction, and Cu2O is an efficient co-catalyst that promotes the separation of photogenerated carriers while metallic Cu can further boost the photocatalytic activity. Besides, it is also noticed that the chemisorbed oxygen on the particle surface blocks the water splitting. By depositing TiO2 films under oxygen rich condition, oxygen vacancy is decreased greatly, which facilitates the removal of chemisorbed oxygen and the formation of metallic Cu during photocatalytic reaction, resulting in an ultra-high H2 evolution rate of 2.80 μmol cm-2 h-1, which is about 55 times higher than that of pure TiO2.

Two-step electrodeposition to fabricate the p-n heterojunction of a Cu2O/BiVO4 photoanode for the enhancement of photoelectrochemical water splitting.

PubMed

Bai, Shouli; Liu, Jingchao; Cui, Meng; Luo, Ruixian; He, Jing; Chen, Aifan

2018-05-15

A Cu2O/BiVO4 p-n heterojunction based photoanode in photoelectrochemical (PEC) water splitting is fabricated by a two-step electrodeposition method on an FTO substrate followed by annealing treatment. The structures and properties of the samples are characterized by XRD, FESEM, HRTEM, XPS and UV-visible spectra. The photoelectrochemical activity of the photoanode in water oxidation has been investigated and measured in a three electrode quartz cell system; the obtained maximum photocurrent density of 1.72 mA cm-2 at 1.23 V vs. RHE is 4.5 times higher than that of pristine BiVO4 thin films (∼0.38 mA cm-2). The heterojunction based photoanode also exhibits a tremendous cathodic shift of the onset potential (∼420 mV) and enhancement in the IPCE value by more than 4-fold. The enhanced photoelectrochemical properties of the Cu2O/BiVO4 photoelectrode are attributed to the efficient separation of the photoexcited electron-hole pairs caused by the inner electronic field (IEF) of the p-n heterojunction.

Fully Depleted Ti-Nb-Ta-Zr-O Nanotubes: Interfacial Charge Dynamics and Solar Hydrogen Production.

PubMed

Chiu, Yi-Hsuan; Lai, Ting-Hsuan; Chen, Chun-Yi; Hsieh, Ping-Yen; Ozasa, Kazunari; Niinomi, Mitsuo; Okada, Kiyoshi; Chang, Tso-Fu Mark; Matsushita, Nobuhiro; Sone, Masato; Hsu, Yung-Jung

2018-05-01

Poor kinetics of hole transportation at the electrode/electrolyte interface is regarded as a primary cause for the mediocre performance of n-type TiO 2 photoelectrodes. By adopting nanotubes as the electrode backbone, light absorption and carrier collection can be spatially decoupled, allowing n-type TiO 2 , with its short hole diffusion length, to maximize the use of the available photoexcited charge carriers during operation in photoelectrochemical (PEC) water splitting. Here, we presented a delicate electrochemical anodization process for the preparation of quaternary Ti-Nb-Ta-Zr-O mixed-oxide (denoted as TNTZO) nanotube arrays and demonstrated their utility in PEC water splitting. The charge-transfer dynamics for the electrodes was investigated using time-resolved photoluminescence, electrochemical impedance spectroscopy, and the decay of open-circuit voltage analysis. Data reveal that the superior photoactivity of TNTZO over pristine TiO 2 originated from the introduction of Nd, Ta, and Zr elements, which enhanced the amount of accessible charge carriers, modified the electronic structure, and improved the hole injection kinetics for expediting water splitting. By modulating the water content of the electrolyte employed in the anodization process, the wall thickness of the grown TNTZO nanotubes can be reduced to a size smaller than that of the depletion layer thickness, realizing a fully depleted state for charge carriers to further advance the PEC performance. Hydrogen evolution tests demonstrate the practical efficacy of TNTZO for realizing solar hydrogen production. Furthermore, with the composition complexity and fully depleted band structure, the present TNTZO nanotube arrays may offer a feasible and universal platform for the loading of other semiconductors to construct a sophisticated heterostructure photoelectrode paradigm, in which the photoexcited charge carriers can be entirely utilized for efficient solar-to-fuel conversion.

Flagged uniform particle splitting for variance reduction in proton and carbon ion track-structure simulations

NASA Astrophysics Data System (ADS)

Ramos-Méndez, José; Schuemann, Jan; Incerti, Sebastien; Paganetti, Harald; Schulte, Reinhard; Faddegon, Bruce

2017-08-01

Flagged uniform particle splitting was implemented with two methods to improve the computational efficiency of Monte Carlo track structure simulations with TOPAS-nBio by enhancing the production of secondary electrons in ionization events. In method 1 the Geant4 kernel was modified. In method 2 Geant4 was not modified. In both methods a unique flag number assigned to each new split electron was inherited by its progeny, permitting reclassification of the split events as if produced by independent histories. Computational efficiency and accuracy were evaluated for simulations of 0.5-20 MeV protons and 1-20 MeV u-1 carbon ions for three endpoints: (1) mean of the ionization cluster size distribution, (2) mean number of DNA single-strand breaks (SSBs) and double-strand breaks (DSBs) classified with DBSCAN, and (3) mean number of SSBs and DSBs classified with a geometry-based algorithm. For endpoint (1), simulation efficiency was 3 times lower when splitting electrons generated by direct ionization events of primary particles than when splitting electrons generated by the first ionization events of secondary electrons. The latter technique was selected for further investigation. The following results are for method 2, with relative efficiencies about 4.5 times lower for method 1. For endpoint (1), relative efficiency at 128 split electrons approached maximum, increasing with energy from 47.2  ±  0.2 to 66.9  ±  0.2 for protons, decreasing with energy from 51.3  ±  0.4 to 41.7  ±  0.2 for carbon. For endpoint (2), relative efficiency increased with energy, from 20.7  ±  0.1 to 50.2  ±  0.3 for protons, 15.6  ±  0.1 to 20.2  ±  0.1 for carbon. For endpoint (3) relative efficiency increased with energy, from 31.0  ±  0.2 to 58.2  ±  0.4 for protons, 23.9  ±  0.1 to 26.2  ±  0.2 for carbon. Simulation results with and without splitting agreed within 1% (2 standard deviations) for endpoints (1) and (2), within 2% (1 standard deviation) for endpoint (3). In conclusion, standard particle splitting variance reduction techniques can be successfully implemented in Monte Carlo track structure codes.

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

NASA Astrophysics Data System (ADS)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery

PubMed Central

Kim, Gonu; Oh, Misol; Park, Yiseul

2016-01-01

As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a “solar water battery”. The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E0 (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge. PMID:27629362

Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery.

PubMed

Kim, Gonu; Oh, Misol; Park, Yiseul

2016-09-15

As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a "solar water battery". The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E(0) (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge.

Photoelectrochemical hydrogen production from biomass derivatives and water.

PubMed

Lu, Xihong; Xie, Shilei; Yang, Hao; Tong, Yexiang; Ji, Hongbing

2014-11-21

Hydrogen, a clean energy carrier with high energy capacity, is a very promising candidate as a primary energy source for the future. Photoelectrochemical (PEC) hydrogen production from renewable biomass derivatives and water is one of the most promising approaches to producing green chemical fuel. Compared to water splitting, hydrogen production from renewable biomass derivatives and water through a PEC process is more efficient from the viewpoint of thermodynamics. Additionally, the carbon dioxide formed can be re-transformed into carbohydrates via photosynthesis in plants. In this review, we focus on the development of photoanodes and systems for PEC hydrogen production from water and renewable biomass derivatives, such as methanol, ethanol, glycerol and sugars. We also discuss the future challenges and opportunities for the design of the state-of-the-art photoanodes and PEC systems for hydrogen production from biomass derivatives and water.

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

NASA Astrophysics Data System (ADS)

May, Matthias M.; Lewerenz, Hans-Joachim; Lackner, David; Dimroth, Frank; Hannappel, Thomas

2015-09-01

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators.

Efficient direct solar-to-hydrogen conversion by in situ interface transformation of a tandem structure

PubMed Central

May, Matthias M.; Lewerenz, Hans-Joachim; Lackner, David; Dimroth, Frank; Hannappel, Thomas

2015-01-01

Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators. PMID:26369620

Hydrogen production from water-glucose solution over NiO/La-NaTaO3 photocatalyst

NASA Astrophysics Data System (ADS)

Mardian, R.; Husin, H.; Pontas, K.; Zaki, M.; Asnawi, T. M.; Ahmadi

2018-03-01

This paper reports the evaluation of La-NaTaO3 photocatalyst performance in producing hydrogen from water-glucose solution. The main goal of the studies is to investigate the influence of glucose as a sacrificial reagent on the photocatalytic efficiency in water splitting reactions under ultraviolet (UV) irradiation. Photocatalyst has been fabricated via sol-gel method and being confirmed using x-ray diffraction (XRD) and scanning electron microscopy (SEM). Nickel loaded La-NaTaO3 photocatalyst are prepared by impregnation method. It was observed that the prepared photocatalysts displayed particle sizes in the 30-250 nm range with orthorhombic structure. Their photocatalytic activity for hydrogen production via water splitting was conducted in a Pyrex glass reactor under UV light irradiation. The aqueous solution contained glucose employed as a renewable organic scavenger. A significant improvement in hydrogen production was observed in glucose-water mixtures and NiO loaded photocatalyst. The prepared La-NaTaO3 showed that the highest activity for hydrogen generation of 35.1 mmol h-1.g-1 was obtained at 0.10 mol.L-1 glucose and 0.3 wt.% NiO. This suggests the important role played by the glucose as electron donor and loading nickel on La-NaTaO3 as a cocatalyst increasing electron storage and suppressing electron-hole recombination.

[Effect of water-nitrogen coupling on photosynthesis and ultrastructure of cucumber leaves under CO2 enrichment].

PubMed

Cui, Qing Qing; Dong, Yan Hong; Li, Man; Zhang, Wen Dong; Liu, Bin Bin; Ai, Xi Zhen; Bi, Huan Gai; Li, Qing Ming

2017-04-18

Using split plot and then-split plot design, effects of water-nitrogen coupling on photosynthesis and ultrastructure of cucumber (Cucumis sativus) (Jinyou No.35) under CO 2 enrichment were investigated. The main plot had two CO 2 concentrations: ambient CO 2 concentration (400 μmol·mol -1 , A) and doubled CO 2 concentration (800±20 μmol·mol -1 , E). The split plot had two treatments: no drought stress (95% of field capacity, W) and drought stress (75% of field capacity, D). The then-split plot contained low nitrogen treatment (450 kg·hm -2 , N 1 ) and high nitrogen treatment (900 kg·hm -2 , N 2 ). The results showed that under the condition of drought and high nitrogen, increasing CO 2 enhanced the cucumber plant height, and no matter what kinds of water treatment, CO 2 enrichment increased the leaf area significantly under high nitrogen. Under the condition of normal irrigation, the photosynthetic rate, stomatal conductance and transpiration rate of high nitrogen treatment were higher than low nitrogen treatment, while it was under the drought condition. Elevated CO 2 enhanced the water use efficiency of cucumber leaf which increased with increasing nitrogen application rate. Under drought stress, cucumber adaxial surface porosity density was increased, and the CO 2 enrichment and high nitrogen significantly reduced the stomatal density. Increasing nitrogen application improved the number of chloroplast, and reduced that of starch grains. Drought stress decreased the number of chloroplast, but tended to promote the number of starch grains. Drought stress increased the chloroplast length and width, and the size of the starch grains, while high nitrogen reduced the length and width of the chloroplast and starch grains. CO 2 enrichment and high nitrogen increased grana thickness and layers (except ADN 2 ), and the slice layer of EDN 2 was significantly higher than that of ADN 2 . In conclusion, CO 2 enrichment and suitable water and nitrogen could promote the development of chloroplast thylakoid membrane system, significantly increase the thickness of grana and the number of grana lamella, and effectively improve the chloroplast structure of cucumber, which would benefit the photosynthesis of cucumber plants and ability to utilize CO 2 and water and nitrogen.

Growth of p-type hematite by atomic layer deposition and its utilization for improved solar water splitting.

PubMed

Lin, Yongjing; Xu, Yang; Mayer, Matthew T; Simpson, Zachary I; McMahon, Gregory; Zhou, Sa; Wang, Dunwei

2012-03-28

Mg-doped hematite (α-Fe(2)O(3)) was synthesized by atomic layer deposition (ALD). The resulting material was identified as p-type with a hole concentration of ca. 1.7 × 10(15) cm(-3). When grown on n-type hematite, the p-type layer was found to create a built-in field that could be used to assist photoelectrochemical water splitting reactions. A nominal 200 mV turn-on voltage shift toward the cathodic direction was measured, which is comparable to what has been measured using water oxidation catalysts. This result suggests that it is possible to achieve desired energetics for solar water splitting directly on metal oxides through advanced material preparations. Similar approaches may be used to mitigate problems caused by energy mismatch between water redox potentials and the band edges of hematite and many other low-cost metal oxides, enabling practical solar water splitting as a means for solar energy storage.

Dual Tuning of Ni-Co-A (A = P, Se, O) Nanosheets by Anion Substitution and Holey Engineering for Efficient Hydrogen Evolution.

PubMed

Fang, Zhiwei; Peng, Lele; Qian, Yumin; Zhang, Xiao; Xie, Yujun; Cha, Judy J; Yu, Guihua

2018-04-18

Seeking earth-abundant electrocatalysts with high efficiency and durability has become the frontier of energy conversion research. Mixed-transition-metal (MTM)-based electrocatalysts, owing to the desirable electrical conductivity, synergistic effect of bimetal atoms, and structural stability, have recently emerged as new-generation hydrogen evolution reaction (HER) electrocatalysts. However, the correlation between anion species and their intrinsic electrocatalytic properties in MTM-based electrocatalysts is still not well understood. Here we present a novel approach to tuning the anion-dependent electrocatalytic characteristics in MTM-based catalyst for HER, using holey Ni/Co-based phosphides/selenides/oxides (Ni-Co-A, A = P, Se, O) as the model materials. The electrochemical results, combined with the electrical conductivity measurement and DFT calculation, reveal that P substitution could modulate the electron configuration, lower the hydrogen adsorption energy, and facilitate the desorption of hydrogen on the active sites in Ni-Co-A holey nanostructures, resulting in superior HER catalytic activity. Accordingly we fabricate the NCP holey nanosheet electrocatalyst for HER with an ultralow onset overpotential of nearly zero, an overpotential of 58 mV, and long-term durability, along with an applied potential of 1.56 V to boost overall water splitting at 10 mA cm -2 , among the best electrocatalysts reported for non-noble-metal catalysts to date. This work not only presents a deeper understanding of the intrinsic HER electrocatalytic properties for MTM-based electrocatalyst with various anion species but also offers new insights to better design efficient and durable water-splitting electrocatalysts.

Splitting efficiency and interference effects in a Cooper pair splitter based on a triple quantum dot with ferromagnetic contacts

NASA Astrophysics Data System (ADS)

Bocian, Kacper; Rudziński, Wojciech; Weymann, Ireneusz

2018-05-01

We theoretically study the spin-resolved subgap transport properties of a Cooper pair splitter based on a triple quantum dot attached to superconducting and ferromagnetic leads. Using the Keldysh Green's function formalism, we analyze the dependence of the Andreev conductance, Cooper pair splitting efficiency, and tunnel magnetoresistance on the gate and bias voltages applied to the system. We show that the system's transport properties are strongly affected by spin dependence of tunneling processes and quantum interference between different local and nonlocal Andreev reflections. We also study the effects of finite hopping between the side quantum dots on the Andreev current. This allows for identifying the optimal conditions for enhancing the Cooper pair splitting efficiency of the device. We find that the splitting efficiency exhibits a nonmonotonic dependence on the degree of spin polarization of the leads and the magnitude and type of hopping between the dots. An almost perfect splitting efficiency is predicted in the nonlinear response regime when the energies of the side quantum dots are tuned to the energies of the corresponding Andreev bound states. In addition, we analyzed features of the tunnel magnetoresistance (TMR) for a wide range of the gate and bias voltages, as well as for different model parameters, finding the corresponding sign changes of the TMR in certain transport regimes. The mechanisms leading to these effects are thoroughly discussed.

An efficient synthesis of symmetric and unsymmetric bis-(β-aminoamides) via Ugi multicomponent reaction.

PubMed

La Spisa, Fabio; Feo, Alberto; Mossetti, Riccardo; Tron, Gian Cesare

2012-12-07

A library of symmetrical and unsymmetrical bis-(β-aminoamides) has been prepared starting from symmetrical secondary diamines by using a double Ugi four-component reaction. A sacrifical Mumm rearrangement, thanks to the use of 2-hydroxymethyl benzoic acid, is necessary to suppress the competing split-Ugi reaction, increasing the yield and simplifying the purification step. The scope, the reaction conditions, and the role of water in trapping the nitrilium intermediate are also discussed.

Oxidation driven ZnS Core-ZnO shell photocatalysts under controlled oxygen atmosphere for improved photocatalytic solar water splitting

NASA Astrophysics Data System (ADS)

Bak, Daegil; Kim, Jung Hyeun

2018-06-01

Zinc type photocatalysts attract great attentions in solar hydrogen production due to their easy availability and benign environmental characteristics. Spherical ZnS particles are synthesized with a facile hydrothermal method, and they are further used as core materials to introduce ZnO shell layer surrounding the core part by partial oxidation under controlled oxygen contents. The resulting ZnS core-ZnO shell photocatalysts represent the heterostructural type II band alignment. The existence of oxide layer also influences on proton adsorption power with an aid of strong base cites derived from highly electronegative oxygen atoms in ZnO shell layer. Photocatalytic water splitting reaction is performed to evaluate catalyst efficiency under standard one sun condition, and the highest hydrogen evolution rate (1665 μmolg-1h-1) is achieved from the sample oxidized at 16.2 kPa oxygen pressure. This highest hydrogen production rate is achieved in cooperation with increased light absorption and promoted charge separations. Photoluminescence analysis reveals that the improved visible light response is obtained after thermal oxidation process due to the oxygen vacancy states in the ZnO shell layer. Therefore, overall photocatalytic efficiency in solar hydrogen production is enhanced by improved charge separations, crystallinity, and visible light responses from the ZnS core-ZnO shell structures induced by thermal oxidation.

S-TiO2/S-reduced graphene oxide for enhanced photoelectrochemical water splitting

NASA Astrophysics Data System (ADS)

Elbakkay, Mohamed H.; El Rouby, Waleed M. A.; El-Dek, S. I.; Farghali, Ahmed A.

2018-05-01

Sulfur-doped titanium oxide on the surface of sulfur-doped reduced graphene oxide nanocomposites (S-TiO2/S-RGO) were successfully synthesized for the first time through a simple low cost solvothermal reaction process. The sulfur doping was detected in both TiO2 matrix and carbon framework structure of reduced graphene oxide using X-ray photoelectron spectroscopy (XPS) and Energy-dispersive X-ray spectroscopy (EDX). Cross-sectional AFM analysis of S-RGO nanosheets reveals a thickness of 0.51 nm which is much thinner than those previously reported of heteroatom doped-RGO, confirming the single-layer feature. When the as-prepared (S-TiO2/S-RGO) nanocomposites are utilized as photoanodes for photoelectrochemical (PEC) water splitting, they exhibited an enhanced photoelectrochemical performance and long-term stability. The photocurrent density of S-TiO2/S-RGO(0.2) photoanode revealed 3.36 mA/cm2 at 1 V vs Ag/AgCl which is considered 3 times compared to bare synthesized TiO2. This improvement in the photocurrent density was attributed to the increased separation rate of photogenerated electrons and holes and efficient visible light harvesting as a result of the successful combination of the S-TiO2 and the S-RGO in the same nanocomposite photoanode. This promising result presents a new approach for the synthesis of high-efficient future metal-free photoelectrocatalysts.

Multilayer Ni/Fe thin films as oxygen evolution catalysts for solar fuel production

NASA Astrophysics Data System (ADS)

Biset-Peiró, M.; Murcia-López, S.; Fàbrega, C.; Morante, J. R.; Andreu, T.

2017-03-01

The slow kinetics and high overpotential of the oxygen evolution reaction is one of the main limiting factors to achieve the minimum required performances of the so-called photoelectrochemical water splitting systems. An oxygen evolution catalyst (OEC) becomes essential in order to perform this process with higher efficiency. Herein, we report the physical, optical and electrochemical characterization of multilayer Ni/Fe thin films as earth-abundant OEC, to avoid the use of platinum group metals (PGM). Uniform films of thicknesses ranging from 1 to 10 nm were fabricated by sequential and alternate thermal evaporation of Ni and Fe. It was found that the successive deposition allows the fabrication of a Ni terminated surface that does not need activation due to the Fe underlayer. The lowest overpotential achieved for NiFe was 370 mV at 10 mA cm-2 and a Tafel slope of 37 mV dec-1 with 1 nm thickness and 95% transmittance. Finally, NiFe OEC was implemented on top of Mo:BiVO4 photoanodes which resulted in a reduction of the open circuit potential of 0.2 V and up to five fold increase of the oxidation efficiency at 0.7 VRHE. The results presented facilitate the practical implementation of BiVO4 photoanodes in tandem configuration for bias free photoassisted water splitting.

Controlled Synthesis of CuS/TiO2 Heterostructured Nanocomposites for Enhanced Photocatalytic Hydrogen Generation through Water Splitting.

PubMed

Chandra, Moumita; Bhunia, Kousik; Pradhan, Debabrata

2018-04-16

Photocatalytic hydrogen (H 2 ) generation through water splitting has attracted substantial attention as a clean and renewable energy generation process that has enormous potential in converting solar-to-chemical energy using suitable photocatalysts. The major bottleneck in the development of semiconductor-based photocatalysts lies in poor light absorption and fast recombination of photogenerated electron-hole pairs. Herein we report the synthesis of CuS/TiO 2 heterostructured nanocomposites with varied TiO 2 contents via simple hydrothermal and solution-based process. The morphology, crystal structure, composition, and optical properties of the as-synthesized CuS/TiO 2 hybrids are evaluated in detail. Controlling the CuS/TiO 2 ratio to an optimum value leads to the highest photocatalytic H 2 production rate of 1262 μmol h -1 g -1 , which is 9.7 and 9.3 times higher than that of pristine TiO 2 nanospindles and CuS nanoflakes under irradiation, respectively. The enhancement in the H 2 evolution rate is attributed to increased light absorption and efficient charge separation with an optimum CuS coverage on TiO 2 . The photoluminescence and photoelectrochemical measurements further confirm the efficient separation of charge carriers in the CuS/TiO 2 hybrid. The mechanism and synergistic role of CuS and TiO 2 semiconductors for enhanced photoactivity is further delineated.

NiSe-Ni0.85 Se Heterostructure Nanoflake Arrays on Carbon Paper as Efficient Electrocatalysts for Overall Water Splitting.

PubMed

Chen, Yajie; Ren, Zhiyu; Fu, Huiying; Zhang, Xin; Tian, Guohui; Fu, Honggang

2018-06-01

Fabricating cost-effective, bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in basic media is critical for renewable energy generation. Here, NiSe/CP, Ni 0.85 Se/CP, and NiSe-Ni 0.85 Se/CP heterostructure catalysts with different phase constitutions are successfully prepared through in situ selenylation of a NiO nanoflake array oriented on carbon paper (CP) by tuning the original Ni/Se molar ratio of the raw materials. The relationship between the crystal phase component and electrocatalytic activity is systematically studied. Benefiting from the synergetic effect of the intrinsic metallic state, facile charge transport, abundant catalytic active sites, and multiple electrolyte transmission paths, the optimized NiSe-Ni 0.85 Se/CP exhibits a remarkably higher catalytic activity for both the HER and OER than single-phase NiSe/CP and Ni 0.85 Se/CP. A current density of 10 mA cm -2 at 1.62 V and a high stability can be obtained by using NiSe-Ni 0.85 Se/CP as both the cathode and anode for overall water splitting under alkaline conditions. Density functional theory calculations confirm that H and OH - can be more easily adsorbed on NiSe-Ni 0.85 Se than on NiSe and Ni 0.85 Se. This study paves the way for enhancing the overall water splitting performance of nickel selenides by fabricating heterophase junctions using nickel selenides with different phases. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Performance of Photoelectrochemical Water Splitting with ITO@α-Fe2O3 Core-Shell Nanowire Array as Photoanode.

PubMed

Yang, Jie; Bao, Chunxiong; Yu, Tao; Hu, Yingfei; Luo, Wenjun; Zhu, Weidong; Fu, Gao; Li, Zhaosheng; Gao, Hao; Li, Faming; Zou, Zhigang

2015-12-09

Hematite (α-Fe2O3) is one of the most promising candidates for photoelectrodes in photoelectrochemical water splitting system. However, the low visible light absorption coefficient and short hole diffusion length of pure α-Fe2O3 limits the performance of α-Fe2O3 photoelectrodes in water splitting. Herein, to overcome these drawbacks, single-crystalline tin-doped indium oxide (ITO) nanowire core and α-Fe2O3 nanocrystal shell (ITO@α-Fe2O3) electrodes were fabricated by covering the chemical vapor deposited ITO nanowire array with compact thin α-Fe2O3 nanocrystal film using chemical bath deposition (CBD) method. The J-V curves and IPCE of ITO@α-Fe2O3 core-shell nanowire array electrode showed nearly twice as high performance as those of the α-Fe2O3 on planar Pt-coated silicon wafers (Pt/Si) and on planar ITO substrates, which was considered to be attributed to more efficient hole collection and more loading of α-Fe2O3 nanocrystals in the core-shell structure than planar structure. Electrochemical impedance spectra (EIS) characterization demonstrated a low interface resistance between α-Fe2O3 and ITO nanowire arrays, which benefits from the well contact between the core and shell. The stability test indicated that the prepared ITO@α-Fe2O3 core-shell nanowire array electrode was stable under AM1.5 illumination during the test period of 40,000 s.

A Ga2O3 underlayer as an isomorphic template for ultrathin hematite films toward efficient photoelectrochemical water splitting.

PubMed

Hisatomi, Takashi; Brillet, Jérémie; Cornuz, Maurin; Le Formal, Florian; Tétreault, Nicolas; Sivula, Kevin; Grätzel, Michael

2012-01-01

Hematite photoanodes for photoelectrochemical (PEC) water splitting are often fabricated as extremely-thin films to minimize charge recombination because of the short diffusion lengths of photoexcited carriers. However, poor crystallinity caused by structural interaction with a substrate negates the potential of ultrathin hematite photoanodes. This study demonstrates that ultrathin Ga2O3 underlayers, which were deposited on conducting substrates prior to hematite layers by atomic layer deposition, served as an isomorphic (corundum-type) structural template for ultrathin hematite and improved the photocurrent onset of PEC water splitting by 0.2 V. The benefit from Ga2O3 underlayers was most pronounced when the thickness of the underlayer was approximately 2 nm. Thinner underlayers did not work effectively as a template presumably because of insufficient crystallinity of the underlayer, while thicker ones diminished the PEC performance of hematite because the underlayer prevented electron injection from hematite to a conductive substrate due to the large conduction band offset. The enhancement of PEC performance by a Ga2O3 underlayer was more significant for thinner hematite layers owing to greater margins for improving the crystallinity of ultrathin hematite. It was confirmed that a Ga2O3 underlayer was applicable to a rough conducting substrate loaded with Sb-doped SnO2 nanoparticles, improving the photocurrent by a factor of 1.4. Accordingly, a Ga2O3 underlayer could push forward the development of host-guest-type nanocomposites consisting of highly-rough substrates and extremely-thin hematite absorbers.

One‐dimensional TiO2 Nanotube Photocatalysts for Solar Water Splitting

PubMed Central

Ge, Mingzheng; Li, Qingsong; Cao, Chunyan; Huang, Jianying; Li, Shuhui; Zhang, Songnan; Chen, Zhong; Zhang, Keqin; Al‐Deyab, Salem S.

2016-01-01

Hydrogen production from water splitting by photo/photoelectron‐catalytic process is a promising route to solve both fossil fuel depletion and environmental pollution at the same time. Titanium dioxide (TiO2) nanotubes have attracted much interest due to their large specific surface area and highly ordered structure, which has led to promising potential applications in photocatalytic degradation, photoreduction of CO2, water splitting, supercapacitors, dye‐sensitized solar cells, lithium‐ion batteries and biomedical devices. Nanotubes can be fabricated via facile hydrothermal method, solvothermal method, template technique and electrochemical anodic oxidation. In this report, we provide a comprehensive review on recent progress of the synthesis and modification of TiO2 nanotubes to be used for photo/photoelectro‐catalytic water splitting. The future development of TiO2 nanotubes is also discussed. PMID:28105391

Highly efficient photocatalytic conversion of solar energy to hydrogen by WO3/BiVO4 core-shell heterojunction nanorods

NASA Astrophysics Data System (ADS)

Kosar, Sonya; Pihosh, Yuriy; Bekarevich, Raman; Mitsuishi, Kazutaka; Mawatari, Kazuma; Kazoe, Yutaka; Kitamori, Takehiko; Tosa, Masahiro; Tarasov, Alexey B.; Goodilin, Eugene A.; Struk, Yaroslav M.; Kondo, Michio; Turkevych, Ivan

2018-04-01

Photocatalytic splitting of water under solar light has proved itself to be a promising approach toward the utilization of solar energy and the generation of environmentally friendly fuel in a form of hydrogen. In this work, we demonstrate highly efficient solar-to-hydrogen conversion efficiency of 7.7% by photovoltaic-photoelectrochemical (PV-PEC) device based on hybrid MAPbI3 perovskite PV cell and WO3/BiVO4 core-shell nanorods PEC cell tandem that utilizes spectral splitting approach. Although BiVO4 is characterized by intrinsically high recombination rate of photogenerated carriers, this is not an issue for WO3/BiVO4 core-shell nanorods, where highly conductive WO3 cores are combined with extremely thin absorber BiVO4 shell layer. Since the BiVO4 layer is thinner than the characteristic carrier diffusion length, the photogenerated charge carriers are separated at the WO3/BiVO4 heterojunction before their recombination. Also, such architecture provides sufficient optical thickness even for extremely thin BiVO4 layer due to efficient light trapping in the core-shell WO3/BiVO4 nanorods with high aspect ratio. We also demonstrate that the concept of fill factor can be used to compare I-V characteristics of different photoanodes regarding their optimization for PV/PEC tandem devices.

Modeling integrated photovoltaic–electrochemical devices using steady-state equivalent circuits

PubMed Central

Winkler, Mark T.; Cox, Casandra R.; Nocera, Daniel G.; Buonassisi, Tonio

2013-01-01

We describe a framework for efficiently coupling the power output of a series-connected string of single-band-gap solar cells to an electrochemical process that produces storable fuels. We identify the fundamental efficiency limitations that arise from using solar cells with a single band gap, an arrangement that describes the use of currently economic solar cell technologies such as Si or CdTe. Steady-state equivalent circuit analysis permits modeling of practical systems. For the water-splitting reaction, modeling defines parameters that enable a solar-to-fuels efficiency exceeding 18% using laboratory GaAs cells and 16% using all earth-abundant components, including commercial Si solar cells and Co- or Ni-based oxygen evolving catalysts. Circuit analysis also provides a predictive tool: given the performance of the separate photovoltaic and electrochemical systems, the behavior of the coupled photovoltaic–electrochemical system can be anticipated. This predictive utility is demonstrated in the case of water oxidation at the surface of a Si solar cell, using a Co–borate catalyst.

Earth Observations by the Expedition 19 crew

NASA Image and Video Library

2009-04-09

ISS019-E-005501 (9 April 2009) --- Split Region in Croatia is featured in this image photographed by an Expedition 19 crewmember on the International Space Station. One the world?s most rugged coastlines are located in Croatia along the Adriatic Sea. This view features the Dalmatian coastline of Croatia around the city of Split. Much of the region can be characterized by northwest-southeast oriented linear islands and embayments of the Adriatic Sea. This distinctive coastal geomorphology is the result of faulting caused by tectonic activity in the region and sea level rise. Split has a long history - the Roman Emperor Diocletian retired to Spalatum (the present-day Split) in 305, and his palace constitutes the core of the city today. The city is a popular resort destination for its historic sites, Mediterranean climate, and ready access to the Adriatic islands (such as Brac to the south). Other large cities in the region include Kastela and Trogir; together with Split, these form an almost continuous urban area bordering the coast (visible as pink regions). A thin zone marking a water boundary is visible in this image between Split and the island of Brac. It may represent a local plankton bloom, or a line of convergence between water masses creating rougher water. A unique combination of geography -- including dramatic topography that channels local winds, the complicated coastline, input of fresh water from rivers, and ample nutrients and surface oils -- makes for interesting mesoscale surface dynamics throughout the Adriatic Sea. Over the years, astronauts have taken images of the Split region using sunglint and changes in water color to highlight features like eddies, water boundaries and mixing zones between fresh waters flowing into the saltier (denser) waters of the Adriatic, and wind-driven surface currents. Split is an important transit center connecting islands in the Adriatic Sea to the Italian peninsula, and an important regional manufacturing center of goods such as solar cells, plastics, and paper products. The city was heavily industrialized during the post World War II period as a member state of Yugoslavia. By the 1980s, the marine environment bordered by Split, Kastela, and Trogir (known as Kastela Bay) had been identified as one of the most polluted areas of the Adriatic from both sewage and industrial wastes. Concerted efforts by the Croatian government and international partners to improve waste handling and treatment infrastructure over the past 10 years seem to have been successful ? both marine species and water polo players have returned to the area.

Strategies to achieve high-solids enzymatic hydrolysis of dilute-acid pretreated corn stover.

PubMed

Geng, Wenhui; Jin, Yongcan; Jameel, Hasan; Park, Sunkyu

2015-01-01

Three strategies were presented to achieve high solids loading while maximizing carbohydrate conversion, which are fed-batch, splitting/thickening, and clarifier processes. Enzymatic hydrolysis was performed at water insoluble solids (WIS) of 15% using washed dilute-acid pretreated corn stover. The carbohydrate concentration increased from 31.8 to 99.3g/L when the insoluble solids content increased from 5% to 15% WIS, while the final carbohydrate conversion was decreased from 78.4% to 73.2%. For the fed-batch process, a carbohydrate conversion efficiency of 76.8% was achieved when solid was split into 60:20:20 ratio, with all enzymes added first. For the splitting/thickening process, a carbohydrate conversion of 76.5% was realized when the filtrate was recycled to simulate a steady-state process. Lastly, the clarifier process was evaluated and the highest carbohydrate conversion of 81.4% was achieved. All of these results suggests the possibility of enzymatic hydrolysis at high solids to make the overall conversion cost-competitive. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

NASA Astrophysics Data System (ADS)

Manser, Joseph S.

The burgeoning class of metal halide perovskites constitutes a paradigm shift in the study and application of solution-processed semiconductors. Advancements in thin film processing and our understanding of the underlying structural, photophysical, and electronic properties of these materials over the past five years have led to development of perovskite solar cells with power conversion efficiencies that rival much more mature first and second-generation commercial technologies. It seems only a matter of time before the real-world impact of these compounds is put to the test. Like oxide perovskites, metal halide perovskites have ABX3 stoichiometry, where typically A is a monovalent cation, B a bivalent post-transition metal, and X a halide anion. Characterizing the behavior of photogenerated charges in metal halide perovskites is integral for understanding the operating principles and fundamental limitations of perovskite optoelectronics. The majority of studies outlined in this dissertation involve fundamental study of the prototypical organic-inorganic compound methylammonium lead iodide (CH3NH3PbI 3). Time-resolved pump-probe spectroscopy serves as a principle tool in these investigations. Excitation of a semiconductor can lead to formation of a number different excited state species and electronic complexes. Through analysis of excited state decay kinetics and optical nonlinearities in perovskite thin films, we identify spontaneous formation of a large fraction of free electrons and holes, whose presence is requisite for efficient photovoltaic operation. Following photogeneration of charge carriers in a semiconductor absorber, these species must travel large distances across the thickness of the material to realize large external quantum efficiencies and efficient carrier extraction. Using a powerful technique known as transient absorption microscopy, we directly image long-range carrier diffusion in a CH3NH3PbI 3 thin film. Charges are unambiguously shown to travel 220 nm over the course of 2 ns after photoexcitation, with an extrapolated diffusion length greater than one micrometer over the full excited state lifetime. The solution-processability of metal halide perovskites necessarily raises questions as to the properties of the solvated precursors and their connection to the final solid-state perovskite phase. Through structural and steady-state and time-resolved absorption studies, the important link between the excited state properties of the precursor components, composed of solvated and solid-state halometallate complexes, and CH3NH3PbI3 is evinced. This connection provides insight into optical nonlinearities and electronic properties of the perovskite phase. Fundamental studies of CH 3NH3PbI3 ultimately serve as a foundation for application of this and other related materials in high-performance devices. In the final chapter, the operation of CH3NH3PbI 3 solar cells in a tandem architecture is presented. The quest for economic, large scale hydrogen production has motivated the search for new materials and device designs capable of splitting water using only energy from the sun. In light of this, we introduce an all solution-processed tandem water splitting assembly composed of a BiVO4 photoanode and a single-junction CH3NH3PbI3 hybrid perovskite solar cell. This unique configuration allows efficient solar photon management, with the metal oxide photoanode selectively harvesting high energy visible photons and the underlying perovskite solar cell capturing lower energy visible-near IR wavelengths in a single-pass excitation. Operating without external bias under standard terrestrial one sun illumination, the photoanode-photovoltaic architecture, in conjunction with an earthabundant cobalt phosphate catalyst, exhibits a solar-to-hydrogen conversion efficiency of 2.5% at neutral pH. The design of low-cost tandem water splitting assemblies employing single-junction hybrid perovskite materials establishes a potentially promising new frontier for solar water splitting research.

The application of condensate water as an additional cooling media intermittently in condenser of a split air conditioning

NASA Astrophysics Data System (ADS)

Ardita, I. N.; Subagia, I. W. A.

2018-01-01

The condensate water produced by indoor a split air conditioning is usually not utilized and thrown away into the environment. The result of measurement shows that the temperature of condensate water produced by split air conditioning is quite low, that is 19-22 °C at the rate of 16-20 mL / min and it has PH balance. Under such conditions, Air Condensate produced by split air conditioning should still be recovered as an additional cooling medium on the condenser. This research will re-investigate the use of condensate water as an intermittent additional cooling of the condenser to increase the cooling capacity and performance of the air conditioning system. This research is done by experimental method whose implementation includes; designing and manufacturing of experimental equipment, mounting measuring tools, experimental data retrieval, data processing and yield analysis. The experimental results show that the use of condensate water as an intermittent additional cooling medium on split air conditioning condenser can increase the refrigeration effect about 2%, cooling capacity about 4% and 7% of COP system. Experimental results also show a decrease in power consumption in the system compressor about 3%

An Inexpensive Co-Intercalated Layered Double Hydroxide Composite with Electron Donor-Acceptor Character for Photoelectrochemical Water Splitting

PubMed Central

Zheng, Shufang; Lu, Jun; Yan, Dongpeng; Qin, Yumei; Li, Hailong; Evans, David G.; Duan, Xue

2015-01-01

In this paper, the inexpensive 4,4-diaminostilbene-2,2-disulfonate (DAS) and 4,4-dinitro-stilbene-2,2- disulfonate (DNS) anions with arbitrary molar ratios were successfully co-intercalated into Zn2Al-layered double hydroxides (LDHs). The DAS(50%)-DNS/LDHs composite exhibited the broad UV-visible light absorption and fluorescence quenching, which was a direct indication of photo-induced electron transfer (PET) process between the intercalated DAS (donor) and DNS (acceptor) anions. This was confirmed by the matched HOMO/LUMO energy levels alignment of the intercalated DAS and DNS anions, which was also compatible for water splitting. The DAS(50%)-DNS/LDHs composite was fabricated as the photoanode and Pt as the cathode. Under the UV-visible light illumination, the enhanced photo-generated current (4.67 mA/cm2 at 0.8 V vs. SCE) was generated in the external circuit, and the photoelectrochemical water split was realized. Furthermore, this photoelectrochemical water splitting performance had excellent crystalline, electrochemical and optical stability. Therefore, this novel inorganic/organic hybrid photoanode exhibited potential application prospect in photoelectrochemical water splitting. PMID:26174201

Controllable Synthesis of Ni xSe (0.5 ≤ x ≤ 1) Nanocrystals for Efficient Rechargeable Zinc-Air Batteries and Water Splitting.

PubMed

Zheng, Xuerong; Han, Xiaopeng; Liu, Hui; Chen, Jianjun; Fu, Dongju; Wang, Jihui; Zhong, Cheng; Deng, Yida; Hu, Wenbin

2018-04-25

The development of earth-abundant, highly active, and corrosion-resistant electrocatalysts to promote the oxygen reduction reaction (ORR) and oxygen and hydrogen evolution reactions (OER/HER) for rechargeable metal-air batteries and water-splitting devices is urgently needed. In this work, Ni x Se (0.5 ≤ x ≤ 1) nanocrystals with different crystal structures and compositions have been controllably synthesized and investigated as potential electrocatalysts for multifunctional ORR, OER, and HER in alkaline conditions. A novel hot-injection process at ambient pressure was developed to control the phase and composition of a series of Ni x Se by simply adjusting the added molar ratio of the nickel resource to triethylenetetramine. Electrochemical analysis reveals that Ni 0.5 Se nanocrystalline exhibits superior OER activity compared to its counterparts and is comparable to RuO 2 in terms of the low overpotential required to reach a current density of 10 mA cm -2 (330 mV), which may benefit from the pyrite-type crystal structure and Se enrichment in Ni 0.5 Se. For the ORR and HER, Ni 0.75 Se nanoparticles achieve the best performance including lower overpotentials and larger apparent current densities. Further investigations demonstrate that Ni 0.75 Se could not only provide an enhanced electrochemical active area but also facilitate electron transfer during the electrocatalytic process, thus contributing to the remarkable catalytic activity. As a practical application, the Ni 0.75 Se electrode enables rechargeable Zn-air battery with a considerable performance including a long cycling lifetime (200 cycles), high specific capacity (609 mA h g -1 based on the consumed Zn), and low overpotential (0.75 V) at 10 mA cm -2 . Meanwhile, the water-splitting cell setup with an anode of Ni 0.5 Se for the HER and a cathode of Ni 0.75 Se for the OER exhibits a considerable performance with low decay in activity of 12.9% under continuous polarization for 10 h. These results suggest the promising potential of nickel selenide nanocrystals as earth-abundant and high-performance electrocatalysts for metal-air batteries and alkaline water splitting.

Light distribution in diffractive multifocal optics and its optimization.

PubMed

Portney, Valdemar

2011-11-01

To expand a geometrical model of diffraction efficiency and its interpretation to the multifocal optic and to introduce formulas for analysis of far and near light distribution and their application to multifocal intraocular lenses (IOLs) and to diffraction efficiency optimization. Medical device consulting firm, Newport Coast, California, USA. Experimental study. Application of a geometrical model to the kinoform (single focus diffractive optical element) was expanded to a multifocal optic to produce analytical definitions of light split between far and near images and light loss to other diffraction orders. The geometrical model gave a simple interpretation of light split in a diffractive multifocal IOL. An analytical definition of light split between far, near, and light loss was introduced as curve fitting formulas. Several examples of application to common multifocal diffractive IOLs were developed; for example, to light-split change with wavelength. The analytical definition of diffraction efficiency may assist in optimization of multifocal diffractive optics that minimize light loss. Formulas for analysis of light split between different foci of multifocal diffractive IOLs are useful in interpreting diffraction efficiency dependence on physical characteristics, such as blaze heights of the diffractive grooves and wavelength of light, as well as for optimizing multifocal diffractive optics. Disclosure is found in the footnotes. Copyright © 2011 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

Application of particle splitting method for both hydrostatic and hydrodynamic cases in SPH

NASA Astrophysics Data System (ADS)

Liu, W. T.; Sun, P. N.; Ming, F. R.; Zhang, A. M.

2018-01-01

Smoothed particle hydrodynamics (SPH) method with numerical diffusive terms shows satisfactory stability and accuracy in some violent fluid-solid interaction problems. However, in most simulations, uniform particle distributions are used and the multi-resolution, which can obviously improve the local accuracy and the overall computational efficiency, has seldom been applied. In this paper, a dynamic particle splitting method is applied and it allows for the simulation of both hydrostatic and hydrodynamic problems. The splitting algorithm is that, when a coarse (mother) particle enters the splitting region, it will be split into four daughter particles, which inherit the physical parameters of the mother particle. In the particle splitting process, conservations of mass, momentum and energy are ensured. Based on the error analysis, the splitting technique is designed to allow the optimal accuracy at the interface between the coarse and refined particles and this is particularly important in the simulation of hydrostatic cases. Finally, the scheme is validated by five basic cases, which demonstrate that the present SPH model with a particle splitting technique is of high accuracy and efficiency and is capable for the simulation of a wide range of hydrodynamic problems.

Direct Z-scheme TiO2/CdS hierarchical photocatalyst for enhanced photocatalytic H2-production activity

NASA Astrophysics Data System (ADS)

Meng, Aiyun; Zhu, Bicheng; Zhong, Bo; Zhang, Liuyang; Cheng, Bei

2017-11-01

Photocatalytic H2 evolution, which utilizes solar energy via water splitting, is a promising route to deal with concerns about energy and environment. Herein, a direct Z-scheme TiO2/CdS binary hierarchical photocatalyst was fabricated via a successive ionic layer adsorption and reaction (SILAR) technique, and photocatalytic H2 production was measured afterwards. The as-prepared TiO2/CdS hybrid photocatalyst exhibited noticeably promoted photocatalytic H2-production activity of 51.4 μmol h-1. The enhancement of photocatalytic activity was ascribed to the hierarchical structure, as well as the efficient charge separation and migration from TiO2 nanosheets to CdS nanoparticles (NPs) at their tight contact interfaces. Moreover, the direct Z-scheme photocatalytic reaction mechanism was demonstrated to elucidate the improved photocatalytic performance of TiO2/CdS composite photocatalyst. The photoluminescence (PL) analysis of hydroxyl radicals were conducted to provide clues for the direct Z-scheme mechanism. This work provides a facile route for the construction of redox mediator-free Z-scheme photocatalytic system for photocatalytic water splitting.

In situ photodeposition of cobalt on CdS nanorod for promoting photocatalytic hydrogen production under visible light irradiation

NASA Astrophysics Data System (ADS)

Chen, Wei; Wang, Yanhong; Liu, Mei; Gao, Li; Mao, Liqun; Fan, Zeyun; Shangguan, Wenfeng

2018-06-01

Non-noble metal Co were loaded on CdS for enhancing photocatalytic activity of water splitting by a simple and efficient in situ photodeposition method. The Co particles with diameter ca. 5 nm were photoreduced and then loaded on the surface of CdS. The loading of Co can not only effectively promote the separation of electrons and holes photoexcited by CdS, but reduce the overpotential of hydrogen evolution as well, thus enhancing photocatalytic activity of water splitting. The highest photocatalytic H2 evolution rate of Co/CdS reaches up to 1299 μmol h-1 under visible light irradiation(λ > 420 nm) when the amount of loading is 1.0 wt%, which is 17 times of that of pure CdS and achieves 80% of that of 0.5 wt%Pt/CdS. This work not only exhibits a pathway to obtain photocatalysts with high photocatalytic activity for hydrogen production, but provides a possibility for the utilization of low cost Co as a substitute for noble metals in photocatalytic hydrogen production.

Fabrication of efficient TiO2-RGO heterojunction composites for hydrogen generation via water-splitting: Comparison between RGO, Au and Pt reduction sites

NASA Astrophysics Data System (ADS)

El-Bery, Haitham M.; Matsushita, Yoshihisa; Abdel-moneim, Ahmed

2017-11-01

A facile one-step synthesis approach of M/TiO2/RGO (M = Au or Pt) ternary composite by hydrothermal treatment for hydrogen generation via water-splitting was investigated. Photocurrent response measurements revealed that TiO2 (P25) nanoparticles anchored on the reduced graphene oxide (RGO) surface exhibited a p-n heterojunction interface by changing the photocurrent direction with the applied bias from reverse to forward potential. H2 evolution rate of TiO2/RGO (5 wt.%) composite was substantially enhanced by 12-fold in comparison to bare TiO2 under simulated solar light irradiation. Cyclic volatmmetry measurements manifested, that the optimized 0.3 wt.% of platinum metal loaded on TiO2/RGO composite was the most active catalytic reduction sites for hydrogen generation reaction with an initial hydrogen rate of 670 μmol h-1. This study sheds the light on the tunable semiconductor type of TiO2/RGO composite fabricated by solution mixing pathway and its merits to improve the photocatalytic activity.

Interface induce growth of intermediate layer for bandgap engineering insights into photoelectrochemical water splitting

PubMed Central

Zhang, Jian; Zhang, Qiaoxia; Wang, Lianhui; Li, Xing’ao; Huang, Wei

2016-01-01

A model of interface induction for interlayer growing is proposed for bandgap engineering insights into photocatalysis. In the interface of CdS/ZnS core/shell nanorods, a lamellar solid solution intermediate with uniform thickness and high crystallinity was formed under interface induction process. Merged the novel charge carrier transfer layer, the photocurrent of the core/shell/shell nanorod (css-NR) array was significantly improved to 14.0 mA cm−2 at 0.0 V vs. SCE, nearly 8 times higher than that of the perfect CdS counterpart and incident photon to electron conversion efficiency (IPCE) values above 50% under AM 1.5G irradiation. In addition, this array photoelectrode showed excellent photocatalytic stability over 6000 s. These results suggest that the CdS/Zn1−xCdxS/ZnS css-NR array photoelectrode provides a scalable charge carrier transfer channel, as well as durability, and therefore is promising to be a large-area nanostructured CdS-based photoanodes in photoelectrochemical (PEC) water splitting system. PMID:27250648

Economizing Production of Diverse 2D Layered Metal Hydroxides for Efficient Overall Water Splitting.

PubMed

Zheng, Zongmin; Lin, Lele; Mo, Shiguang; Ou, Daohui; Tao, Jing; Qin, Ruixuan; Fang, Xiaoliang; Zheng, Nanfeng

2018-06-01

2D layered metal hydroxides (LMH) are promising materials for electrochemical energy conversion and storage. Compared with exfoliation of bulk layered materials, wet chemistry synthesis of 2D LMH materials under mild conditions still remains a big challenge. Here, an "MgO-mediated strategy" for mass production of various 2D LMH nanosheets is presented by hydrolyzing MgO in metal salt aqueous solutions at room temperature. Benefiting from this economical and scalable strategy, ultrathin LMH nanosheets (M = Ni, Fe, Co, NiFe, and NiCo) and their derivatives (e.g., metal oxides and sulfides) can be synthesized in high yields. More importantly, this strategy opens up opportunities to fabricate hierarchically structured LMH nanosheets, resulting in high-performance electrocatalysts for the oxygen- and hydrogen-evolution reactions to realize stable overall water splitting with a low cell voltage of 1.55 V at 10 mA cm -2 . This work provides a powerful platform for the synthesis and applications of 2D materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

DOE PAGES

Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.; ...

2016-11-07

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. We demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co 3 O 4 /Co(OH) 2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. Furthermore, these films comprise compact and continuous nanocrystalline Co 3 O 4more » spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH) 2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p + n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.« less

Generalized field-splitting algorithms for optimal IMRT delivery efficiency.

PubMed

Kamath, Srijit; Sahni, Sartaj; Li, Jonathan; Ranka, Sanjay; Palta, Jatinder

2007-09-21

Intensity-modulated radiation therapy (IMRT) uses radiation beams of varying intensities to deliver varying doses of radiation to different areas of the tissue. The use of IMRT has allowed the delivery of higher doses of radiation to the tumor and lower doses to the surrounding healthy tissue. It is not uncommon for head and neck tumors, for example, to have large treatment widths that are not deliverable using a single field. In such cases, the intensity matrix generated by the optimizer needs to be split into two or three matrices, each of which may be delivered using a single field. Existing field-splitting algorithms used the pre-specified arbitrary split line or region where the intensity matrix is split along a column, i.e., all rows of the matrix are split along the same column (with or without the overlapping of split fields, i.e., feathering). If three fields result, then the two splits are along the same two columns for all rows. In this paper we study the problem of splitting a large field into two or three subfields with the field width as the only constraint, allowing for an arbitrary overlap of the split fields, so that the total MU efficiency of delivering the split fields is maximized. Proof of optimality is provided for the proposed algorithm. An average decrease of 18.8% is found in the total MUs when compared to the split generated by a commercial treatment planning system and that of 10% is found in the total MUs when compared to the split generated by our previously published algorithm.

Hybrid bioinorganic approach to solar-to-chemical conversion.

PubMed

Nichols, Eva M; Gallagher, Joseph J; Liu, Chong; Su, Yude; Resasco, Joaquin; Yu, Yi; Sun, Yujie; Yang, Peidong; Chang, Michelle C Y; Chang, Christopher J

2015-09-15

Natural photosynthesis harnesses solar energy to convert CO2 and water to value-added chemical products for sustaining life. We present a hybrid bioinorganic approach to solar-to-chemical conversion in which sustainable electrical and/or solar input drives production of hydrogen from water splitting using biocompatible inorganic catalysts. The hydrogen is then used by living cells as a source of reducing equivalents for conversion of CO2 to the value-added chemical product methane. Using platinum or an earth-abundant substitute, α-NiS, as biocompatible hydrogen evolution reaction (HER) electrocatalysts and Methanosarcina barkeri as a biocatalyst for CO2 fixation, we demonstrate robust and efficient electrochemical CO2 to CH4 conversion at up to 86% overall Faradaic efficiency for ≥ 7 d. Introduction of indium phosphide photocathodes and titanium dioxide photoanodes affords a fully solar-driven system for methane generation from water and CO2, establishing that compatible inorganic and biological components can synergistically couple light-harvesting and catalytic functions for solar-to-chemical conversion.

Hybrid bioinorganic approach to solar-to-chemical conversion

PubMed Central

Nichols, Eva M.; Gallagher, Joseph J.; Liu, Chong; Su, Yude; Resasco, Joaquin; Yu, Yi; Sun, Yujie; Yang, Peidong; Chang, Michelle C. Y.; Chang, Christopher J.

2015-01-01

Natural photosynthesis harnesses solar energy to convert CO2 and water to value-added chemical products for sustaining life. We present a hybrid bioinorganic approach to solar-to-chemical conversion in which sustainable electrical and/or solar input drives production of hydrogen from water splitting using biocompatible inorganic catalysts. The hydrogen is then used by living cells as a source of reducing equivalents for conversion of CO2 to the value-added chemical product methane. Using platinum or an earth-abundant substitute, α-NiS, as biocompatible hydrogen evolution reaction (HER) electrocatalysts and Methanosarcina barkeri as a biocatalyst for CO2 fixation, we demonstrate robust and efficient electrochemical CO2 to CH4 conversion at up to 86% overall Faradaic efficiency for ≥7 d. Introduction of indium phosphide photocathodes and titanium dioxide photoanodes affords a fully solar-driven system for methane generation from water and CO2, establishing that compatible inorganic and biological components can synergistically couple light-harvesting and catalytic functions for solar-to-chemical conversion. PMID:26305947

Novel high-efficiency visible-light responsive Ag 4(GeO 4) photocatalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xianglin; Wang, Peng; Li, Mengmeng

A novel high-efficiency visible-light responsive Ag 4(GeO 4) photocatalyst was prepared by a facile hydrothermal method. The photocatalytic activity of as-prepared Ag 4(GeO 4) was evaluated by photodegradation of methylene blue (MB) dye and water splitting experiments. The photodegradation efficiency and oxygen production efficiency of Ag 4(GeO 4) were detected to be 2.9 and 1.9 times higher than those of Ag 2O. UVvis diffuse reflectance spectroscopy (DRS), photoluminescence experiment and photoelectric effect experiments prove that the good light response and high carrier separation efficiency facilitated by the internal electric field are the main reasons for Ag 4(GeO 4)'s excellent catalyticmore » activity. Radical-trapping experiments reveal that the photogenerated holes are the main active species. Lastly, first-principles theoretical calculations provide more insight into understanding the photocatalytic mechanism of the Ag 4(GeO 4) catalyst.« less

Novel high-efficiency visible-light responsive Ag 4(GeO 4) photocatalyst

DOE PAGES

Zhu, Xianglin; Wang, Peng; Li, Mengmeng; ...

2017-04-25

A novel high-efficiency visible-light responsive Ag 4(GeO 4) photocatalyst was prepared by a facile hydrothermal method. The photocatalytic activity of as-prepared Ag 4(GeO 4) was evaluated by photodegradation of methylene blue (MB) dye and water splitting experiments. The photodegradation efficiency and oxygen production efficiency of Ag 4(GeO 4) were detected to be 2.9 and 1.9 times higher than those of Ag 2O. UVvis diffuse reflectance spectroscopy (DRS), photoluminescence experiment and photoelectric effect experiments prove that the good light response and high carrier separation efficiency facilitated by the internal electric field are the main reasons for Ag 4(GeO 4)'s excellent catalyticmore » activity. Radical-trapping experiments reveal that the photogenerated holes are the main active species. Lastly, first-principles theoretical calculations provide more insight into understanding the photocatalytic mechanism of the Ag 4(GeO 4) catalyst.« less

Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

DOE PAGES

Lichterman, Michael F.; Sun, Ke; Hu, Shu; ...

2015-10-25

Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation aremore » unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.« less

Rational Design of an Electron-Reservoir Pt(II) Complex for Efficient Photocatalytic Hydrogen Production from Water.

PubMed

Whang, Dong Ryeol; Park, Soo Young

2015-10-12

Herein we report a Pt(II) complex containing a 4,4'-bis[4-(triphenylsilyl)phenyl]-2,2'-bipyridine ligand as a molecular catalyst for water splitting. Systematic studies of the electrochemical and electronic properties of this catalyst, in comparison with two control complexes, reveal electron-reservoir characteristics upon two-electron reduction. A turnover number of 510,000 was recorded by employing this complex as a water reduction catalyst in combination with a state-of-the-art photosensitizer and N,N-dimethylaniline as a sacrificial electron donor, which represents a large improvement over the control complexes that do not contain the tetraphenylsilyl ligand substitution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

PubMed Central

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

2015-01-01

In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

Behavior of pharmaceuticals and drugs of abuse in a drinking water treatment plant (DWTP) using combined conventional and ultrafiltration and reverse osmosis (UF/RO) treatments.

PubMed

Boleda, M A Rosa; Galceran, M A Teresa; Ventura, Francesc

2011-06-01

The behavior along the potabilization process of 29 pharmaceuticals and 12 drugs of abuse identified from a total of 81 compounds at the intake of a drinking water treatment plant (DWTP) has been studied. The DWTP has a common treatment consisting of dioxychlorination, coagulation/flocculation and sand filtration and then water is splitted in two parallel treatment lines: conventional (ozonation and carbon filtration) and advanced (ultrafiltration and reverse osmosis) to be further blended, chlorinated and distributed. Full removals were reached for most of the compounds. Iopromide (up to 17.2 ng/L), nicotine (13.7 ng/L), benzoylecgonine (1.9 ng/L), cotinine (3.6 ng/L), acetaminophen (15.6 ng/L), erythromycin (2.0 ng/L) and caffeine (6.0 ng/L) with elimination efficiencies ≥ 94%, were the sole compounds found in the treated water. The advanced treatment process showed a slightly better efficiency than the conventional treatment to eliminate pharmaceuticals and drugs of abuse. Copyright © 2011 Elsevier Ltd. All rights reserved.

Characterization and evaluation of cadmium indate photocatalysts for solar hydrogen conversion

NASA Astrophysics Data System (ADS)

Thornton, Jason M.

Alternative energy sources are needed to respond to the continued increase in the global energy needs and a potential decrease in the future supplies of fossil fuels. Solar hydrogen conversion in which sunlight is harnessed to split water into H2 fuel and O2 is a promising source of energy because it is renewable and produces no CO2. A number of semiconducting oxide materials have shown promise for overall water splitting for the generation of hydrogen over the years. In this work we focus on the synthesis and analysis of undoped and C-doped cadmium indate (CdIn2O 4) thin films and nanoparticle powders, and their evaluation for hydrogen evolution via water splitting. The catalyst was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis, scanning electron microscopy (SEM), and BET surface adsorption measurements. Spray and sol-gel pyrolysis methods were used for the synthesis of the materials. Doping C into CdIn 2O4 leads to enhancement in light absorption and the band gap was determined to be 2.3 eV in the nanoparticle powders. Carbon doping improves the photocurrent density by 33% and the H2 evolution rate by a factor of two. The performance of C-doped CdIn2O4 were optimized with respect to several synthetic parameters, including the In:Cd molar ratio and glucose concentration, calcination temperature, and the film thickness while the nanoparticles were additionally optimized to F127 concentration and platinum cocatalyst loading. Hydrogen generation activity was evaluated under UV-visible irradiation without the use of a sacrificial reagent and using bandpass filters the quantum efficiency was determined. Compared to platinized TiO2 in methanol C-CdIn2O4 showed a 4-fold increase in hydrogen production. The material was capable of hydrogen generation using visible light only and with good efficiency even at 510 nm. Using natural sunlight illumination, the material evolved hydrogen at a rate of 17 micromol h-1. These studies show carbon-doped cadmium indate to be a promising catalyst for solar hydrogen conversion.

Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chidambaram, Dev; Misra, Mano; Heske, Clemens

2014-12-21

The objectives included: Develop high efficiency metal oxide nanotubular array photo-anodes for generating hydrogen by water splitting; Develop density functional theory to understand the effect of the morphology of the nanotubes on the photo-electrochemical (PEC) properties of the photo-anodes; Develop kinetics and formation mechanism of the metal oxide nanotubes under different synthesis conditions; Develop combinatorial approach to prepare hybrid photo-anodes having multiple hetero-atoms incorporation in a single photo anode; Improve the durability of the material; and Scale up the laboratory demonstration to production unit.

Synergistic Effect of a Molecular Cocatalyst and a Heterojunction in a 1 D Semiconductor Photocatalyst for Robust and Highly Efficient Solar Hydrogen Production.

PubMed

Jiang, Daochuan; Irfan, Rana Muhammad; Sun, Zijun; Lu, Dapeng; Du, Pingwu

2016-11-09

Photocatalytic production of hydrogen by water splitting is a promising pathway for the conversion of solar energy into chemical energy. However, the photocatalytic conversion efficiency is often limited by the sluggish transfer of the photogenerated charge carriers, charge recombination, and subsequent slow catalytic reactions. Herein, we report a highly active noble-metal-free photocatalytic system for hydrogen production in water. The system contains a water-soluble nickel complex as a molecular cocatalyst and zinc sulfide on 1D cadmium sulfide as the heterojunction photocatalyst. The complex can efficiently transport photogenerated electrons and holes over a heterojunction photocatalyst to hamper charge recombination, leading to highly improved catalytic efficiency and durability of a heterojunction photocatalyst- molecular cocatalyst system. The results show that under optimal conditions, the average apparent quantum yield was approximately 58.3 % after 7 h of irradiation with monochromatic 420 nm light. In contrast, the value is only 16.8 % if the molecular cocatalyst is absent. Such a remarkable performance in a molecular cocatalyst-based photocatalytic system without any noble metal loading has, to the best of our knowledge, not been reported to date. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-destructive splitter of twisted light based on modes splitting in a ring cavity.

PubMed

Li, Yan; Zhou, Zhi-Yuan; Ding, Dong-Sheng; Zhang, Wei; Shi, Shuai; Shi, Bao-Sen; Guo, Guang-Can

2016-02-08

Efficiently discriminating beams carrying different orbital angular momentum (OAM) is of fundamental importance for various applications including high capacity optical communication and quantum information processing. We design and experimentally verify a distinguished method for effectively splitting different OAM-carried beams by introducing Dove prisms in a ring cavity. Because of rotational symmetry broken of two OAM-carried beams with opposite topological charges, their transmission spectra will split. When mode and impedance matches between the cavity and one OAM-carried beam are achieved, this beam will transmit through the cavity and other beam will be reflected, both beams keep their spatial shapes. In this case, the cavity acts like a polarized beam splitter. Besides, the transmitting beam can be selected at your will, the splitting efficiency can reach unity if the cavity is lossless and it completely matches the beam. Furthermore, beams carry multi-OAMs can also be split by cascading ring cavities.

Enhanced photoelectrochemical water splitting of BiVO4 photonic crystal photoanode by decorating with MoS2 nanosheets

NASA Astrophysics Data System (ADS)

Nan, Feng; Cai, Tianyi; Ju, Sheng; Fang, Liang

2018-04-01

Bismuth vanadate (BiVO4) has been considered as one of the promising Photoelectrochemical (PEC) photoanode materials. However, the performances remain poorly rated due to inefficient carrier separation, short carrier diffusion length, and sluggish water oxidation kinetics. Herein, a photoanode consisting of MoS2 nanosheet coating on the three-dimensional ordered BiVO4 inverse opal is fabricated by a facile combination of nanosphere lithography and hydrothermal methods. By taking advantage of the photonic crystal and two-dimensional material, the optimized MoS2/BiVO4 inverse opal photoanode exhibits a 560% improvement of the photocurrent density and threefold enhancement of the incident photon-to-current efficiency than that of the pristine BiVO4 film photoanode. Systematic studies reveal that the excellent PEC activity should be attributed to enhanced light harvesting and charge separation efficiency.

Nanostructured tungsten trioxide thin films synthesized for photoelectrocatalytic water oxidation: a review.

PubMed

Zhu, Tao; Chong, Meng Nan; Chan, Eng Seng

2014-11-01

The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron refrigeration in hybrid structures with spin-split superconductors

NASA Astrophysics Data System (ADS)

Rouco, M.; Heikkilä, T. T.; Bergeret, F. S.

2018-01-01

Electron tunneling between superconductors and normal metals has been used for an efficient refrigeration of electrons in the latter. Such cooling is a nonlinear effect and usually requires a large voltage. Here we study the electron cooling in heterostructures based on superconductors with a spin-splitting field coupled to normal metals via spin-filtering barriers. The cooling power shows a linear term in the applied voltage. This improves the coefficient of performance of electron refrigeration in the normal metal by shifting its optimum cooling to lower voltage, and also allows for cooling the spin-split superconductor by reverting the sign of the voltage. We also show how tunnel coupling spin-split superconductors with regular ones allows for a highly efficient refrigeration of the latter.

Thermodynamics and Transport Phenomena in High Temperature Steam Electrolysis Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

James E. O'Brien

2012-03-01

Hydrogen can be produced from water splitting with relatively high efficiency using high temperature electrolysis. This technology makes use of solid-oxide cells, running in the electrolysis mode to produce hydrogen from steam, while consuming electricity and high temperature process heat. The overall thermal-to-hydrogen efficiency for high temperature electrolysis can be as high as 50%, which is about double the overall efficiency of conventional low-temperature electrolysis. Current large-scale hydrogen production is based almost exclusively on steam reforming of methane, a method that consumes a precious fossil fuel while emitting carbon dioxide to the atmosphere. An overview of high temperature electrolysis technologymore » will be presented, including basic thermodynamics, experimental methods, heat and mass transfer phenomena, and computational fluid dynamics modeling.« less

One Electron-Initiated Two-Electron Oxidation of Water by Aluminum Porphyrins with Earth's Most Abundant Metal.

PubMed

Kuttassery, Fazalurahman; Mathew, Siby; Sagawa, Shogo; Remello, Sebastian Nybin; Thomas, Arun; Yamamoto, Daisuke; Onuki, Satomi; Nabetani, Yu; Tachibana, Hiroshi; Inoue, Haruo

2017-05-09

We report herein a new molecular catalyst for efficient water splitting, aluminum porphyrins (tetra-methylpyridiniumylporphyrinatealuminum: AlTMPyP), containing earth's most abundant metal as the central ion. One-electron oxidation of the aluminum porphyrin initiates the two-electron oxidation of water to form hydrogen peroxide as the primary reaction product with the lowest known overpotential (97 mV). The aluminum-peroxo complex was detected by a cold-spray ionization mass-spectrometry in high-resolution MS (HRMS) mode and the structure of the intermediate species was further confirmed using laser Raman spectroscopy, indicating the hydroperoxy complex of AlTMPyP to be the key intermediate in the reaction. The two-electron oxidation of water to form hydrogen peroxide was essentially quantitative, with a Faradaic efficiency of 99 %. The catalytic reaction was found to be highly efficient, with a turnover frequency up to ∼2×10 4  s -1 . A reaction mechanism is proposed involving oxygen-oxygen bond formation by the attack of a hydroxide ion on the oxyl-radical-like axial ligand oxygen atom in the one-electron-oxidized form of AlTMPyP(O - ) 2 , followed by a second electron transfer to the electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical synthesis of nanoporous tungsten carbide and its application as electrocatalysts for photoelectrochemical cells.

PubMed

Kang, Jin Soo; Kim, Jin; Lee, Myeong Jae; Son, Yoon Jun; Jeong, Juwon; Chung, Dong Young; Lim, Ahyoun; Choe, Heeman; Park, Hyun S; Sung, Yung-Eun

2017-05-04

Photoelectrochemical (PEC) cells are promising tools for renewable and sustainable solar energy conversion. Currently, their inadequate performance and high cost of the noble metals used in the electrocatalytic counter electrode have postponed the practical use of PEC cells. In this study, we report the electrochemical synthesis of nanoporous tungsten carbide and its application as a reduction catalyst in PEC cells, namely, dye-sensitized solar cells (DSCs) and PEC water splitting cells, for the first time. The method employed in this study involves the anodization of tungsten foil followed by post heat treatment in a CO atmosphere to produce highly crystalline tungsten carbide film with an interconnected nanostructure. This exhibited high catalytic activity for the reduction of cobalt bipyridine species, which represent state-of-the-art redox couples for DSCs. The performance of tungsten carbide even surpassed that of Pt, and a substantial increase (∼25%) in energy conversion efficiency was achieved when Pt was substituted by tungsten carbide film as the counter electrode. In addition, tungsten carbide displayed decent activity as a catalyst for the hydrogen evolution reaction, suggesting the high feasibility for its utilization as a cathode material for PEC water splitting cells, which was also verified in a two-electrode water photoelectrolyzer.

An efficient unstructured WENO method for supersonic reactive flows

NASA Astrophysics Data System (ADS)

Zhao, Wen-Geng; Zheng, Hong-Wei; Liu, Feng-Jun; Shi, Xiao-Tian; Gao, Jun; Hu, Ning; Lv, Meng; Chen, Si-Cong; Zhao, Hong-Da

2018-03-01

An efficient high-order numerical method for supersonic reactive flows is proposed in this article. The reactive source term and convection term are solved separately by splitting scheme. In the reaction step, an adaptive time-step method is presented, which can improve the efficiency greatly. In the convection step, a third-order accurate weighted essentially non-oscillatory (WENO) method is adopted to reconstruct the solution in the unstructured grids. Numerical results show that our new method can capture the correct propagation speed of the detonation wave exactly even in coarse grids, while high order accuracy can be achieved in the smooth region. In addition, the proposed adaptive splitting method can reduce the computational cost greatly compared with the traditional splitting method.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Siyu; Zhang, Xiao; Zhou, Wu

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCatmore » 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Carbon-armored Co9S8 nanoparticles as all-pH efficient and durable H2-evolving electrocatalysts.

PubMed

Feng, Liang-Liang; Li, Guo-Dong; Liu, Yipu; Wu, Yuanyuan; Chen, Hui; Wang, Yun; Zou, Yong-Cun; Wang, Dejun; Zou, Xiaoxin

2015-01-14

Splitting water to produce hydrogen requires the development of non-noble-metal catalysts that are able to make this reaction feasible and energy efficient. Herein, we show that cobalt pentlandite (Co9S8) nanoparticles can serve as an electrochemically active, noble-metal-free material toward hydrogen evolution reaction, and they work stably in neutral solution (pH 7) but not in acidic (pH 0) and basic (pH 14) media. We, therefore, further present a carbon-armoring strategy to increase the durability and activity of Co9S8 over a wider pH range. In particular, carbon-armored Co9S8 nanoparticles (Co9S8@C) are prepared by direct thermal treatment of a mixture of cobalt nitrate and trithiocyanuric acid at 700 °C in N2 atmosphere. Trithiocyanuric acid functions as both sulfur and carbon sources in the reaction system. The resulting Co9S8@C material operates well with high activity over a broad pH range, from pH 0 to 14, and gives nearly 100% Faradaic yield during hydrogen evolution reaction under acidic (pH 0), neutral (pH 7), and basic (pH 14) media. To the best of our knowledge, this is the first time that a transition-metal chalcogenide material is shown to have all-pH efficient and durable electrocatalytic activity. Identifying Co9S8 as the catalytically active phase and developing carbon-armoring as the improvement strategy are anticipated to give a fresh impetus to rational design of high-performance noble-metal-free water splitting catalysts.

Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

DOE PAGES

Yao, Siyu; Zhang, Xiao; Zhou, Wu; ...

2017-06-22

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCmore » at 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting

NASA Astrophysics Data System (ADS)

Liu, Jian; Li, Xi-Bo; Wang, Da; Lau, Woon-Ming; Peng, Ping; Liu, Li-Min

2014-02-01

The family of bulk metal phosphorus trichalcogenides (APX3, A = MII, M_{0.5}^IM_{0.5}^{III}; X = S, Se; MI, MII, and MIII represent Group-I, Group-II, and Group-III metals, respectively) has attracted great attentions because such materials not only own magnetic and ferroelectric properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here we present a systematical study of single-layer metal phosphorus trichalcogenides by density functional theory calculations. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX3 should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calculated band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe3, CdPSe3, Ag0.5Sc0.5PSe3, and Ag0.5In0.5PX3 (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag0.5Sc0.5PSe3 is a direct band gap semiconductor, and the calculated optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting.

Design and fabrication of cascaded dichromate gelatin holographic filters for spectrum-splitting PV systems

NASA Astrophysics Data System (ADS)

Wu, Yuechen; Chrysler, Benjamin; Kostuk, Raymond K.

2018-01-01

The technique of designing, optimizing, and fabricating broadband volume transmission holograms using dichromate gelatin (DCG) is summarized for solar spectrum-splitting applications. The spectrum-splitting photovoltaic (PV) system uses a series of single-bandgap PV cells that have different spectral conversion efficiency properties to more fully utilize the solar spectrum. In such a system, one or more high-performance optical filters are usually required to split the solar spectrum and efficiently send them to the corresponding PV cells. An ideal spectral filter should have a rectangular shape with sharp transition wavelengths. A methodology of designing and modeling a transmission DCG hologram using coupled wave analysis for different PV bandgap combinations is described. To achieve a broad diffraction bandwidth and sharp cutoff wavelength, a cascaded structure of multiple thick holograms is described. A search algorithm is then developed to optimize both single- and two-layer cascaded holographic spectrum-splitting elements for the best bandgap combinations of two- and three-junction spectrum-splitting photovoltaic (SSPV) systems illuminated under the AM1.5 solar spectrum. The power conversion efficiencies of the optimized systems are found to be 42.56% and 48.41%, respectively, using the detailed balance method, and show an improvement compared with a tandem multijunction system. A fabrication method for cascaded DCG holographic filters is also described and used to prototype the optimized filter for the three-junction SSPV system.

Ir4+-Doped NiFe LDH to expedite hydrogen evolution kinetics as a Pt-like electrocatalyst for water splitting.

PubMed

Chen, Qian-Qian; Hou, Chun-Chao; Wang, Chuan-Jun; Yang, Xiao; Shi, Rui; Chen, Yong

2018-06-06

NiFe-layered double hydroxide (NiFe LDH) is a state-of-the-art oxygen evolution reaction (OER) electrocatalyst, yet it suffers from rather poor catalytic activity for the hydrogen evolution reaction (HER) due to its extremely sluggish water dissociation kinetics, severely restricting its application in overall water splitting. Herein, we report a novel strategy to expedite the HER kinetics of NiFe LDH by an Ir4+-doping strategy to accelerate the water dissociation process (Volmer step), and thus this catalyst exhibits superior and robust catalytic activity for finally oriented overall water splitting in 1 M KOH requiring only a low initial voltage of 1.41 V delivering at 20 mA cm-2 for more than 50 h.

Hydrogen generation due to water splitting on Si - terminated 4H-Sic(0001) surfaces

NASA Astrophysics Data System (ADS)

Li, Qingfang; Li, Qiqi; Yang, Cuihong; Rao, Weifeng

2018-02-01

The chemical reactions of hydrogen gas generation via water splitting on Si-terminated 4H-SiC surfaces with or without C/Si vacancies were studied by using first-principles. We studied the reaction mechanisms of hydrogen generation on the 4H-SiC(0001) surface. Our calculations demonstrate that there are major rearrangements in surface when H2O approaches the SiC(0001) surface. The first H splitting from water can occur with ground-state electronic structures. The second H splitting involves an energy barrier of 0.65 eV. However, the energy barrier for two H atoms desorbing from the Si-face and forming H2 gas is 3.04 eV. In addition, it is found that C and Si vacancies can form easier in SiC(0001)surfaces than in SiC bulk and nanoribbons. The C/Si vacancies introduced can enhance photocatalytic activities. It is easier to split OH on SiC(0001) surface with vacancies compared to the case of clean SiC surface. H2 can form on the 4H-SiC(0001) surface with C and Si vacancies if the energy barriers of 1.02 and 2.28 eV are surmounted, respectively. Therefore, SiC(0001) surface with C vacancy has potential applications in photocatalytic water-splitting.

Nano-sized layered Mn oxides as promising and biomimetic water oxidizing catalysts for water splitting in artificial photosynthetic systems.

PubMed

Najafpour, Mohammad Mahdi; Heidari, Sima; Amini, Emad; Khatamian, Masoumeh; Carpentier, Robert; Allakhverdiev, Suleyman I

2014-04-05

One challenge in artificial photosynthetic systems is the development of artificial model compounds to oxidize water. The water-oxidizing complex of Photosystem II which is responsible for biological water oxidation contains a cluster of four Mn ions bridged by five oxygen atoms. Layered Mn oxides as efficient, stable, low cost, environmentally friendly and easy to use, synthesize, and manufacture compounds could be considered as functional and structural models for the site. Because of the related structure of these Mn oxides and the catalytic centre of the active site of the water oxidizing complex of Photosystem II, the study of layered Mn oxides may also help to understand more about the mechanism of water oxidation by the natural site. This review provides an overview of the current status of layered Mn oxides in artificial photosynthesis and discuss the sophisticated design strategies for Mn oxides as water oxidizing catalysts. Copyright © 2014 Elsevier B.V. All rights reserved.

Hollow TiO2@Co9S8 Core–Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production

PubMed Central

Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang; Wang, Yadong; Wang, Xiuli; Tu, Jiangping

2017-01-01

Abstract Designing ever more efficient and cost‐effective bifunctional electrocatalysts for oxygen/hydrogen evolution reactions (OER/HER) is greatly vital and challenging. Here, a new type of binder‐free hollow TiO2@Co9S8 core–branch arrays is developed as highly active OER and HER electrocatalysts for stable overall water splitting. Hollow core–branch arrays of TiO2@Co9S8 are readily realized by the rational combination of crosslinked Co9S8 nanoflakes on TiO2 core via a facile and powerful sulfurization strategy. Arising from larger active surface area, richer/shorter transfer channels for ions/electrons, and reinforced structural stability, the as‐obtained TiO2@Co9S8 core–branch arrays show noticeable exceptional electrocatalytic performance, with low overpotentials of 240 and 139 mV at 10 mA cm−2 as well as low Tafel slopes of 55 and 65 mV Dec−1 for OER and HER in alkaline medium, respectively. Impressively, the electrolysis cell based on the TiO2@Co9S8 arrays as both cathode and anode exhibits a remarkably low water splitting voltage of 1.56 V at 10 mA cm−2 and long‐term durability with no decay after 10 d. The versatile fabrication protocol and smart branch‐core design provide a new way to construct other advanced metal sulfides for energy conversion and storage. PMID:29593976

Hollow TiO2@Co9S8 Core-Branch Arrays as Bifunctional Electrocatalysts for Efficient Oxygen/Hydrogen Production.

PubMed

Deng, Shengjue; Zhong, Yu; Zeng, Yinxiang; Wang, Yadong; Wang, Xiuli; Lu, Xihong; Xia, Xinhui; Tu, Jiangping

2018-03-01

Designing ever more efficient and cost-effective bifunctional electrocatalysts for oxygen/hydrogen evolution reactions (OER/HER) is greatly vital and challenging. Here, a new type of binder-free hollow TiO 2 @Co 9 S 8 core-branch arrays is developed as highly active OER and HER electrocatalysts for stable overall water splitting. Hollow core-branch arrays of TiO 2 @Co 9 S 8 are readily realized by the rational combination of crosslinked Co 9 S 8 nanoflakes on TiO 2 core via a facile and powerful sulfurization strategy. Arising from larger active surface area, richer/shorter transfer channels for ions/electrons, and reinforced structural stability, the as-obtained TiO 2 @Co 9 S 8 core-branch arrays show noticeable exceptional electrocatalytic performance, with low overpotentials of 240 and 139 mV at 10 mA cm -2 as well as low Tafel slopes of 55 and 65 mV Dec -1 for OER and HER in alkaline medium, respectively. Impressively, the electrolysis cell based on the TiO 2 @Co 9 S 8 arrays as both cathode and anode exhibits a remarkably low water splitting voltage of 1.56 V at 10 mA cm -2 and long-term durability with no decay after 10 d. The versatile fabrication protocol and smart branch-core design provide a new way to construct other advanced metal sulfides for energy conversion and storage.

Differences in results of analyses of concurrent and split stream-water samples collected and analyzed by the US Geological Survey and the Illinois Environmental Protection Agency, 1985-91

USGS Publications Warehouse

Melching, C.S.; Coupe, R.H.

1995-01-01

During water years 1985-91, the U.S. Geological Survey (USGS) and the Illinois Environmental Protection Agency (IEPA) cooperated in the collection and analysis of concurrent and split stream-water samples from selected sites in Illinois. Concurrent samples were collected independently by field personnel from each agency at the same time and sent to the IEPA laboratory, whereas the split samples were collected by USGS field personnel and divided into aliquots that were sent to each agency's laboratory for analysis. The water-quality data from these programs were examined by means of the Wilcoxon signed ranks test to identify statistically significant differences between results of the USGS and IEPA analyses. The data sets for constituents and properties identified by the Wilcoxon test as having significant differences were further examined by use of the paired t-test, mean relative percentage difference, and scattergrams to determine if the differences were important. Of the 63 constituents and properties in the concurrent-sample analysis, differences in only 2 (pH and ammonia) were statistically significant and large enough to concern water-quality engineers and planners. Of the 27 constituents and properties in the split-sample analysis, differences in 9 (turbidity, dissolved potassium, ammonia, total phosphorus, dissolved aluminum, dissolved barium, dissolved iron, dissolved manganese, and dissolved nickel) were statistically significant and large enough to con- cern water-quality engineers and planners. The differences in concentration between pairs of the concurrent samples were compared to the precision of the laboratory or field method used. The differences in concentration between pairs of the concurrent samples were compared to the precision of the laboratory or field method used. The differences in concentration between paris of split samples were compared to the precision of the laboratory method used and the interlaboratory precision of measuring a given concentration or property. Consideration of method precision indicated that differences between concurrent samples were insignificant for all concentrations and properties except pH, and that differences between split samples were significant for all concentrations and properties. Consideration of interlaboratory precision indicated that the differences between the split samples were not unusually large. The results for the split samples illustrate the difficulty in obtaining comparable and accurate water-quality data.

New Earth-abundant Materials for Large-scale Solar Fuels Generation.

PubMed

Prabhakar, Rajiv Ramanujam; Cui, Wei; Tilley, S David

2018-05-30

The solar resource is immense, but the power density of light striking the Earth's surface is relatively dilute, necessitating large area solar conversion devices in order to harvest substantial amounts of power for renewable energy applications. In addition, energy storage is a key challenge for intermittent renewable resources such as solar and wind, which adds significant cost to these energies. As the majority of humanity's present-day energy consumption is based on fuels, an ideal solution is to generate renewable fuels from abundant resources such as sunlight and water. In this account, we detail our recent work towards generating highly efficient and stable Earth-abundant semiconducting materials for solar water splitting to generate renewable hydrogen fuel.

One‐Dimensional Earth‐Abundant Nanomaterials for Water‐Splitting Electrocatalysts

PubMed Central

Li, Jun

2016-01-01

Hydrogen fuel acquisition based on electrochemical or photoelectrochemical water splitting represents one of the most promising means for the fast increase of global energy need, capable of offering a clean and sustainable energy resource with zero carbon footprints in the environment. The key to the success of this goal is the realization of robust earth‐abundant materials and cost‐effective reaction processes that can catalyze both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with high efficiency and stability. In the past decade, one‐dimensional (1D) nanomaterials and nanostructures have been substantially investigated for their potential in serving as these electrocatalysts for reducing overpotentials and increasing catalytic activity, due to their high electrochemically active surface area, fast charge transport, efficient mass transport of reactant species, and effective release of gas produced. In this review, we summarize the recent progress in developing new 1D nanomaterials as catalysts for HER, OER, as well as bifunctional electrocatalysts for both half reactions. Different categories of earth‐abundant materials including metal‐based and metal‐free catalysts are introduced, with their representative results presented. The challenges and perspectives in this field are also discussed. PMID:28331791

Imaging nanobubble nucleation and hydrogen spillover during electrocatalytic water splitting.

PubMed

Hao, Rui; Fan, Yunshan; Howard, Marco D; Vaughan, Joshua C; Zhang, Bo

2018-06-05

Nucleation and growth of hydrogen nanobubbles are key initial steps in electrochemical water splitting. These processes remain largely unexplored due to a lack of proper tools to probe the nanobubble's interfacial structure with sufficient spatial and temporal resolution. We report the use of superresolution microscopy to image transient formation and growth of single hydrogen nanobubbles at the electrode/solution interface during electrocatalytic water splitting. We found hydrogen nanobubbles can be generated even at very early stages in water electrolysis, i.e., ∼500 mV before reaching its thermodynamic reduction potential. The ability to image single nanobubbles on an electrode enabled us to observe in real time the process of hydrogen spillover from ultrathin gold nanocatalysts supported on indium-tin oxide.

[Interactive impact of water and nitrogen on yield, quality of watermelon and use of water and nitrogen in gravel-mulched field].

PubMed

Du, Shao-ping; Ma, Zhong-ming; Xue, Liang

2015-12-01

In order to develop the optimal coupling model of water and nitrogen of watermelon under limited irrigation in gravel-mulched field, a field experiment with split-plot design was conducted to study the effects of supplementary irrigation volume, nitrogen fertilization, and their interactions on the growth, yield, quality and water and nitrogen use efficiency of watermelon with 4 supplementary irrigation levels (W: 0, 35, 70, and 105 m³ · hm⁻²) in main plots and 3 nitrogen fertilization levels (N: 0, 120, and 200 kg N · hm⁻²) in sub-plots. The results showed that the photosynthetic rate, yield, and water and nitrogen use efficiency of watermelon increased with the increasing supplementary irrigation, but the nitrogen partial productivity and nitrogen use efficiency decreased with increasing nitrogen fertilization level. The photosynthetic rate and quality indicators increased with increasing nitrogen fertilization level as the nitrogen rate changed from 0 to 120 kg N · hm⁻², but no further significant increase as the nitrogen rate exceeded 120 kg · hm⁻². The interactive effects between water and nitrogen was significant for yield and water and nitrogen use efficiency of watermelon, supplementary irrigation volume was a key factor for the increase yield compared with the nitrogen fertilizer, and the yield reached the highest for the W₇₀N₂₀₀ and W₁₀₅ N₁₂₀ treatments, for which the yield increased by 42.4% and 40.4% compared to CK. Water use efficiency (WUE) was improved by supplementary irrigation and nitrogen rate, the WUE of all nitrogen fertilizer treatments were more than 26 kg · m⁻³ under supplemental irrigation levels 70 m³ · hm⁻² and 105 m³ · hm⁻². The nitrogen partial productivity and nitrogen use efficiency reached the highest in the treatment of W₁₀₅N₁₂₀. It was considered that under the experimental condition, 105 m³ · hm⁻² of supplementary irrigation plus 120 kg · hm⁻² of nitrogen fertilization was the optimal combination of obtaining the high yield and high efficiency.

Enhanced light trapping and high charge transmission capacities of novel structures for efficient photoelectrochemical water splitting.

PubMed

Mu, Jianglong; Miao, Hui; Liu, Enzhou; Feng, Juan; Teng, Feng; Zhang, Dekai; Kou, Yumeng; Jin, Yanping; Fan, Jun; Hu, Xiaoyun

2018-06-13

Excellent PEC efficiency, good reusability and the super stability of trap-like SnS2/TiO2 nanotube arrays (NTs)-based photoanodes are reported. Specifically, the SnS2/TiO2-180 °C (ST-180) photoanode exhibited the highest photocurrent density (1.05 mA cm-2) and an optimal η (0.73%) at 0.5 V (vs. SCE) under simulated light irradiation (AM 1.5G), which are 4.6 and 3.8 times higher than those of pure TiO2 NTs (0.23 mA cm-2 and 0.19%). The IPCE values of ST-180 can reach 21.5% (365 nm) and 13.8% (420 nm), which are much higher than those of pure TiO2 NTs (10.6% at 365 nm and 0.8% at 420 nm). The APCE values of the pure TiO2 NTs photoelectrode are 12.8% (365 nm) and 1.1% (420 nm), while the ST-180 values are 22.3% and 14.2%, respectively. Furthermore, the generation rates of H2 and O2 for the ST-180 photoanode are 47.2 and 23.1 μmol cm-2 h-1 at 0.5 V under AM 1.5G, corresponding to faradaic efficiencies of around 80.1% and 78.3%, respectively. In short, the high-efficiency PEC water splitting performance of this SnS2/TiO2 photoanode results from the enhanced light harvesting ability of the trap-like SnS2 structure, accelerated carrier transportation properties of TiO2 NTs, and effective carrier separation of the type-II heterojunction structure. This work may offer a combinatorial strategy for the preparation of heterojunction structures with high PEC performance and can be a model structure for similar photoanode materials.

The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting

DOE PAGES

Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia; ...

2018-01-01

We report the discovery of a new class of oxides – poly-cation oxides (PCOs) – that consist of multiple cations and can thermochemically split water in a two-step cycle to produce hydrogen (H 2 ) and oxygen (O 2 ).

Nano-ferrites for Water Splitting: Unprecedented High Photocatalytic Hydrogen Production under Visible Light

EPA Science Inventory

In the present investigation, hydrogen production via water splitting by nano ferrites has been studied using ethanol as the sacrificial donor. The nano ferrite has shown great potential in hydrogen generation with hydrogen yield of 8275 9moles/h/ g of photocatalyst under visible...

Realizing InGaN monolithic solar-photoelectrochemical cells for artificial photosynthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dahal, R.; Pantha, B. N.; Li, J.

2014-04-07

InGaN alloys are very promising for solar water splitting because they have direct bandgaps that cover almost the whole solar spectrum. The demonstration of direct solar-to-fuel conversion without external bias with the sunlight being the only energy input would pave the way for realizing photoelectrochemical (PEC) production of hydrogen by using InGaN. A monolithic solar-PEC cell based on InGaN/GaN multiple quantum wells capable to directly generate hydrogen gas under zero bias via solar water splitting is reported. Under the irradiation by a simulated sunlight (1-sun with 100 mW/cm{sup 2}), a 1.5% solar-to-fuel conversion efficiency has been achieved under zero bias,more » setting a fresh benchmark of employing III-nitrides for artificial photosynthesis. Time dependent hydrogen gas production photocurrent measured over a prolonged period (measured for 7 days) revealed an excellent chemical stability of InGaN in aqueous solution of hydrobromic acid. The results provide insights into the architecture design of using InGaN for artificial photosynthesis to provide usable clean fuel (hydrogen gas) with the sunlight being the only energy input.« less

Coating polymeric carbon nitride photoanodes on conductive Y:ZnO nanorod arrays for overall water splitting.

PubMed

Fang, Yuanxing; Xu, Yuntao; Li, Xiaochun; Ma, Yiwen; Wang, Xinchen

2018-06-14

Solar-to-fuel conversion via photoelectrochemical (PEC) water splitting has the potential to ease current energy and environmental concerns. In pursuit of sustainability, polymeric carbon nitride (PCN) photosensitizers are receiving increasing attention as replacements for their inorganic counterparts. However, intense charge recombination, primarily because of the numerous surface defects, limits the use of PCN in PEC systems. Herein, photoanodes are designed by coating PCN films onto highly conductive yttrium (Y) doped zinc oxide (ZnO) nanorods (NRs) serving as charge collectors. The generation of charge carriers can therefore be promoted by this type II heterostructure. Accordingly, the charge collectors would be kept nearby for charge separation and transport to be used in the interfacial redox reactions. As such, the photocurrent density of the polymer electrode is improved to an exceptional value of 0.4 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE) in a Na2SO4 electrolyte solution under AM 1.5 illumination. The result reveals a more than 50-fold enhancement over the PCN films achieved by powder, and the efficiency can be preserved at ca. 95% for 160 minutes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substitutional Doping for Aluminosilicate Mineral and Superior Water Splitting Performance.

PubMed

Zhang, Yi; Fu, Liangjie; Shu, Zhan; Yang, Huaming; Tang, Aidong; Jiang, Tao

2017-12-01

Substitutional doping is a strategy in which atomic impurities are optionally added to a host material to promote its properties, while the geometric and electronic structure evolution of natural nanoclay mineral upon substitutional metal doping is still ambiguous. This paper first designed an efficient lanthanum (La) doping strategy for nanotubular clay (halloysite nanotube, HNT) through the dynamic equilibrium of a substitutional atom in the presence of saturated AlCl 3 solution, and systematic characterization of the samples was performed. Further density functional theory (DFT) calculations were carried out to reveal the geometric and electronic structure evolution upon metal doping, as well as to verify the atom-level effect of the La doping. The CdS loading and its corresponding water splitting performance could demonstrate the effect of La doping. CdS nanoparticles (11 wt.%) were uniformly deposited on the surface of La-doped halloysite nanotube (La-HNT) with the average size of 5 nm, and the notable photocatalytic hydrogen evolution rate of CdS/La-HNT reached up to 47.5 μmol/h. The results could provide a new strategy for metal ion doping and constructive insight into the substitutional doping mechanism.

Substitutional Doping for Aluminosilicate Mineral and Superior Water Splitting Performance

NASA Astrophysics Data System (ADS)

Zhang, Yi; Fu, Liangjie; Shu, Zhan; Yang, Huaming; Tang, Aidong; Jiang, Tao

2017-07-01

Substitutional doping is a strategy in which atomic impurities are optionally added to a host material to promote its properties, while the geometric and electronic structure evolution of natural nanoclay mineral upon substitutional metal doping is still ambiguous. This paper first designed an efficient lanthanum (La) doping strategy for nanotubular clay (halloysite nanotube, HNT) through the dynamic equilibrium of a substitutional atom in the presence of saturated AlCl3 solution, and systematic characterization of the samples was performed. Further density functional theory (DFT) calculations were carried out to reveal the geometric and electronic structure evolution upon metal doping, as well as to verify the atom-level effect of the La doping. The CdS loading and its corresponding water splitting performance could demonstrate the effect of La doping. CdS nanoparticles (11 wt.%) were uniformly deposited on the surface of La-doped halloysite nanotube (La-HNT) with the average size of 5 nm, and the notable photocatalytic hydrogen evolution rate of CdS/La-HNT reached up to 47.5 μmol/h. The results could provide a new strategy for metal ion doping and constructive insight into the substitutional doping mechanism.

Unassisted Water Splitting Using a GaSb xP (1- x ) Photoanode

DOE PAGES

Martinez-Garcia, Alejandro; Russell, Harry B.; Paxton, William; ...

2018-02-21

Here in this work, unbiased water splitting with 2% solar-to-hydrogen efficiency under AM 1.5 G illumination using new materials based on GaSb 0.03P 0.97 alloy is reported. Freestanding GaSb xP 1-x is grown using halide vapor phase epitaxy. The native conductivity type of the alloy is modified by silicon doping, resulting in an open-circuit potential (OCP) of 750 mV, photocurrents of 7 mA cm -2 at 10 sun illumination, and corrosion resistance in an aqueous acidic environment. Alloying GaP with Sb at 3 at% improves the absorption of high-energy photons above 2.68 eV compared to pure GaP material. Electrochemical Impedancemore » Spectroscopy and illuminated OCP measurements show that the conduction band of GaSb xP 1-x is at -0.55 V versus RHE irrespective of the Sb concentration, while photocurrent spectroscopy indicates that only radiation with photon energies greater than 2.68 eV generate mobile and extractable charges, thus suggesting that the higher-laying conduction bands in the Γ 1 valley of the alloys are responsible for exciton generation.« less

Unassisted Water Splitting Using a GaSb xP (1- x ) Photoanode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez-Garcia, Alejandro; Russell, Harry B.; Paxton, William

Here in this work, unbiased water splitting with 2% solar-to-hydrogen efficiency under AM 1.5 G illumination using new materials based on GaSb 0.03P 0.97 alloy is reported. Freestanding GaSb xP 1-x is grown using halide vapor phase epitaxy. The native conductivity type of the alloy is modified by silicon doping, resulting in an open-circuit potential (OCP) of 750 mV, photocurrents of 7 mA cm -2 at 10 sun illumination, and corrosion resistance in an aqueous acidic environment. Alloying GaP with Sb at 3 at% improves the absorption of high-energy photons above 2.68 eV compared to pure GaP material. Electrochemical Impedancemore » Spectroscopy and illuminated OCP measurements show that the conduction band of GaSb xP 1-x is at -0.55 V versus RHE irrespective of the Sb concentration, while photocurrent spectroscopy indicates that only radiation with photon energies greater than 2.68 eV generate mobile and extractable charges, thus suggesting that the higher-laying conduction bands in the Γ 1 valley of the alloys are responsible for exciton generation.« less

Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

NASA Astrophysics Data System (ADS)

Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin

2015-02-01

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.

Transparent ALD-grown Ta2O5 protective layer for highly stable ZnO photoelectrode in solar water splitting.

PubMed

Li, Chengcheng; Wang, Tuo; Luo, Zhibin; Zhang, Dong; Gong, Jinlong

2015-04-30

This communication describes a highly stable ZnO/Ta2O5 photoanode with Ta2O5 deposited by atomic layer deposition. The ultrathin Ta2O5 protective layer prevents corrosion of ZnO and reduces surface carrier recombination, leading to a nearly two-fold increase of photo-conversion efficiency. The transparency of Ta2O5 to sunlight is identified as the main reason for the excellent stability of the photoelectrode for 5 hours.

Developing resilient green roofs in a dry climate.

PubMed

Razzaghmanesh, M; Beecham, S; Brien, C J

2014-08-15

Living roofs are an emerging green infrastructure technology that can potentially be used to ameliorate both climate change and urban heat island effects. There is not much information regarding the design of green roofs for dry climates and so the aim of this study was to develop low maintenance and unfertilized green roofs for a dry climate. This paper describes the effects of four important elements of green roofs namely slope, depth, growing media and plant species and their possible interactions in terms of plant growth responses in a dry climate. Sixteen medium-scale green roofs were set up and monitored during a one year period. This experiment consisted of twelve vegetated platforms and four non-vegetated platforms as controls. The design for the experiment was a split-split-plot design in which the factors Slope (1° and 25°) and Depth (100mm, 300 mm) were randomized to the platforms (main plots). Root depth and volume, average height of plants, final dry biomass and ground cover, relative growth rate, final dry shoot-root ratio, water use efficiency and leaf succulence were studied during a twelve month period. The results showed little growth of the plants in media type A, whilst the growth was significant in both media types B and C. On average, a 90% survival rate of plants was observed. Also the growth indices indicated that some plants can grow efficiently in the harsh environment created by green roofs in a dry climate. The root growth pattern showed that retained water in the drainage layer is an alternative source of water for plants. It was also shown that stormwater can be used as a source of irrigation water for green roofs during six months of the year at the study site. In summary, mild sloping intensive systems containing media type C and planted with either Chrysocephalum apiculatum or Disphyma crassifolium showed the best performance. Copyright © 2014 Elsevier B.V. All rights reserved.

Ionic and electronic behaviors of earth-abundant semiconductor materials and their applications toward solar energy harvesting

NASA Astrophysics Data System (ADS)

Mayer, Matthew T.

Semiconductor devices offer promise for efficient conversion of sunlight into other useful forms of energy, in either photovoltaic or photoelectrochemical cell configurations to produce electrical power or chemical energy, respectively. This dissertation examines ionic and electronic phenomena in some candidate semiconductors and seeks to understand their implications toward solar energy conversion applications. First, copper sulfide (Cu2S) was examined as a candidate photovoltaic material. It was discovered that its unique property of cation diffusion allows the room-temperature synthesis of vertically-aligned nanowire arrays, a morphology which facilitates study of the diffusion processes. This diffusivity was found to induce hysteresis in the electronic behavior, leading to the phenomena of resistive switching and negative differential resistance. The Cu2S were then demonstrated as morphological templates for solid-state conversion into different types of heterostructures, including segmented and rod-in-tube morphologies. Near-complete conversion to ZnS, enabled by the out-diffusion of Cu back into the substrate, was also achieved. While the ion diffusion property likely hinders the reliability of Cu 2S in photovoltaic applications, it was shown to enable useful electronic and ionic behaviors. Secondly, iron oxide (Fe2O3, hematite) was examined as a photoanode for photoelectrochemical water splitting. Its energetic limitations toward the water electrolysis reactions were addressed using two approaches aimed at achieving greater photovoltages and thereby improved water splitting efficiencies. In the first, a built-in n-p junction produced an internal field to drive charge separation and generate photovoltage. In the second, Fe 2O3 was deposited onto a smaller band gap material, silicon, to form a device capable of producing enhanced total photovoltage by a dual-absorber Z-scheme mechanism. Both approaches resulted in a cathodic shift of the photocurrent onset potential, signifying enhanced power output and progress toward the unassisted photoelectrolysis of water.

Division of methods for counting helminths' eggs and the problem of efficiency of these methods.

PubMed

Jaromin-Gleń, Katarzyna; Kłapeć, Teresa; Łagód, Grzegorz; Karamon, Jacek; Malicki, Jacek; Skowrońska, Agata; Bieganowski, Andrzej

2017-03-21

From the sanitary and epidemiological aspects, information concerning the developmental forms of intestinal parasites, especially the eggs of helminths present in our environment in: water, soil, sandpits, sewage sludge, crops watered with wastewater are very important. The methods described in the relevant literature may be classified in various ways, primarily according to the methodology of the preparation of samples from environmental matrices prepared for analysis, and the sole methods of counting and chambers/instruments used for this purpose. In addition, there is a possibility to perform the classification of the research methods analyzed from the aspect of the method and time of identification of the individuals counted, or the necessity for staining them. Standard methods for identification of helminths' eggs from environmental matrices are usually characterized by low efficiency, i.e. from 30% to approximately 80%. The efficiency of the method applied may be measured in a dual way, either by using the method of internal standard or the 'Split/Spike' method. While measuring simultaneously in an examined object the efficiency of the method and the number of eggs, the 'actual' number of eggs may be calculated by multiplying the obtained value of the discovered eggs of helminths by inverse efficiency.

Carbon dioxide splitting in a dielectric barrier discharge plasma: a combined experimental and computational study.

PubMed

Aerts, Robby; Somers, Wesley; Bogaerts, Annemie

2015-02-01

Plasma technology is gaining increasing interest for the splitting of CO2 into CO and O2 . We have performed experiments to study this process in a dielectric barrier discharge (DBD) plasma with a wide range of parameters. The frequency and dielectric material did not affect the CO2 conversion and energy efficiency, but the discharge gap can have a considerable effect. The specific energy input has the most important effect on the CO2 conversion and energy efficiency. We have also presented a plasma chemistry model for CO2 splitting, which shows reasonable agreement with the experimental conversion and energy efficiency. This model is used to elucidate the critical reactions that are mostly responsible for the CO2 conversion. Finally, we have compared our results with other CO2 splitting techniques and we identified the limitations as well as the benefits and future possibilities in terms of modifications of DBD plasmas for greenhouse gas conversion in general. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Novel and Functional Single-Layer Sheet of ZnSe

DOE PAGES

Zhou, Jia; Sumpter, Bobby G.; Kent, Paul R. C.; ...

2014-12-23

In this Communication, we report a novel singlelayer sheet of ZnSe, with a three-atomic thickness, which demonstrates a strong quantum confinement effect by exhibiting a large blue shift of 2.0 eV in its absorption edge relative to the zinc blende (ZB) bulk phase. Theoretical optical absorbance shows that the largest absorption of this ultrathin single-layer sheet of ZnSe occurs at a wavelength similar to its four-atom-thick doublelayer counterpart but with higher photoabsorption efficiency, suggesting a superior behavior on incident photon-to-current conversion efficiency for solar water splitting, among other potential applications. The results presented herein for ZnSe may be generalized tomore » other group II-VI analogues.« less

Maximizing omnidirectional light harvesting in metal oxide hyperbranched array architectures

NASA Astrophysics Data System (ADS)

Wu, Wu-Qiang; Feng, Hao-Lin; Rao, Hua-Shang; Xu, Yang-Fan; Kuang, Dai-Bin; Su, Cheng-Yong

2014-05-01

The scrupulous design of nanoarchitectures and smart hybridization of specific active materials are closely related to the overall photovoltaic performance of an anode electrode. Here we present a solution-based strategy for the fabrication of well-aligned metal oxide-based nanowire-nanosheet-nanorod hyperbranched arrays on transparent conducting oxide substrates. For these hyperbranched arrays, we observe a twofold increment in dye adsorption and enhanced light trapping and scattering capability compared with the pristine titanium dioxide nanowires, and thus a power conversion efficiency of 9.09% is achieved. Our growth approach presents a strategy to broaden the photoresponse and maximize the light-harvesting efficiency of arrays architectures, and may lead to applications for energy conversion and storage, catalysis, water splitting and gas sensing.

Maximizing omnidirectional light harvesting in metal oxide hyperbranched array architectures.

PubMed

Wu, Wu-Qiang; Feng, Hao-Lin; Rao, Hua-Shang; Xu, Yang-Fan; Kuang, Dai-Bin; Su, Cheng-Yong

2014-05-29

The scrupulous design of nanoarchitectures and smart hybridization of specific active materials are closely related to the overall photovoltaic performance of an anode electrode. Here we present a solution-based strategy for the fabrication of well-aligned metal oxide-based nanowire-nanosheet-nanorod hyperbranched arrays on transparent conducting oxide substrates. For these hyperbranched arrays, we observe a twofold increment in dye adsorption and enhanced light trapping and scattering capability compared with the pristine titanium dioxide nanowires, and thus a power conversion efficiency of 9.09% is achieved. Our growth approach presents a strategy to broaden the photoresponse and maximize the light-harvesting efficiency of arrays architectures, and may lead to applications for energy conversion and storage, catalysis, water splitting and gas sensing.

Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape-Controlled Au Nanoparticles.

PubMed

Lee, Mi Gyoung; Moon, Cheon Woo; Park, Hoonkee; Sohn, Woonbae; Kang, Sung Bum; Lee, Sanghan; Choi, Kyoung Jin; Jang, Ho Won

2017-10-01

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape-controlled Au NPs on bismuth vanadate (BiVO 4 ) are studied, and a largely enhanced photoactivity of BiVO 4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO 4 achieves 2.4 mA cm -2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO 4 . It is the highest value among the previously reported plasmonic Au NPs/BiVO 4 . Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape-controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operational Testing of Satellite based Hydrological Model (SHM)

NASA Astrophysics Data System (ADS)

Gaur, Srishti; Paul, Pranesh Kumar; Singh, Rajendra; Mishra, Ashok; Gupta, Praveen Kumar; Singh, Raghavendra P.

2017-04-01

Incorporation of the concept of transposability in model testing is one of the prominent ways to check the credibility of a hydrological model. Successful testing ensures ability of hydrological models to deal with changing conditions, along with its extrapolation capacity. For a newly developed model, a number of contradictions arises regarding its applicability, therefore testing of credibility of model is essential to proficiently assess its strength and limitations. This concept emphasizes to perform 'Hierarchical Operational Testing' of Satellite based Hydrological Model (SHM), a newly developed surface water-groundwater coupled model, under PRACRITI-2 program initiated by Space Application Centre (SAC), Ahmedabad. SHM aims at sustainable water resources management using remote sensing data from Indian satellites. It consists of grid cells of 5km x 5km resolution and comprises of five modules namely: Surface Water (SW), Forest (F), Snow (S), Groundwater (GW) and Routing (ROU). SW module (functions in the grid cells with land cover other than forest and snow) deals with estimation of surface runoff, soil moisture and evapotranspiration by using NRCS-CN method, water balance and Hragreaves method, respectively. The hydrology of F module is dependent entirely on sub-surface processes and water balance is calculated based on it. GW module generates baseflow (depending on water table variation with the level of water in streams) using Boussinesq equation. ROU module is grounded on a cell-to-cell routing technique based on the principle of Time Variant Spatially Distributed Direct Runoff Hydrograph (SDDH) to route the generated runoff and baseflow by different modules up to the outlet. For this study Subarnarekha river basin, flood prone zone of eastern India, has been chosen for hierarchical operational testing scheme which includes tests under stationary as well as transitory conditions. For this the basin has been divided into three sub-basins using three flow gauging sites as reference, viz., Muri, Jamshedpur and Ghatshila. Individual model set-up has been prepared for these sub-basins and calibration and validation using Split-sample test, first level of operational testing scheme is in progress. Subsequently for geographic transposability, Proxy-basin test will be done using Muri and Jamshedpur as proxy basins. Climatic transposability will be tested for dry and wet years using Differential split-sample test. For incorporating both geographic and climatic transposability Proxy-basin differential split sample test will be used. For quantitative evaluation of SHM, during Split-sample test Nash-Sutcliffe efficiency (NSE), Coefficient of Determination (R R^2)) and Percent BIAS (PBIAS) are being used. However, for transposability, a productive approach involving these performance measures, i.e. NSE*R R^2)*PBIAS will be used to decide the best value of parameters. Keywords: SHM, credibility, operational testing, transposability.

Efficient solar-driven synthesis, carbon capture, and desalinization, STEP: solar thermal electrochemical production of fuels, metals, bleach.

PubMed

Licht, S

2011-12-15

STEP (solar thermal electrochemical production) theory is derived and experimentally verified for the electrosynthesis of energetic molecules at solar energy efficiency greater than any photovoltaic conversion efficiency. In STEP the efficient formation of metals, fuels, chlorine, and carbon capture is driven by solar thermal heated endothermic electrolyses of concentrated reactants occuring at a voltage below that of the room temperature energy stored in the products. One example is CO(2) , which is reduced to either fuels or storable carbon at a solar efficiency of over 50% due to a synergy of efficient solar thermal absorption and electrochemical conversion at high temperature and reactant concentration. CO(2) -free production of iron by STEP, from iron ore, occurs via Fe(III) in molten carbonate. Water is efficiently split to hydrogen by molten hydroxide electrolysis, and chlorine, sodium, and magnesium from molten chlorides. A pathway is provided for the STEP decrease of atmospheric carbon dioxide levels to pre-industial age levels in 10 years. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tandem Core–Shell Si–Ta 3N 5 Photoanodes for Photoelectrochemical Water Splitting

DOE PAGES

Narkeviciute, Ieva; Chakthranont, Pongkarn; Mackus, Adriaan J. M.; ...

2016-11-22

Here, nanostructured core–shell Si–Ta 3N 5 photoanodes were designed and synthesized to overcome charge transport limitations of Ta 3N 5 for photoelectrochemical water splitting. The core–shell devices were fabricated by atomic layer deposition of amorphous Ta 2O 5 onto nanostructured Si and subsequent nitridation to crystalline Ta 3N 5. Nanostructuring with a thin shell of Ta 3N 5 results in a 10-fold improvement in photocurrent compared to a planar device of the same thickness. In examining thickness dependence of the Ta 3N 5 shell from 10 to 70 nm, superior photocurrent and absorbed-photon-to-current efficiencies are obtained from the thinner Tamore » 3N 5 shells, indicating minority carrier diffusion lengths on the order of tens of nanometers. The fabrication of a heterostructure based on a semiconducting, n-type Si core produced a tandem photoanode with a photocurrent onset shifted to lower potentials by 200 mV. CoTiO x and NiO x water oxidation cocatalysts were deposited onto the Si–Ta 3N 5 to yield active photoanodes that with NiO x retained 50–60% of their maximum photocurrent after 24 h chronoamperometry experiments and are thus among the most stable Ta 3N 5 photoanodes reported to date.« less

Photoelectrochemical Properties and Behavior of α-SnWO4 Photoanodes Synthesized by Hydrothermal Conversion of WO3 Films.

PubMed

Zhu, Zhehao; Sarker, Pranab; Zhao, Chenqi; Zhou, Lite; Grimm, Ronald L; Huda, Muhammad N; Rao, Pratap M

2017-01-18

Metal oxides with moderate band gaps are desired for efficient production of hydrogen from sunlight and water via photoelectrochemical (PEC) water splitting. Here, we report an α-SnWO 4 photoanode synthesized by hydrothermal conversion of WO 3 films that achieves photon to current conversion at wavelengths up to 700 nm (1.78 eV). This photoanode is promising for overall PEC water-splitting because the flat-band potential and voltage of photocurrent onset are more negative than the potential of hydrogen evolution. Furthermore, the photoanode utilizes a large portion of the solar spectrum. However, the photocurrent density reaches only a small fraction of that which is theoretically possible. Density functional theory based thermodynamic and electronic structure calculations were performed to elucidate the nature and impact of defects in α-SnWO 4 prepared by this synthetic route, from which hole localization at Sn-at-W antisite defects was determined to be a likely cause for the poor photocurrent. Measurements further showed that the photocurrent decreases over time due to surface oxidation, which was suppressed by improving the kinetics of hole transfer at the semiconductor/electrolyte interface. Alternative synthetic methods and the addition of protective coatings and/or oxygen evolution catalysts are suggested to improve the PEC performance and stability of this promising α-SnWO 4 material.

Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study

NASA Astrophysics Data System (ADS)

Li, Yi; Fu, Yuqing; Ni, Bilian; Ding, Kaining; Chen, Wenkai; Wu, Kechen; Huang, Xin; Zhang, Yongfan

2018-03-01

The first principle calculations have been performed to investigate the geometries, band structures and optical absorptions of a series of MIL-125 MOFs, in which the 1,4-benzenedicarboxylate (BDC) linkers are modified by different types and amounts of chemical groups, including NH2, OH, and NO2. Our results indicate that new energy bands will appear in the band gap of pristine MIL-125 after introducing new group into BDC linker, but the components of these band gap states and the valence band edge position are sensitive to the type of functional group as well as the corresponding amount. Especially, only the incorporation of amino group can obviously decrease the band gap of MIL-125, and the further reduction of the band gap can be observed if the amount of NH2 is increased. Although MIL-125 functionalized by NH2 group exhibits relatively weak or no activity for the photocatalytic O2 evolution by splitting water, such ligand modification can effectively improve the efficiency in H2 production because now the optical absorption in the visible light region is significantly enhanced. Furthermore, the adsorption of water molecule becomes more favorable after introducing of amino group, which is also beneficial for the water-splitting reaction. The present study can provide theoretical insights to design new photocatalysts based on MIL-125.

Interfacial band-edge engineered TiO2 protection layer on Cu2O photocathodes for efficient water reduction reaction

NASA Astrophysics Data System (ADS)

Choi, Jaesuk; Song, Jun Tae; Jang, Ho Seong; Choi, Min-Jae; Sim, Dong Min; Yim, Soonmin; Lim, Hunhee; Jung, Yeon Sik; Oh, Jihun

2017-01-01

Photoelectrochemical (PEC) water splitting has emerged as a potential pathway to produce sustainable and renewable chemical fuels. Here, we present a highly active Cu2O/TiO2 photocathode for H2 production by enhancing the interfacial band-edge energetics of the TiO2 layer, which is realized by controlling the fixed charge density of the TiO2 protection layer. The band-edge engineered Cu2O/TiO2 (where TiO2 was grown at 80 °C via atomic layer deposition) enhances the photocurrent density up to -2.04 mA/cm2 at 0 V vs. RHE under 1 sun illumination, corresponding to about a 1,200% enhancement compared to the photocurrent density of the photocathode protected with TiO2 grown at 150 °C. Moreover, band-edge engineering of the TiO2 protection layer prevents electron accumulation at the TiO2 layer and enhances both the Faraday efficiency and the stability for hydrogen production during the PEC water reduction reaction. This facile control over the TiO2/electrolyte interface will also provide new insight for designing highly efficient and stable protection layers for various other photoelectrodes such as Si, InP, and GaAs. [Figure not available: see fulltext.

Role of Adsorbed Water on Charge Carrier Dynamics in Photoexcited TiO2

PubMed Central

2017-01-01

Overall photocatalytic water splitting is one of the most sought after processes for sustainable solar-to-chemical energy conversion. The efficiency of this process strongly depends on charge carrier recombination and interaction with surface adsorbates at different time scales. Here, we investigated how hydration of TiO2 P25 affects dynamics of photogenerated electrons at the millisecond to minute time scale characteristic for chemical reactions. We used rapid scan diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS). The decay of photogenerated electron absorption was substantially slower in the presence of associated water. For hydrated samples, the charge carrier recombination rates followed an Arrhenius-type behavior in the temperature range of 273–423 K; these became temperature-independent when the material was dehydrated at temperatures above 423 K or cooled below 273 K. A DFT+U analysis revealed that hydrogen bonding with adsorbed water stabilizes surface-trapped holes at anatase TiO2(101) facet and lowers the barriers for hole migration. Hence, hole mobility should be higher in the hydrated material than in the dehydrated system. This demonstrates that adsorbed associated water can efficiently stabilize photogenerated charge carriers in nanocrystalline TiO2 and suppress their recombination at the time scale up to minutes. PMID:28413570

[How did the earth's oxygen atmosphere originate?].

PubMed

Schäfer, G

2004-09-01

The planet earth did not carry an oxygen atmosphere from the beginning. Though oxygen could arise from radiation mediated water splitting, these processes were not efficient enough to create a global gas atmosphere. Oxygen in the latter is a product of the photosynthetic activity of early green organisms. Only after biological mass-formation of oxygen the UV-protective ozone layer could develop, then enabeling life to move from water onto land. This took billions of years. The basics of the processes of biological oxygen liberation and utilization are described in the following as well as the importance of their steady state equilibrium. Also a hint is given to oxygen as a toxic compound though being a chemical prerequisite for aerobic life on earth.

Bioelectrochemical oxidation of water.

PubMed

Pita, Marcos; Mate, Diana M; Gonzalez-Perez, David; Shleev, Sergey; Fernandez, Victor M; Alcalde, Miguel; De Lacey, Antonio L

2014-04-23

The electrolysis of water provides a link between electrical energy and hydrogen, a high energy density fuel and a versatile energy carrier, but the process is very expensive. Indeed, the main challenge is to reduce energy consumption for large-scale applications using efficient renewable catalysts that can be produced at low cost. Here we present for the first time that laccase can catalyze electrooxidation of H2O to molecular oxygen. Native and laboratory-evolved laccases immobilized onto electrodes serve as bioelectrocatalytic systems with low overpotential and a high O2 evolution ratio against H2O2 production during H2O electrolysis. Our results open new research ground on H2O splitting, as they overcome serious practical limitations associated with artificial electrocatalysts currently used for O2 evolution.

Enhancing Photon Utilization Efficiency for Astaxanthin Production from Haematococcus lacustris Using a Split-Column Photobioreactor.

PubMed

Kim, Z-Hun; Park, Hanwool; Lee, Ho-Sang; Lee, Choul-Gyun

2016-07-28

A split-column photobioreactor (SC-PBR), consisting of two bubble columns with different sizes, was developed to enhance the photon utilization efficiency in an astaxanthin production process from Haematococcus lacustris. Among the two columns, only the smaller column of SC-PBR was illuminated. Astaxanthin productivities and photon efficiencies of the SC-PBRs were compared with a standard bubble-column PBR (BC-PBR). Astaxanthin productivity of SC-PBR was improved by 28%, and the photon utilization efficiencies were 28-366% higher than the original BC-PBR. The results clearly show that the effective light regime of SC-PBR could enhance the production of astaxanthin.

Ray-splitting correction to the Weyl formula: Experiment versus theory

NASA Astrophysics Data System (ADS)

Blumel, Reinhold

2004-03-01

Ray splitting is a phenomenon we are all familiar with: A light ray hitting a water surface at an angle is split into a transmitted and a reflected ray. Ray splitting is not restricted to light and water, but occurs generally in all wave systems in which the properties of the propagation medium change rapidly on the scale of a wave length. It was predicted by Prange et al. [Phys. Rev. E 53, 207 (1996)] that ray splitting produces universal corrections to the Weyl formula, i.e. the average density of states. Following a brief review of Weyl's theory and the theory of ray splitting, this talk presents recent results of a first experimental confirmation of the existence of ray-splitting corrections to the Weyl formula. The experiment, a quasi two-dimensional microwave cavity loaded with two dielectric bars, has been carried out by Corrie Vaa and Peter Koch at the State University of New York at Stony Brook [C. Vaa, P. M. Koch, and R. Blumel, Phys. Rev. Lett. 90, 194102 (2003)]. This research is supported by the NSF under Grant Numbers PHY-9732443, PHY-0099398 and PHY-9984075.

Decoupling Hydrogen and Oxygen Production in Acidic Water Electrolysis Using a Polytriphenylamine-Based Battery Electrode.

PubMed

Ma, Yuanyuan; Dong, Xiaoli; Wang, Yonggang; Xia, Yongyao

2018-03-05

Hydrogen production through water splitting is considered a promising approach for solar energy harvesting. However, the variable and intermittent nature of solar energy and the co-production of H 2 and O 2 significantly reduce the flexibility of this approach, increasing the costs of its use in practical applications. Herein, using the reversible n-type doping/de-doping reaction of the solid-state polytriphenylamine-based battery electrode, we decouple the H 2 and O 2 production in acid water electrolysis. In this architecture, the H 2 and O 2 production occur at different times, which eliminates the issue of gas mixing and adapts to the variable and intermittent nature of solar energy, facilitating the conversion of solar energy to hydrogen (STH). Furthermore, for the first time, we demonstrate a membrane-free solar water splitting through commercial photovoltaics and the decoupled acid water electrolysis, which potentially paves the way for a new approach for solar water splitting. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

On the Role of Fe2O3 Surface States for Water Splitting

NASA Astrophysics Data System (ADS)

Caspary Toroker, Maytal

Understanding the chemical nature and role of electrode surface states is crucial for improved electrochemical cell operation. For iron (III) oxide (α-Fe2O3) , which is one of the most widely studied anode electrodes used for water splitting, surface states were related to the appearance of a dominant absorption peak during water splitting. The chemical origin of this signature is still unclear and this open question has provoked tremendous debate. In order to pin down the origin and role of surface states, we perform first principle calculations with density functional theory +U on several possible adsorbates at the α-Fe2O3(0001) surface. We show that the origin of the surface absorption peak could be a Fe-Otype bond that functions as an essential intermediate of water oxidation

Novel MOF-Derived Co@N-C Bifunctional Catalysts for Highly Efficient Zn-Air Batteries and Water Splitting.

PubMed

Zhang, Mingdao; Dai, Quanbin; Zheng, Hegen; Chen, Mindong; Dai, Liming

2018-03-01

Metal-organic frameworks (MOFs) and MOF-derived materials have recently attracted considerable interest as alternatives to noble-metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N-C materials (C-MOF-C2-T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C-MOF-C2-900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N-doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO 2 , respectively. Primary Zn-air batteries based on C-MOF-900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g Zn -1 under 10 mA cm -2 . Rechargeable Zn-air batteries based on C-MOF-C2-900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm -2 ), along with an excellent cycling stability with no increase in polarization even after 120 h - outperform their counterparts based on noble-metal-based air electrodes. The resultant rechargeable Zn-air batteries are used to efficiently power electrochemical water-splitting systems, demonstrating promising potential as integrated green energy systems for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactor Experiments at the University of Minnesota.

DTIC Science & Technology

1987-07-15

metallurgy; zinc, zinc oxide; solar thermal,’ solar Pi% thermoelectrochemical’ water splitting, separation devices; reactors e, ? 20. AeSiRACT (Continue oe...reported. Water splitting, recovery of hydrogen 4. and sulfur from hydrogen sulfide, electrolysis of zinc oxide in vapor and liquid phases, oil...CH4-CO2 reforming process. 2. Hydrogen production from water and the production of hydrogen and sulfur (or ammonia and sulfuric acid) from H2S. 3

Conceptual Design and Optimal Power Control Strategy for AN Eco-Friendly Hybrid Vehicle

NASA Astrophysics Data System (ADS)

Nasiri, N. Mir; Chieng, Frederick T. A.

2011-06-01

This paper presents a new concept for a hybrid vehicle using a torque and speed splitting technique. It is implemented by the newly developed controller in combination with a two degree of freedom epicyclic gear transmission. This approach enables optimization of the power split between the less powerful electrical motor and more powerful engine while driving a car load. The power split is fundamentally a dual-energy integration mechanism as it is implemented by using the epicyclic gear transmission that has two inputs and one output for a proper power distribution. The developed power split control system manages the operation of both the inputs to have a known output with the condition of maintaining optimum operating efficiency of the internal combustion engine and electrical motor. This system has a huge potential as it is possible to integrate all the features of hybrid vehicle known to-date such as the regenerative braking system, series hybrid, parallel hybrid, series/parallel hybrid, and even complex hybrid (bidirectional). By using the new power split system it is possible to further reduce fuel consumption and increase overall efficiency.

Energy distribution analysis in boosted HCCI-like / LTGC engines – Understanding the trade-offs to maximize the thermal efficiency

DOE PAGES

Dernotte, Jeremie; Dec, John E.; Ji, Chunsheng

2015-04-14

A detailed understanding of the various factors affecting the trends in gross-indicated thermal efficiency with changes in key operating parameters has been carried out, applied to a one-liter displacement single-cylinder boosted Low-Temperature Gasoline Combustion (LTGC) engine. This work systematically investigates how the supplied fuel energy splits into the following four energy pathways: gross-indicated thermal efficiency, combustion inefficiency, heat transfer and exhaust losses, and how this split changes with operating conditions. Additional analysis is performed to determine the influence of variations in the ratio of specific heat capacities (γ) and the effective expansion ratio, related to the combustion-phasing retard (CA50), onmore » the energy split. Heat transfer and exhaust losses are computed using multiple standard cycle analysis techniques. Furthermore, the various methods are evaluated in order to validate the trends.« less

Performance evaluation of four different methods for circulating water in commercial-scale, split-pond aquaculture systems

USDA-ARS?s Scientific Manuscript database

The split-pond consists of a fish-culture basin that is connected to a waste-treatment lagoon by two conveyance structures. Water is circulated between the two basins with high-volume pumps and many different pumping systems are being used on commercial farms. Pump performance was evaluated with fou...

Local error estimates for adaptive simulation of the Reaction–Diffusion Master Equation via operator splitting

PubMed Central

Hellander, Andreas; Lawson, Michael J; Drawert, Brian; Petzold, Linda

2015-01-01

The efficiency of exact simulation methods for the reaction-diffusion master equation (RDME) is severely limited by the large number of diffusion events if the mesh is fine or if diffusion constants are large. Furthermore, inherent properties of exact kinetic-Monte Carlo simulation methods limit the efficiency of parallel implementations. Several approximate and hybrid methods have appeared that enable more efficient simulation of the RDME. A common feature to most of them is that they rely on splitting the system into its reaction and diffusion parts and updating them sequentially over a discrete timestep. This use of operator splitting enables more efficient simulation but it comes at the price of a temporal discretization error that depends on the size of the timestep. So far, existing methods have not attempted to estimate or control this error in a systematic manner. This makes the solvers hard to use for practitioners since they must guess an appropriate timestep. It also makes the solvers potentially less efficient than if the timesteps are adapted to control the error. Here, we derive estimates of the local error and propose a strategy to adaptively select the timestep when the RDME is simulated via a first order operator splitting. While the strategy is general and applicable to a wide range of approximate and hybrid methods, we exemplify it here by extending a previously published approximate method, the Diffusive Finite-State Projection (DFSP) method, to incorporate temporal adaptivity. PMID:26865735

Local error estimates for adaptive simulation of the Reaction-Diffusion Master Equation via operator splitting.

PubMed

Hellander, Andreas; Lawson, Michael J; Drawert, Brian; Petzold, Linda

2014-06-01

The efficiency of exact simulation methods for the reaction-diffusion master equation (RDME) is severely limited by the large number of diffusion events if the mesh is fine or if diffusion constants are large. Furthermore, inherent properties of exact kinetic-Monte Carlo simulation methods limit the efficiency of parallel implementations. Several approximate and hybrid methods have appeared that enable more efficient simulation of the RDME. A common feature to most of them is that they rely on splitting the system into its reaction and diffusion parts and updating them sequentially over a discrete timestep. This use of operator splitting enables more efficient simulation but it comes at the price of a temporal discretization error that depends on the size of the timestep. So far, existing methods have not attempted to estimate or control this error in a systematic manner. This makes the solvers hard to use for practitioners since they must guess an appropriate timestep. It also makes the solvers potentially less efficient than if the timesteps are adapted to control the error. Here, we derive estimates of the local error and propose a strategy to adaptively select the timestep when the RDME is simulated via a first order operator splitting. While the strategy is general and applicable to a wide range of approximate and hybrid methods, we exemplify it here by extending a previously published approximate method, the Diffusive Finite-State Projection (DFSP) method, to incorporate temporal adaptivity.

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

DOE PAGES

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.; ...

2013-12-30

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

p-Type CuRhO 2 as a Self-Healing Photoelectrode for Water Reduction under Visible Light

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Jing; Krizan, Jason W.; Gibson, Quinn D.

Polycrystalline CuRhO 2 is investigated as a photocathode for the splitting of water under visible irradiation. The band edge positions of this material straddle the water oxidation and reduction redox potentials. Thus, photogenerated conduction band electrons are sufficiently energetic to reduce water, while the associated valence band holes are energetically able to oxidize water to O 2. Under visible illumination, H 2 production is observed with ~0.2 V underpotential in an air-saturated solution. In contrast, H 2 production in an Ar-saturated solution was found to be unstable. This instability is associated with the reduction of the semiconductor forming Cu(s). However,more » in the presence of air or O 2, bulk Cu(s) was not detected, implying that CuRhO 2 is self-healing when air is present. Here, this property allows for the stable formation of H 2 with ca. 80% Faradaic efficiency.« less

Reversible Hydrophobic to Hydrophilic Transition in Graphene via Water Splitting Induced by UV Irradiation

PubMed Central

Xu, Zhemi; Ao, Zhimin; Chu, Dewei; Younis, Adnan; Li, Chang Ming; Li, Sean

2014-01-01

Although the reversible wettability transition between hydrophobic and hydrophilic graphene under ultraviolet (UV) irradiation has been observed, the mechanism for this phenomenon remains unclear. In this work, experimental and theoretical investigations demonstrate that the H2O molecules are split into hydrogen and hydroxyl radicals, which are then captured by the graphene surface through chemical binding in an ambient environment under UV irradiation. The dissociative adsorption of H2O molecules induces the wettability transition in graphene from hydrophobic to hydrophilic. Our discovery may hold promise for the potential application of graphene in water splitting. PMID:25245110

Structure and tunneling dynamics in a model system of peptide co-solvents: rotational spectroscopy of the 2,2,2-trifluoroethanol⋯water complex.

PubMed

Thomas, Javix; Xu, Yunjie

2014-06-21

The hydrogen-bonding topology and tunneling dynamics of the binary adduct, 2,2,2-trifluoroethanol (TFE)⋯water, were investigated using chirped pulse and cavity based Fourier transform microwave spectroscopy with the aid of high level ab initio calculations. Rotational spectra of the most stable binary TFE⋯water conformer and five of its deuterium isotopologues were assigned. A strong preference for the insertion binding topology where water is inserted into the existing intramolecular hydrogen-bonded ring of TFE was observed. Tunneling splittings were detected in all of the measured rotational transitions of TFE⋯water. Based on the relative intensity of the two tunneling components and additional isotopic data, the splitting can be unambiguously attributed to the tunneling motion of the water subunit, i.e., the interchange of the bonded and nonbonded hydrogen atoms of water. The absence of any other splitting in the rotational transitions of all isotopologues observed indicates that the tunneling between g+ and g- TFE is quenched in the TFE⋯H2O complex.

Time-splitting combined with exponential wave integrator fourier pseudospectral method for Schrödinger-Boussinesq system

NASA Astrophysics Data System (ADS)

Liao, Feng; Zhang, Luming; Wang, Shanshan

2018-02-01

In this article, we formulate an efficient and accurate numerical method for approximations of the coupled Schrödinger-Boussinesq (SBq) system. The main features of our method are based on: (i) the applications of a time-splitting Fourier spectral method for Schrödinger-like equation in SBq system, (ii) the utilizations of exponential wave integrator Fourier pseudospectral for spatial derivatives in the Boussinesq-like equation. The scheme is fully explicit and efficient due to fast Fourier transform. The numerical examples are presented to show the efficiency and accuracy of our method.

Unitary limit in crossed Andreev transport

DOE PAGES

Sadovskyy, I. A.; Lesovik, G. B.; Vinokur, V. M.

2015-10-08

One of the most promising approaches for generating spin- and energy-entangled electron pairs is splitting a Cooper pair into the metal through spatially separated terminals. Utilizing hybrid systems with the energy-dependent barriers at the superconductor/normal metal (NS) interfaces, one can achieve a practically 100% efficiency outcome of entangled electrons. We investigate a minimalistic one-dimensional model comprising a superconductor and two metallic leads and derive an expression for an electron-to-hole transmission probability as a measure of splitting efficiency. We find the conditions for achieving 100% efficiency and present analytical results for the differential conductance and differential noise.

0D-2D Quantum Dot: Metal Dichalcogenide Nanocomposite Photocatalyst Achieves Efficient Hydrogen Generation.

PubMed

Liu, Xiao-Yuan; Chen, Hao; Wang, Ruili; Shang, Yuequn; Zhang, Qiong; Li, Wei; Zhang, Guozhen; Su, Juan; Dinh, Cao Thang; de Arquer, F Pelayo García; Li, Jie; Jiang, Jun; Mi, Qixi; Si, Rui; Li, Xiaopeng; Sun, Yuhan; Long, Yi-Tao; Tian, He; Sargent, Edward H; Ning, Zhijun

2017-06-01

Hydrogen generation via photocatalysis-driven water splitting provides a convenient approach to turn solar energy into chemical fuel. The development of photocatalysis system that can effectively harvest visible light for hydrogen generation is an essential task in order to utilize this technology. Herein, a kind of cadmium free Zn-Ag-In-S (ZAIS) colloidal quantum dots (CQDs) that shows remarkably photocatalytic efficiency in the visible region is developed. More importantly, a nanocomposite based on the combination of 0D ZAIS CQDs and 2D MoS 2 nanosheet is developed. This can leverage the strong light harvesting capability of CQDs and catalytic performance of MoS 2 simultaneously. As a result, an excellent external quantum efficiency of 40.8% at 400 nm is achieved for CQD-based hydrogen generation catalyst. This work presents a new platform for the development of high-efficiency photocatalyst based on 0D-2D nanocomposite. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Efficient Perovskite-Perovskite Tandem Solar Cells Reaching 80% of the Theoretical Limit in Photovoltage.

PubMed

Rajagopal, Adharsh; Yang, Zhibin; Jo, Sae Byeok; Braly, Ian L; Liang, Po-Wei; Hillhouse, Hugh W; Jen, Alex K-Y

2017-09-01

Organic-inorganic hybrid perovskite multijunction solar cells have immense potential to realize power conversion efficiencies (PCEs) beyond the Shockley-Queisser limit of single-junction solar cells; however, they are limited by large nonideal photovoltage loss (V oc,loss ) in small- and large-bandgap subcells. Here, an integrated approach is utilized to improve the V oc of subcells with optimized bandgaps and fabricate perovskite-perovskite tandem solar cells with small V oc,loss . A fullerene variant, Indene-C 60 bis-adduct, is used to achieve optimized interfacial contact in a small-bandgap (≈1.2 eV) subcell, which facilitates higher quasi-Fermi level splitting, reduces nonradiative recombination, alleviates hysteresis instabilities, and improves V oc to 0.84 V. Compositional engineering of large-bandgap (≈1.8 eV) perovskite is employed to realize a subcell with a transparent top electrode and photostabilized V oc of 1.22 V. The resultant monolithic perovskite-perovskite tandem solar cell shows a high V oc of 1.98 V (approaching 80% of the theoretical limit) and a stabilized PCE of 18.5%. The significantly minimized nonideal V oc,loss is better than state-of-the-art silicon-perovskite tandem solar cells, which highlights the prospects of using perovskite-perovskite tandems for solar-energy generation. It also unlocks opportunities for solar water splitting using hybrid perovskites with solar-to-hydrogen efficiencies beyond 15%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stabilized CdSe-CoPi composite photoanode for light-assisted water oxidation by transformation of a CdSe/cobalt metal thin film.

PubMed

Costi, Ronny; Young, Elizabeth R; Bulović, Vladimir; Nocera, Daniel G

2013-04-10

Integration of water splitting catalysts with visible-light-absorbing semiconductors would enable direct solar-energy-to-fuel conversion schemes such as those based on water splitting. A disadvantage of some common semiconductors that possess desirable optical bandgaps is their chemical instability under the conditions needed for oxygen evolution reaction (OER). In this study, we demonstrate the dual benefits gained from using a cobalt metal thin-film as the precursor for the preparation of cobalt-phosphate (CoPi) OER catalyst on cadmium chalcogenide photoanodes. The cobalt layer protects the underlying semiconductor from oxidation and degradation while forming the catalyst and simultaneously facilitates the advantageous incorporation of the cadmium chalcogenide layer into the CoPi layer during continued processing of the electrode. The resulting hybrid material forms a stable photoactive anode for light-assisted water splitting.

Utilization of Metal Sulfide Material of (CuGa)(1-x)Zn(2x)S2 Solid Solution with Visible Light Response in Photocatalytic and Photoelectrochemical Solar Water Splitting Systems.

PubMed

Kato, Takaaki; Hakari, Yuichiro; Ikeda, Satoru; Jia, Qingxin; Iwase, Akihide; Kudo, Akihiko

2015-03-19

Upon forming a solid solution between CuGaS2 and ZnS, we have successfully developed a highly active (CuGa)(1-x)Zn(2x)S2 photocatalyst for H2 evolution in the presence of sacrificial reagents under visible light irradiation. The Ru-loaded (CuGa)0.8Zn0.4S2 functioned as a H2-evolving photocatalyst in a Z-scheme system with BiVO4 of an O2-evolving photocatalyst and Co complexes of an electron mediator. The Z-scheme system split water into H2 and O2 under visible light and simulated sunlight irradiation. The (CuGa)(1-x)Zn(2x)S2 possessed a p-type semiconductor character. The photoelectrochemical cell with a Ru-loaded (CuGa)0.5ZnS2 photocathode and a CoO(x)-modified BiVO4 photoanode split water even without applying an external bias. Thus, we successfully demonstrated that the metal sulfide material group can be available for Z-scheme and electrochemical systems to achieve solar water splitting into H2 and O2.

Enhancing electrochemical water-splitting kinetics by polarization-driven formation of near-surface iron(0): an in situ XPS study on perovskite-type electrodes.

PubMed

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

2015-02-23

In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6 Sr0.4 FeO3-δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe(0) on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Artificial photosynthesis: understanding water splitting in nature

PubMed Central

Cox, Nicholas; Pantazis, Dimitrios A.; Neese, Frank; Lubitz, Wolfgang

2015-01-01

In the context of a global artificial photosynthesis (GAP) project, we review our current work on nature's water splitting catalyst. In a recent report (Cox et al. 2014 Science 345, 804–808 (doi:10.1126/science.1254910)), we showed that the catalyst—a Mn4O5Ca cofactor—converts into an ‘activated’ form immediately prior to the O–O bond formation step. This activated state, which represents an all MnIV complex, is similar to the structure observed by X-ray crystallography but requires the coordination of an additional water molecule. Such a structure locates two oxygens, both derived from water, in close proximity, which probably come together to form the product O2 molecule. We speculate that formation of the activated catalyst state requires inherent structural flexibility. These features represent new design criteria for the development of biomimetic and bioinspired model systems for water splitting catalysts using first-row transition metals with the aim of delivering globally deployable artificial photosynthesis technologies. PMID:26052426

Light-driven water oxidation for solar fuels

PubMed Central

Young, Karin J.; Martini, Lauren A.; Milot, Rebecca L.; III, Robert C. Snoeberger; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

2014-01-01

Light-driven water oxidation is an essential step for conversion of sunlight into storable chemical fuels. Fujishima and Honda reported the first example of photoelectrochemical water oxidation in 1972. In their system, TiO2 was irradiated with ultraviolet light, producing oxygen at the anode and hydrogen at a platinum cathode. Inspired by this system, more recent work has focused on functionalizing nanoporous TiO2 or other semiconductor surfaces with molecular adsorbates, including chromophores and catalysts that absorb visible light and generate electricity (i.e., dye-sensitized solar cells) or trigger water oxidation at low overpotentials (i.e., photocatalytic cells). The physics involved in harnessing multiple photochemical events for multielectron reactions, as required in the four-electron water oxidation process, has been the subject of much experimental and computational study. In spite of significant advances with regard to individual components, the development of highly efficient photocatalytic cells for solar water splitting remains an outstanding challenge. This article reviews recent progress in the field with emphasis on water-oxidation photoanodes inspired by the design of functionalized thin film semiconductors of typical dye-sensitized solar cells. PMID:25364029

Preparation of cauliflower-like CdS/ZnS/ZnO nanostructure and its photoelectric properties

NASA Astrophysics Data System (ADS)

Liu, Zhifeng; Guo, Keying; Wang, Yun; Zheng, Xuerong; Ya, Jing; Li, Junwei; Han, Li; Liu, Zhichao; Han, Jianhua

2014-06-01

Cauliflower-like CdS/ZnS/ZnO nanostructure is fabricated via a simple hydrothermal method. Factors such as concentration of reaction solution, reaction temperature, as well as reaction time in the synthetic process are investigated, and the working mechanism of the nanostructure is suggested. Hydrogen generation efficiency of 4.69 % at 0.29 V versus saturated calomel electrode is achieved using synthesized nanostructure as electrode due to the improved absorption and appropriate energy gap structure, which is confirmed by enhanced absorption spectrum. The expected products have potential application in photoelectrochemical water splitting.

DOE Zero Energy Ready Home Case Study: Healthy Efficient Homes - Spirit Lake, Iowa

DOE Office of Scientific and Technical Information (OSTI.GOV)

none,

2014-11-01

This case study describes a DOE Zero Energy Ready Home in Spirit Lake, Iowa, that scored HERS 41 without PV and HERS 28 with PV. This 3,048 ft2 custom home has advanced framed walls filled with 1.5 inches closed-cell spray foam, a vented attic with spray foam-sealed top plates and blown fiberglass over the ceiling deck. R-23 basement walls are ICF plus two 2-inch layers of EPS. The house also has a mini-split heat pump, fresh air fan intake, and a solar hot water heater.

Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation

NASA Astrophysics Data System (ADS)

Joya, Khurram S.; Sinatra, Lutfan; Abdulhalim, Lina G.; Joshi, Chakra P.; Hedhili, M. N.; Bakr, Osman M.; Hussain, Irshad

2016-05-01

Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation. Electronic supplementary information (ESI) available: CCDC 1419754 and 1419731. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6nr00709k

Two biomechanical strategies for locomotor adaptation to split-belt treadmill walking in subjects with and without transtibial amputation.

PubMed

Selgrade, Brian P; Toney, Megan E; Chang, Young-Hui

2017-02-28

Locomotor adaptation is commonly studied using split-belt treadmill walking, in which each foot is placed on a belt moving at a different speed. As subjects adapt to split-belt walking, they reduce metabolic power, but the biomechanical mechanism behind this improved efficiency is unknown. Analyzing mechanical work performed by the legs and joints during split-belt adaptation could reveal this mechanism. Because ankle work in the step-to-step transition is more efficient than hip work, we hypothesized that control subjects would reduce hip work on the fast belt and increase ankle work during the step-to-step transition as they adapted. We further hypothesized that subjects with unilateral, trans-tibial amputation would instead increase propulsive work from their intact leg on the slow belt. Control subjects reduced hip work and shifted more ankle work to the step-to-step transition, supporting our hypothesis. Contrary to our second hypothesis, intact leg work, ankle work and hip work in amputees were unchanged during adaptation. Furthermore, all subjects increased collisional energy loss on the fast belt, but did not increase propulsive work. This was possible because subjects moved further backward during fast leg single support in late adaptation than in early adaptation, compensating by reducing backward movement in slow leg single support. In summary, subjects used two strategies to improve mechanical efficiency in split-belt walking adaptation: a CoM displacement strategy that allows for less forward propulsion on the fast belt; and, an ankle timing strategy that allows efficient ankle work in the step-to-step transition to increase while reducing inefficient hip work. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fully coupled approach to modeling shallow water flow, sediment transport, and bed evolution in rivers

NASA Astrophysics Data System (ADS)

Li, Shuangcai; Duffy, Christopher J.

2011-03-01

Our ability to predict complex environmental fluid flow and transport hinges on accurate and efficient simulations of multiple physical phenomenon operating simultaneously over a wide range of spatial and temporal scales, including overbank floods, coastal storm surge events, drying and wetting bed conditions, and simultaneous bed form evolution. This research implements a fully coupled strategy for solving shallow water hydrodynamics, sediment transport, and morphological bed evolution in rivers and floodplains (PIHM_Hydro) and applies the model to field and laboratory experiments that cover a wide range of spatial and temporal scales. The model uses a standard upwind finite volume method and Roe's approximate Riemann solver for unstructured grids. A multidimensional linear reconstruction and slope limiter are implemented, achieving second-order spatial accuracy. Model efficiency and stability are treated using an explicit-implicit method for temporal discretization with operator splitting. Laboratory-and field-scale experiments were compiled where coupled processes across a range of scales were observed and where higher-order spatial and temporal accuracy might be needed for accurate and efficient solutions. These experiments demonstrate the ability of the fully coupled strategy in capturing dynamics of field-scale flood waves and small-scale drying-wetting processes.

Reservoir simulation with the cubic plus (cross-) association equation of state for water, CO2, hydrocarbons, and tracers

NASA Astrophysics Data System (ADS)

Moortgat, Joachim

2018-04-01

This work presents an efficient reservoir simulation framework for multicomponent, multiphase, compressible flow, based on the cubic-plus-association (CPA) equation of state (EOS). CPA is an accurate EOS for mixtures that contain non-polar hydrocarbons, self-associating polar water, and cross-associating molecules like methane, ethane, unsaturated hydrocarbons, CO2, and H2S. While CPA is accurate, its mathematical formulation is highly non-linear, resulting in excessive computational costs that have made the EOS unfeasible for large scale reservoir simulations. This work presents algorithms that overcome these bottlenecks and achieve an efficiency comparable to the much simpler cubic EOS approach. The main applications that require such accurate phase behavior modeling are 1) the study of methane leakage from high-pressure production wells and its potential impact on groundwater resources, 2) modeling of geological CO2 sequestration in brine aquifers when one is interested in more than the CO2 and H2O components, e.g. methane, other light hydrocarbons, and various tracers, and 3) enhanced oil recovery by CO2 injection in reservoirs that have previously been waterflooded or contain connate water. We present numerical examples of all those scenarios, extensive validation of the CPA EOS with experimental data, and analyses of the efficiency of our proposed numerical schemes. The accuracy, efficiency, and robustness of the presented phase split computations pave the way to more widespread adoption of CPA in reservoir simulators.

Dynamics of photogenerated holes in surface modified α-Fe2O3 photoanodes for solar water splitting

PubMed Central

Barroso, Monica; Mesa, Camilo A.; Pendlebury, Stephanie R.; Cowan, Alexander J.; Hisatomi, Takashi; Sivula, Kevin; Grätzel, Michael; Klug, David R.; Durrant, James R.

2012-01-01

This paper addresses the origin of the decrease in the external electrical bias required for water photoelectrolysis with hematite photoanodes, observed following surface treatments of such electrodes. We consider two alternative surface modifications: a cobalt oxo/hydroxo-based (CoOx) overlayer, reported previously to function as an efficient water oxidation electrocatalyst, and a Ga2O3 overlayer, reported to passivate hematite surface states. Transient absorption studies of these composite electrodes under applied bias showed that the cathodic shift of the photocurrent onset observed after each of the surface modifications is accompanied by a similar cathodic shift of the appearance of long-lived hematite photoholes, due to a retardation of electron/hole recombination. The origin of the slower electron/hole recombination is assigned primarily to enhanced electron depletion in the Fe2O3 for a given applied bias. PMID:22802673

Effect of doping (C or N) and co-doping (C+N) on the photoactive properties of magnetron sputtered titania coatings for the application of solar water-splitting.

PubMed

Rahman, M; Dang, B H Q; McDonnell, K; MacElroy, J M D; Dowling, D P

2012-06-01

The photocatalytic splitting of water into hydrogen and oxygen using a photoelectrochemical (PEC) cell containing titanium dioxide (TiO2) photoanode is a potentially renewable source of chemical fuels. However, the size of the band gap (-3.2 eV) of the TiO2 photocatalyst leads to its relatively low photoactivity toward visible light in a PEC cell. The development of materials with smaller band gaps of approximately 2.4 eV is therefore necessary to operate PEC cells efficiently. This study investigates the effect of dopant (C or N) and co-dopant (C+N) on the physical, structural and photoactivity of TiO2 nano thick coating. TiO2 nano-thick coatings were deposited using a closed field DC reactive magnetron sputtering technique, from titanium target in argon plasma with trace addition of oxygen. In order to study the influence of doping such as C, N and C+N inclusions in the TiO2 coatings, trace levels of CO2 or N2 or CO2+N2 gas were introduced into the deposition chamber respectively. The properties of the deposited nano-coatings were determined using Spectroscopic Ellipsometry, SEM, AFM, Optical profilometry, XPS, Raman, X-ray diffraction UV-Vis spectroscopy and tri-electrode potentiostat measurements. Coating growth rate, structure, surface morphology and roughness were found to be significantly influenced by the types and amount of doping. Substitutional type of doping in all doped sample were confirmed by XPS. UV-vis measurement confirmed that doping (especially for C doped sample) facilitate photoactivity of sputtered deposited titania coating toward visible light by reducing bandgap. The photocurrent density (indirect indication of water splitting performance) of the C-doped photoanode was approximately 26% higher in comparison with un-doped photoanode. However, coating doped with nitrogen (N or N+C) does not exhibit good performance in the photoelectrochemical cell due to their higher charge recombination properties.

Diverse and tunable electronic structures of single-layer metal phosphorus trichalcogenides for photocatalytic water splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jian; Beijing Computational Science Research Center, Beijing 100084; College of Electrical and Information Engineering, Hunan Institute of Engineering, Xiangtan 411105, Hunan

2014-02-07

The family of bulk metal phosphorus trichalcogenides (APX{sub 3}, A = M{sup II}, M{sub 0.5}{sup I}M{sub 0.5}{sup III}; X = S, Se; M{sup I}, M{sup II}, and M{sup III} represent Group-I, Group-II, and Group-III metals, respectively) has attracted great attentions because such materials not only own magnetic and ferroelectric properties, but also exhibit excellent properties in hydrogen storage and lithium battery because of the layered structures. Many layered materials have been exfoliated into two-dimensional (2D) materials, and they show distinct electronic properties compared with their bulks. Here we present a systematical study of single-layer metal phosphorus trichalcogenides by density functionalmore » theory calculations. The results show that the single layer metal phosphorus trichalcogenides have very low formation energies, which indicates that the exfoliation of single layer APX{sub 3} should not be difficult. The family of single layer metal phosphorus trichalcogenides exhibits a large range of band gaps from 1.77 to 3.94 eV, and the electronic structures are greatly affected by the metal or the chalcogenide atoms. The calculated band edges of metal phosphorus trichalcogenides further reveal that single-layer ZnPSe{sub 3}, CdPSe{sub 3}, Ag{sub 0.5}Sc{sub 0.5}PSe{sub 3}, and Ag{sub 0.5}In{sub 0.5}PX{sub 3} (X = S and Se) have both suitable band gaps for visible-light driving and sufficient over-potentials for water splitting. More fascinatingly, single-layer Ag{sub 0.5}Sc{sub 0.5}PSe{sub 3} is a direct band gap semiconductor, and the calculated optical absorption further convinces that such materials own outstanding properties for light absorption. Such results demonstrate that the single layer metal phosphorus trichalcogenides own high stability, versatile electronic properties, and high optical absorption, thus such materials have great chances to be high efficient photocatalysts for water-splitting.« less

Synergistic effects of graphene quantum dot sensitization and nitrogen doping of ordered mesoporous TiO2 thin films for water splitting photocatalysis(Conference Presentation)

NASA Astrophysics Data System (ADS)

Islam, Syed Z.; Wanninayake, Namal; Reed, Allen D.; Kim, Doo-Young; Rankin, Stephen E.

2016-10-01

The optical and electronic properties of TiO2 thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO2, critical challenges include the innate inability of TiO2 to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, we prepared ordered mesoporous TiO2 films co-modified by graphene quantum dot sensitization and nitrogen doping (GQD-N-TiO2) for hydrogen production from photoelectrochemical water splitting under visible light irradiation. First, cubic ordered mesoporous TiO2 films were prepared by a surfactant templated sol-gel method. Then, TiO2 films were treated with N2/Ar plasma for the incorporation of substitutional N atoms into the lattice of TiO2. GQDs were prepared by chemically oxidizing carbon nano-onions. The immobilization of GQDs was accomplished by reacting carboxyl groups of GQDs with amine groups of N-TiO2 developed by the prior immobilization of (3-aminopropyl)triethoxysilane (APTES). Successful immobilization of GQDs onto N-TiO2 was probed by UV-Vis, FT-IR, and scanning electron microscopy. Further, zeta potential and contact angle measurements showed enhanced surface charge and hydrophilicity, confirming the successful immobilization of GQDs. The GQD-N-TiO2, N-TiO2 and GQD-TiO2 films showed 400 times, 130 times and 8 times photocurrent enhancement, respectively, compared to TiO2 films for water splitting with a halogen bulb light source. This outstanding enhancement is attributed to the high surface area of mesoporous films and synergistic effects of nitrogen doping and GQD sensitization resulting in enhanced visible light absorption, efficient charge separation and transport.

High efficiency solar cells combining a perovskite and a silicon heterojunction solar cells via an optical splitting system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uzu, Hisashi, E-mail: Hisashi.Uzu@kaneka.co.jp, E-mail: npark@skku.edu; Ichikawa, Mitsuru; Hino, Masashi

2015-01-05

We have applied an optical splitting system in order to achieve very high conversion efficiency for a full spectrum multi-junction solar cell. This system consists of multiple solar cells with different band gap optically coupled via an “optical splitter.” An optical splitter is a multi-layered beam splitter with very high reflection in the shorter-wave-length range and very high transmission in the longer-wave-length range. By splitting the incident solar spectrum and distributing it to each solar cell, the solar energy can be managed more efficiently. We have fabricated optical splitters and used them with a wide-gap amorphous silicon (a-Si) solar cellmore » or a CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cell as top cells, combined with mono-crystalline silicon heterojunction (HJ) solar cells as bottom cells. We have achieved with a 550 nm cutoff splitter an active area conversion efficiency of over 25% using a-Si and HJ solar cells and 28% using perovskite and HJ solar cells.« less

Off-axis holographic lens spectrum-splitting photovoltaic system for direct and diffuse solar energy conversion.

PubMed

Vorndran, Shelby D; Chrysler, Benjamin; Wheelwright, Brian; Angel, Roger; Holman, Zachary; Kostuk, Raymond

2016-09-20

This paper describes a high-efficiency, spectrum-splitting photovoltaic module that uses an off-axis volume holographic lens to focus and disperse incident solar illumination to a rectangular shaped high-bandgap indium gallium phosphide cell surrounded by strips of silicon cells. The holographic lens design allows efficient collection of both direct and diffuse illumination to maximize energy yield. We modeled the volume diffraction characteristics using rigorous coupled-wave analysis, and simulated system performance using nonsequential ray tracing and PV cell data from the literature. Under AM 1.5 illumination conditions the simulated module obtained a 30.6% conversion efficiency. This efficiency is a 19.7% relative improvement compared to the more efficient cell in the system (silicon). The module was also simulated under a typical meteorological year of direct and diffuse irradiance in Tucson, Arizona, and Seattle, Washington. Compared to a flat panel silicon module, the holographic spectrum splitting module obtained a relative improvement in energy yield of 17.1% in Tucson and 14.0% in Seattle. An experimental proof-of-concept volume holographic lens was also fabricated in dichromated gelatin to verify the main characteristics of the system. The lens obtained an average first-order diffraction efficiency of 85.4% across the aperture at 532 nm.

Synthesis of GaN:ZnO solid solution by solution combustion method and characterization for photocatalytic application

NASA Astrophysics Data System (ADS)

Menon, Sumithra Sivadas; Anitha, R.; Gupta, Bhavana; Baskar, K.; Singh, Shubra

2016-05-01

GaN-ZnO solid solution has emerged as a successful and reproducible photocatalyst for overall water splitting by one-step photoexcitation, with a bandgap in visible region. When the solid solution is formed, some of the Zn and O ions are replaced by Ga and N ions respectively and there is a narrowing of bandgap which is hypothesized as due to Zn3d-N2p repulsion. The traditional method of synthesis of GaN-ZnO solid solution is by nitridation of the starting oxides under constant ammonia flow. Here we report a solution combustion technique for the synthesis of the solid solution at a temperature about 500 ° C in a muffle furnace with metal nitrates as precursors and urea as the fuel. The as prepared samples showed change in color with the increased concentration of ZnO in the solution. The structural, microstructural, morphological and optical properties of the samples were realized by Powder X ray diffraction, Scanning electron microscopy, Energy dispersive X ray analysis, Transmission electron microscopy and Photoluminescence. Finally the hydrogen production efficiency of the GaN-ZnO nanopowders by water splitting was found, using methanol as a scavenger. The apparent quantum yield (AQY) of 0.048% is obtained for GaN-ZnO solid solution.

Development and Implementation of a Transport Method for the Transport and Reaction Simulation Engine (TaRSE) based on the Godunov-Mixed Finite Element Method

USGS Publications Warehouse

James, Andrew I.; Jawitz, James W.; Munoz-Carpena, Rafael

2009-01-01

A model to simulate transport of materials in surface water and ground water has been developed to numerically approximate solutions to the advection-dispersion equation. This model, known as the Transport and Reaction Simulation Engine (TaRSE), uses an algorithm that incorporates a time-splitting technique where the advective part of the equation is solved separately from the dispersive part. An explicit finite-volume Godunov method is used to approximate the advective part, while a mixed-finite element technique is used to approximate the dispersive part. The dispersive part uses an implicit discretization, which allows it to run stably with a larger time step than the explicit advective step. The potential exists to develop algorithms that run several advective steps, and then one dispersive step that encompasses the time interval of the advective steps. Because the dispersive step is computationally most expensive, schemes can be implemented that are more computationally efficient than non-time-split algorithms. This technique enables scientists to solve problems with high grid Peclet numbers, such as transport problems with sharp solute fronts, without spurious oscillations in the numerical approximation to the solution and with virtually no artificial diffusion.

Tuning Cu dopant of Zn 0.5 Cd 0.5 S nanocrystals enables high-performance photocatalytic H 2 evolution from water splitting under visible-light irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mei, Zongwei; Zhang, Bingkai; Zheng, Jiaxin

2016-08-01

Cu-doping into Zn1-xCdxS can greatly enhance the photocatalytic H2 evolution from water splitting under visible-light irradiation. However, it is still controversial for how the Cu-dopant improves this performance. Here, we report that appropriate Cu-doped Zn0.5Cd0.5S nanocrystals reach 21.4 mmol/h/g of H2 evolution rate without cocatalyst in the visible-light region, which is also 2.8 times as high as that of the undoped counterpart, and the corresponding apparent quantum efficiency is 18.8% at 428 nm. It is firstly confirmed that the Cu2+ changes into Cu+ after being doped by soft X-ray absorption spectroscopy (sXAS). We theoretically propose that the transformation of 2Cu2+more » to 2Cu+ results in one adjacent S2- vacancy (VS) in host during the doping process, while the Cu+-dopant and VS attract the photoexcited holes and electrons, respectively. Accordingly, the photocatalytic activity is improved due to the enhanced separation of photoexcited carriers accompanied with the enhanced light absorption resulting from the Cu+-dopant and 2Cu+/VS complex as possible active site for photocatalytic H2 evolution.« less

A kinetic flux vector splitting scheme for shallow water equations incorporating variable bottom topography and horizontal temperature gradients.

PubMed

Saleem, M Rehan; Ashraf, Waqas; Zia, Saqib; Ali, Ishtiaq; Qamar, Shamsul

2018-01-01

This paper is concerned with the derivation of a well-balanced kinetic scheme to approximate a shallow flow model incorporating non-flat bottom topography and horizontal temperature gradients. The considered model equations, also called as Ripa system, are the non-homogeneous shallow water equations considering temperature gradients and non-uniform bottom topography. Due to the presence of temperature gradient terms, the steady state at rest is of primary interest from the physical point of view. However, capturing of this steady state is a challenging task for the applied numerical methods. The proposed well-balanced kinetic flux vector splitting (KFVS) scheme is non-oscillatory and second order accurate. The second order accuracy of the scheme is obtained by considering a MUSCL-type initial reconstruction and Runge-Kutta time stepping method. The scheme is applied to solve the model equations in one and two space dimensions. Several numerical case studies are carried out to validate the proposed numerical algorithm. The numerical results obtained are compared with those of staggered central NT scheme. The results obtained are also in good agreement with the recently published results in the literature, verifying the potential, efficiency, accuracy and robustness of the suggested numerical scheme.

A kinetic flux vector splitting scheme for shallow water equations incorporating variable bottom topography and horizontal temperature gradients

PubMed Central

2018-01-01

This paper is concerned with the derivation of a well-balanced kinetic scheme to approximate a shallow flow model incorporating non-flat bottom topography and horizontal temperature gradients. The considered model equations, also called as Ripa system, are the non-homogeneous shallow water equations considering temperature gradients and non-uniform bottom topography. Due to the presence of temperature gradient terms, the steady state at rest is of primary interest from the physical point of view. However, capturing of this steady state is a challenging task for the applied numerical methods. The proposed well-balanced kinetic flux vector splitting (KFVS) scheme is non-oscillatory and second order accurate. The second order accuracy of the scheme is obtained by considering a MUSCL-type initial reconstruction and Runge-Kutta time stepping method. The scheme is applied to solve the model equations in one and two space dimensions. Several numerical case studies are carried out to validate the proposed numerical algorithm. The numerical results obtained are compared with those of staggered central NT scheme. The results obtained are also in good agreement with the recently published results in the literature, verifying the potential, efficiency, accuracy and robustness of the suggested numerical scheme. PMID:29851978

Three-phase compositional modeling of CO2 injection by higher-order finite element methods with CPA equation of state for aqueous phase

NASA Astrophysics Data System (ADS)

Moortgat, Joachim; Li, Zhidong; Firoozabadi, Abbas

2012-12-01

Most simulators for subsurface flow of water, gas, and oil phases use empirical correlations, such as Henry's law, for the CO2 composition in the aqueous phase, and equations of state (EOS) that do not represent the polar interactions between CO2and water. Widely used simulators are also based on lowest-order finite difference methods and suffer from numerical dispersion and grid sensitivity. They may not capture the viscous and gravitational fingering that can negatively affect hydrocarbon (HC) recovery, or aid carbon sequestration in aquifers. We present a three-phase compositional model based on higher-order finite element methods and incorporate rigorous and efficient three-phase-split computations for either three HC phases or water-oil-gas systems. For HC phases, we use the Peng-Robinson EOS. We allow solubility of CO2in water and adopt a new cubic-plus-association (CPA) EOS, which accounts for cross association between H2O and CO2 molecules, and association between H2O molecules. The CPA-EOS is highly accurate over a broad range of pressures and temperatures. The main novelty of this work is the formulation of a reservoir simulator with new EOS-based unique three-phase-split computations, which satisfy both the equalities of fugacities in all three phases and the global minimum of Gibbs free energy. We provide five examples that demonstrate twice the convergence rate of our method compared with a finite difference approach, and compare with experimental data and other simulators. The examples consider gravitational fingering during CO2sequestration in aquifers, viscous fingering in water-alternating-gas injection, and full compositional modeling of three HC phases.

Quantum-splitting oxide-based phosphors, method of producing, and rules for designing the same

DOEpatents

Setlur, Anant Achyut; Comanzo, Holly Ann; Srivastava, Alok Mani

2003-09-16

Strontium and strontium calcium aluminates and lanthanum and lanthanum magnesium borates activated with Pr.sup.3+ and Mn.sup.2+ exhibit characteristics of quantum-splitting phosphors. Improved quantum efficiency may be obtained by further doping with Gd.sup.3+. Refined rules for designing quantum-splitting phosphors include the requirement of incorporation of Gd.sup.3+ and Mn.sup.2+ in the host lattice for facilitation of energy migration.

Simultaneous and semi-alternating projection algorithms for solving split equality problems.

PubMed

Dong, Qiao-Li; Jiang, Dan

2018-01-01

In this article, we first introduce two simultaneous projection algorithms for solving the split equality problem by using a new choice of the stepsize, and then propose two semi-alternating projection algorithms. The weak convergence of the proposed algorithms is analyzed under standard conditions. As applications, we extend the results to solve the split feasibility problem. Finally, a numerical example is presented to illustrate the efficiency and advantage of the proposed algorithms.

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

Highly active catalyst derived from a 3D foam of Fe(PO3)2/Ni2P for extremely efficient water oxidation

PubMed Central

Zhou, Haiqing; Yu, Fang; Sun, Jingying; He, Ran; Chen, Shuo; Chu, Ching-Wu; Ren, Zhifeng

2017-01-01

Commercial hydrogen production by electrocatalytic water splitting will benefit from the realization of more efficient and less expensive catalysts compared with noble metal catalysts, especially for the oxygen evolution reaction, which requires a current density of 500 mA/cm2 at an overpotential below 300 mV with long-term stability. Here we report a robust oxygen-evolving electrocatalyst consisting of ferrous metaphosphate on self-supported conductive nickel foam that is commercially available in large scale. We find that this catalyst, which may be associated with the in situ generated nickel–iron oxide/hydroxide and iron oxyhydroxide catalysts at the surface, yields current densities of 10 mA/cm2 at an overpotential of 177 mV, 500 mA/cm2 at only 265 mV, and 1,705 mA/cm2 at 300 mV, with high durability in alkaline electrolyte of 1 M KOH even after 10,000 cycles, representing activity enhancement by a factor of 49 in boosting water oxidation at 300 mV relative to the state-of-the-art IrO2 catalyst. PMID:28507120

Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lianwei; Cai, Zhengxu; Wu, Qinghe

Developing high efficient photocatalyts for splitting water into oxygen and hydrogen is one of the biggest chemical challenges in solar energy utilization. In this paper, we report our effort in rationally designing conjugated porous polymer (CPP) photocatalysts for photocatalytic hydrogen production (PHP) from water. A series of CPP photocatalysts with different chromophore components and bipyridyl (bpy) contents were synthesized and found to evolve hydrogen photocatalytically from water. The PHP activity of bpy-containing CPPs can be greatly enhanced due to the improved light absorption, better wettability, higher crystallinity and the improved charge separation process. Moreover, the CPP photocatalyst made of strongmore » and fully conjugated donor chromo-phore DBD shows the highest hydrogen production rate ~ 33 μmol/h. The results indicate that copolymerization between a strong donor and weak acceptor is a useful strategy for the devel-opment of efficient photocatalysts. This study clarifies that the residual palladium in the CPP networks plays a key role for the catalytic performance. The PHP activity of CPP photocatalyst can be further enhanced to 164 μmol/h with an apparent quantum yield of 1.8% at 350 nm by loading 2 wt% of extra platinum cocat-alyst.« less

Nature-driven photochemistry for catalytic solar hydrogen production: a Photosystem I-transition metal catalyst hybrid.

PubMed

Utschig, Lisa M; Silver, Sunshine C; Mulfort, Karen L; Tiede, David M

2011-10-19

Solar energy conversion of water into the environmentally clean fuel hydrogen offers one of the best long-term solutions for meeting future energy demands. Nature provides highly evolved, finely tuned molecular machinery for solar energy conversion that exquisitely manages photon capture and conversion processes to drive oxygenic water-splitting and carbon fixation. Herein, we use one of Nature's specialized energy-converters, the Photosystem I (PSI) protein, to drive hydrogen production from a synthetic molecular catalyst comprised of inexpensive, earth-abundant materials. PSI and a cobaloxime catalyst self-assemble, and the resultant complex rapidly produces hydrogen in aqueous solution upon exposure to visible light. This work establishes a strategy for enhancing photosynthetic efficiency for solar fuel production by augmenting natural photosynthetic systems with synthetically tunable abiotic catalysts.

TiO2 Processed by pressurized hot solvents as a novel photocatalyst for photocatalytic reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Reli, Martin; Kobielusz, Marcin; Matějová, Lenka; Daniš, Stanislav; Macyk, Wojciech; Obalová, Lucie; Kuśtrowski, Piotr; Rokicińska, Anna; Kočí, Kamila

2017-01-01

Anatase-brookite TiO2 photocatalysts were prepared by the sol-gel process controlled within reverse micelles and processing by pressurized hot solvents-water/methanol/water (TiO2(M)) and water/ethanol/water (TiO2(E)), as an unconventional alternative to common calcination. The main goal of this work was to prepare anatase-brookite mixtures by processing by two different alcohols (methanol and ethanol) and evaluate the influence of the alcohol on the photocatalytic activity. Prepared photocatalysts were characterized by organic elemental analysis, nitrogen physisorption, XRD, UV-vis, photoelectrochemical and spectroelectrochemical measurements and XPS. The prepared photocatalysts efficiency was tested on the photocatalytic reduction of carbon dioxide and compared with commercial TiO2 Evonik P25. Both prepared nanocomposites were more efficient towards methane production but Evonik P25 was the most efficient towards hydrogen generated through water splitting. The higher performance of anatase-brookite mixture towards methane production can be explained by (i) a higher photocatalytic activity of brookite than rutile; (ii) a large surface area of anatase-brookite composites enabling better carbon dioxide adsorption; (iii) the photoinduced electron transfer from the brookite conduction band to the anatase conduction band. On the other hand, a higher production of hydrogen in the presence of Evonik P25 is caused by a better charge separation in anatase-rutile than anatase-brookite phase compositions. TiO2(M) appeared more active than TiO2(E) in the photocatalytic reduction of carbon dioxide due to a lower density of defects created in the crystal lattice.

Incentive and Architecture of Multi-Band Enabled Small Cell and UE for Up-/Down-Link and Control-/User-Plane Splitting for 5G Mobile Networks

NASA Astrophysics Data System (ADS)

Saha, Rony Kumer; Aswakul, Chaodit

2017-01-01

In this paper, a multi-band enabled femtocell base station (FCBS) and user equipment (UE) architecture is proposed in a multi-tier network that consists of small cells, including femtocells and picocells deployed over the coverage of a macrocell for splitting uplink and downlink (UL/DL) as well as control-plane and user-plane (C-/U-plane) for 5G mobile networks. Since splitting is performed at the same FCBS, we define this architecture as the same base station based split architecture (SBSA). For multiple bands, we consider co-channel (CC) microwave and different frequency (DF) 60 GHz millimeter wave (mmWave) bands for FCBSs and UEs with respect to the microwave band used by their over-laid macrocell base station. All femtocells are assumed to be deployed in a 3-dimensional multi-storage building. For CC microwave band, cross-tier CC interference of femtocells with macrocell is avoided using almost blank subframe based enhanced inter-cell interference coordination techniques. The co-existence of CC microwave and DF mmWave bands for SBSA on the same FCBS and UE is first studied to show their performance disparities in terms of system capacity and spectral efficiency in order to provide incentives for employing multiple bands at the same FCBS and UE and identify a suitable band for routing decoupled UL/DL or C-/U-plane traffic. We then present a number of disruptive architectural design alternatives of multi-band enabled SBSA for 5G mobile networks for UL/DL and C-/U-plane splitting, including a disruptive and complete splitting of UL/DL and C-/U-plane as well as a combined UL/DL and C-/U-plane splitting, by exploiting dual connectivity on CC microwave and DF mmWave bands. The outperformances of SBSA in terms of system level capacity, average spectral efficiency, energy efficiency, and control-plane overhead traffic capacity in comparison with different base stations based split architecture (DBSA) are shown. Finally, a number of technical and business perspectives as well as key research issues of SBSA are discussed.

Policy options for the split incentive: Increasing energy efficiency for low-income renters.

PubMed

Bird, Stephen; Hernández, Diana

2012-09-01

The split incentive problem concerns the lack of appropriate incentives to implement energy efficiency measures. In particular, low income tenants face a phenomenon of energy poverty in which they allocate significantly more of their household income to energy expenditures than other renters. This problem is substantial, affecting 1.89% of all United States' energy use. If effectively addressed, it would create a range of savings between 4 and 11 billion dollars per year for many of the nation's poorest residents. We argue that a carefully designed program of incentives for participants (including landlords) in conjunction with a unique type of utility-managed on-bill financing mechanism has significant potential to solve many of the complications. We focus on three kinds of split incentives, five concerns inherent to addressing split incentive problems (scale, endurance, incentives, savings, political disfavor), and provide a detailed policy proposal designed to surpass those problems, with a particular focus on low-income tenants in a U.S.

Policy options for the split incentive: Increasing energy efficiency for low-income renters

PubMed Central

Bird, Stephen; Hernández, Diana

2016-01-01

The split incentive problem concerns the lack of appropriate incentives to implement energy efficiency measures. In particular, low income tenants face a phenomenon of energy poverty in which they allocate significantly more of their household income to energy expenditures than other renters. This problem is substantial, affecting 1.89% of all United States' energy use. If effectively addressed, it would create a range of savings between 4 and 11 billion dollars per year for many of the nation's poorest residents. We argue that a carefully designed program of incentives for participants (including landlords) in conjunction with a unique type of utility-managed on-bill financing mechanism has significant potential to solve many of the complications. We focus on three kinds of split incentives, five concerns inherent to addressing split incentive problems (scale, endurance, incentives, savings, political disfavor), and provide a detailed policy proposal designed to surpass those problems, with a particular focus on low-income tenants in a U.S. context. PMID:27053828

Open-framework gallium borate with boric and metaboric acid molecules inside structural channels showing photocatalysis to water splitting.

PubMed

Gao, Wenliang; Jing, Yan; Yang, Jia; Zhou, Zhengyang; Yang, Dingfeng; Sun, Junliang; Lin, Jianhua; Cong, Rihong; Yang, Tao

2014-03-03

An open-framework gallium borate with intrinsic photocatalytic activities to water splitting has been discovered. Small inorganic molecules, H3BO3 and H3B3O6, are confined inside structural channels by multiple hydrogen bonds. It is the first example to experimentally show the structural template effect of boric acid in flux synthesis.

Accuracy of tablet splitting and liquid measurements: an examination of who, what and how.

PubMed

Abu-Geras, Dana; Hadziomerovic, Dunja; Leau, Andrew; Khan, Ramzan Nazim; Gudka, Sajni; Locher, Cornelia; Razaghikashani, Maryam; Lim, Lee Yong

2017-05-01

To examine factors that might affect the ability of patients to accurately halve tablets or measure a 5-ml liquid dose. Eighty-eight participants split four different placebo tablets by hand and using a tablet splitter, while 85 participants measured 5 ml of water, 0.5% methylcellulose (MC) and 1% MC using a syringe and dosing cup. Accuracy of manipulation was determined by mass measurements. The general population was less able than pharmacy students to break tablets into equal parts, although age, gender and prior experience were insignificant factors. Greater accuracy of tablet halving was observed with tablet splitter, with scored tablets split more equally than unscored tablets. Tablet size did not affect the accuracy of splitting. However, >25% of small scored tablets failed to be split by hand, and 41% of large unscored tablets were split into >2 portions in the tablet splitter. In liquid measurement, the syringe provided more accurate volume measurements than the dosing cup, with higher accuracy observed for the more viscous MC solutions than water. Formulation characteristics and manipulation technique have greater influences on the accuracy of medication modification and should be considered in off-label drug use in vulnerable populations. © 2016 Royal Pharmaceutical Society.

Interim results of quality-control sampling of surface water for the Upper Colorado River National Water-Quality Assessment Study Unit, water years 1995-96

USGS Publications Warehouse

Spahr, N.E.; Boulger, R.W.

1997-01-01

Quality-control samples provide part of the information needed to estimate the bias and variability that result from sample collection, processing, and analysis. Quality-control samples of surface water collected for the Upper Colorado River National Water-Quality Assessment study unit for water years 1995?96 are presented and analyzed in this report. The types of quality-control samples collected include pre-processing split replicates, concurrent replicates, sequential replicates, post-processing split replicates, and field blanks. Analysis of the pre-processing split replicates, concurrent replicates, sequential replicates, and post-processing split replicates is based on differences between analytical results of the environmental samples and analytical results of the quality-control samples. Results of these comparisons indicate that variability introduced by sample collection, processing, and handling is low and will not affect interpretation of the environmental data. The differences for most water-quality constituents is on the order of plus or minus 1 or 2 lowest rounding units. A lowest rounding unit is equivalent to the magnitude of the least significant figure reported for analytical results. The use of lowest rounding units avoids some of the difficulty in comparing differences between pairs of samples when concentrations span orders of magnitude and provides a measure of the practical significance of the effect of variability. Analysis of field-blank quality-control samples indicates that with the exception of chloride and silica, no systematic contamination of samples is apparent. Chloride contamination probably was the result of incomplete rinsing of the dilute cleaning solution from the outlet ports of the decaport sample splitter. Silica contamination seems to have been introduced by the blank water. Sampling and processing procedures for water year 1997 have been modified as a result of these analyses.

Tree branch-shaped cupric oxide for highly effective photoelectrochemical water reduction

NASA Astrophysics Data System (ADS)

Jang, Youn Jeong; Jang, Ji-Wook; Choi, Sun Hee; Kim, Jae Young; Kim, Ju Hun; Youn, Duck Hyun; Kim, Won Yong; Han, Suenghoon; Sung Lee, Jae

2015-04-01

Highly efficient tree branch-shaped CuO photocathodes are fabricated using the hybrid microwave annealing process with a silicon susceptor within 10 minutes. The unique hierarchical, one-dimensional structure provides more facile charge transport, larger surface areas, and increased crystallinity and crystal ordering with less defects compared to irregular-shaped CuO prepared by conventional thermal annealing. As a result, the photocathode fabricated with the tree branch-shaped CuO produces an unprecedently high photocurrent density of -4.4 mA cm-2 at 0 VRHE under AM 1.5 G simulated sunlight compared to -1.44 mA cm-2 observed for a photocathode fabricated by thermal annealing. It is also confirmed that stoichiometric hydrogen and oxygen are produced from photoelectrochemical water splitting on the tree branch-shaped CuO photocathode and a platinum anode.Highly efficient tree branch-shaped CuO photocathodes are fabricated using the hybrid microwave annealing process with a silicon susceptor within 10 minutes. The unique hierarchical, one-dimensional structure provides more facile charge transport, larger surface areas, and increased crystallinity and crystal ordering with less defects compared to irregular-shaped CuO prepared by conventional thermal annealing. As a result, the photocathode fabricated with the tree branch-shaped CuO produces an unprecedently high photocurrent density of -4.4 mA cm-2 at 0 VRHE under AM 1.5 G simulated sunlight compared to -1.44 mA cm-2 observed for a photocathode fabricated by thermal annealing. It is also confirmed that stoichiometric hydrogen and oxygen are produced from photoelectrochemical water splitting on the tree branch-shaped CuO photocathode and a platinum anode. Electronic supplementary information (ESI) available: The detailed schematic diagram for the HMA process, XRD results, the temperature profile during HMA, derivative XANES results, TEM images, J-V curves, lists of previously reported copper oxide photocathode, and parameters extracted from EIS. See DOI: 10.1039/c5nr00208g

Solution Plasma-assisted Bimetallic Oxide Alloy Nanoparticles of Pt and Pd Embedded within Two-dimensional Ti3C2Tx Nanosheets as Highly Active Electrocatalysts for Overall Water-splitting.

PubMed

Cui, Bingbing; Hu, Bin; Liu, Jiameng; Wang, Minghua; Song, Yingpan; Tian, Kuan; Zhang, Zhihong; He, Linghao

2018-06-25

Exploiting high-efficiency and low-cost bifunctional electrocatalysts for hydrogen evolution (HER) and oxygen evolution reactions (OER) has been actively encouraged because of their potential applications in the field of clean energy. In this paper, we reported a novel electrocatalyst based on an exfoliated two-dimensional (2D) MXene (Ti3C2Tx) loaded with bimetallic oxide alloy nanoparticles (NPs) of Pt and Pd (represented by PtOaPdObNPs@Ti3C2Tx), which was synthesized via solution plasma (SP) modification. The prepared materials were then utilized as highly efficient bifunctional electrocatalysts toward HER and OER in alkaline solution. At a high plasma input power (200 W), bimetallic oxide alloy nanoparticles of Pt and Pd or nanoclusters with different metallic valence states deposited onto the Ti3C2Tx nanosheets. Due to the synergism of the noble metal NPs and the Ti3C2Tx nanosheets, the electrocatalytic results revealed that the as-prepared PtOaPdObNPs@Ti3C2Tx nanosheets under the plasma input power of 200 W for 3 min catalyst only required a low overpotential to attain 10 mA cm-2 for HER (57 mV) in 0.5 M H2SO4 solution and OER (1.63 V) in 0.1 M KOH sollution. Moreover, water electrolysis using this catalyst achieved a water splitting current density of 10 mA cm-2 at a low cell voltage of 1.53 V in 1.0 M KOH solution. These results suggested that the hybridization of the ultra-extremely low usage of PtOa/PdOb NPs (1.07 μg cm-2) and Ti3C2Tx nanosheets by SP will expand the applications of other clean energy reactions to achieve sustainable energy.

Hydrogen as the solar energy translator. [in photochemical and photovoltaic processes

NASA Technical Reports Server (NTRS)

Kelley, J. H.

1979-01-01

Many concepts are being investigated to convert sunlight to workable energy forms with emphasis on electricity and thermal energy. The electrical alternatives include direct conversion of photons to electricity via photovoltaic solar cells and solar/thermal production of electricity via heat-energy cycles. Solar cells, when commercialized, are expected to have efficiencies of about 12 to 14 percent. The cells would be active about eight hours per day. However, solar-operated water-splitting process research, initiated through JPL, shows promise for direct production of hydrogen from sunlight with efficiencies of up to 35 to 40 percent. The hydrogen, a valuable commodity in itself, can also serve as a storable energy form, easily and efficiently converted to electricity by fuel cells and other advanced-technology devices on a 24-hour basis or on demand with an overall efficiency of 25 to 30 percent. Thus, hydrogen serves as the fundamental translator of energy from its solar form to electrical form more effectively, and possibly more efficiently, than direct conversion. Hydrogen also can produce other chemical energy forms using solar energy.

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

DOE PAGES

Phivilay, Somphonh Peter; Roberts, Charles; Gamalski, Andrew; ...

2018-06-08

The supported mixed oxide (Rh 2-yCr yO 3)/(Ga 1-xZn x)(N 1-xO x) photocatalyst, highly active for splitting of H 2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga 1-xZn x)(N 1-xO x) support are not perturbed by the deposition of the (Rh 2-yCr yO 3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga 1-xZn x)(N 1-xO x) support is the source of excited electrons/holes and the (Rh 2-yCr yO 3) NPs greatly reducemore » the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh 2-yCr yO 3) NPs consist of Rh +3 and Cr +3 mixed oxide species. In Situ AP-XPS help to reveal that the Rh+3 and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga 1-xZn x)(N 1-xO x) support and on CrO x NPs were found to be the photocatalytic active sites for H 2 generation and N and Zn sites from the (Ga 1-xZn x)(N 1-xO x) support are the photocatalytic active site for O 2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.« less

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phivilay, Somphonh Peter; Roberts, Charles; Gamalski, Andrew

The supported mixed oxide (Rh 2-yCr yO 3)/(Ga 1-xZn x)(N 1-xO x) photocatalyst, highly active for splitting of H 2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga 1-xZn x)(N 1-xO x) support are not perturbed by the deposition of the (Rh 2-yCr yO 3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga 1-xZn x)(N 1-xO x) support is the source of excited electrons/holes and the (Rh 2-yCr yO 3) NPs greatly reducemore » the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh 2-yCr yO 3) NPs consist of Rh +3 and Cr +3 mixed oxide species. In Situ AP-XPS help to reveal that the Rh+3 and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga 1-xZn x)(N 1-xO x) support and on CrO x NPs were found to be the photocatalytic active sites for H 2 generation and N and Zn sites from the (Ga 1-xZn x)(N 1-xO x) support are the photocatalytic active site for O 2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.« less

Light harvesting proteins for solar fuel generation in bioengineered photoelectrochemical cells.

PubMed

Ihssen, Julian; Braun, Artur; Faccio, Greta; Gajda-Schrantz, Krisztina; Thöny-Meyer, Linda

2014-01-01

The sun is the primary energy source of our planet and potentially can supply all societies with more than just their basic energy needs. Demand of electric energy can be satisfied with photovoltaics, however the global demand for fuels is even higher. The direct way to produce the solar fuel hydrogen is by water splitting in photoelectrochemical (PEC) cells, an artificial mimic of photosynthesis. There is currently strong resurging interest for solar fuels produced by PEC cells, but some fundamental technological problems need to be solved to make PEC water splitting an economic, competitive alternative. One of the problems is to provide a low cost, high performing water oxidizing and oxygen evolving photoanode in an environmentally benign setting. Hematite, α-Fe2O3, satisfies many requirements for a good PEC photoanode, but its efficiency is insufficient in its pristine form. A promising strategy for enhancing photocurrent density takes advantage of photosynthetic proteins. In this paper we give an overview of how electrode surfaces in general and hematite photoanodes in particular can be functionalized with light harvesting proteins. Specifically, we demonstrate how low-cost biomaterials such as cyanobacterial phycocyanin and enzymatically produced melanin increase the overall performance of virtually no-cost metal oxide photoanodes in a PEC system. The implementation of biomaterials changes the overall nature of the photoanode assembly in a way that aggressive alkaline electrolytes such as concentrated KOH are not required anymore. Rather, a more environmentally benign and pH neutral electrolyte can be used.

Holographic spectrum-splitting optical systems for solar photovoltaics

NASA Astrophysics Data System (ADS)

Zhang, Deming

Solar energy is the most abundant source of renewable energy available. The relatively high cost prevents solar photovoltaic (PV) from replacing fossil fuel on a larger scale. In solar PV power generation the cost is reduced with more efficient PV technologies. In this dissertation, methods to improve PV conversion efficiency with holographic optical components are discussed. The tandem multiple-junction approach has achieved very high conversion efficiency. However it is impossible to manufacture tandem PV cells at a low cost due to stringent fabrication standards and limited material types that satisfy lattice compatibility. Current produced by the tandem multi-junction PV cell is limited by the lowest junction due to series connection. Spectrum-splitting is a lateral multi-junction concept that is free of lattice and current matching constraints. Each PV cell can be optimized towards full absorption of a spectral band with tailored light-trapping schemes. Holographic optical components are designed to achieve spectrum-splitting PV energy conversion. The incident solar spectrum is separated onto multiple PV cells that are matched to the corresponding spectral band. Holographic spectrum-splitting can take advantage of existing and future low-cost technologies that produces high efficiency thin-film solar cells. Spectrum-splitting optical systems are designed and analyzed with both transmission and reflection holographic optical components. Prototype holograms are fabricated and high optical efficiency is achieved. Light-trapping in PV cells increases the effective optical path-length in the semiconductor material leading to improved absorption and conversion efficiency. It has been shown that the effective optical path length can be increased by a factor of 4n2 using diffusive surfaces. Ultra-light-trapping can be achieved with optical filters that limit the escape angle of the diffused light. Holographic reflection gratings have been shown to act as angle-wavelength selective filters that can function as ultra-light-trapping filters. Results from an experimental reflection hologram are used to model the absorption enhancement factor for a silicon solar cell and light-trapping filter. The result shows a significant improvement in current generation for thin-film silicon solar cells under typical operating conditions.

NiO nanoparticles anchored on P-doped α-Fe2O3 nanoarrays: an efficient hole extraction p-n heterojunction photoanode for water oxidation.

PubMed

Li, Feng; Li, Jing; Zhang, Jie; Gao, Lili; Long, Xuefeng; Hu, Yiping; Li, Shuwen; Jin, Jun; Ma, Jiantai

2018-05-16

The photoelectrochemical (PEC) water splitting efficiency of hematite-based photoanode is still far from the theoretical value due to its poor surface reaction kinetics and high density of surface trapping states. To solve these drawbacks, a photoanode consisting of NiO nanoparticles anchored on a gradient P-doped α-Fe2O3 nanorod (NR) array (NiO/P-α-Fe2O3) was fabricated to achieve optimal light absorption and charge separation, and rapid surface reaction kinetic. Specifically, the photoanode with the NR arrays structure allowed high mass transport rate to be achieved while the P-doping effectively decreased surface trapping sites and improved the electrical conductivity of α-Fe2O3. Furthermore, the p-n junction formed between the NiO and P-α-Fe2O3 can further improve the PEC performance due to the efficient hole extraction property and water oxidization catalytic activity of NiO. Consequently, the NiO/P-α-Fe2O3 NR photoanode produced a high photocurrent density of 2.08 mA cm-2 at 1.23V vs. RHE and a 110 mV cathodic shift of the onset potential. This rational design of structure offers a new perspective in exploring high performance PEC photoanodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling seasonal water balance based on catchments' hedging strategy on evapotranspiration for climate seasonality

NASA Astrophysics Data System (ADS)

Wu, S.; Zhao, J.; Wang, H.

2017-12-01

This paper develops a seasonal water balance model based on the hypothesis that natural catchments utilize hedging strategy on evapotranspiration for climate seasonality. According to the monthly aridity index, one year is split into wet season and dry season. A seasonal water balance model is developed by analogy to a two-stage reservoir operation model, in which seasonal rainfall infiltration, evapotranspiration and saturation-excess runoff is corresponding to the inflow, release and surplus of the catchment system. Then the optimal hedging between wet season and dry season evapotranspiration is analytically derived with marginal benefit principle. Water budget data sets of 320 catchments in the United States covering the period from 1980 to 2010 are used to evaluate the performance of this model. The Nash-Sutcliffe Efficiency coefficient for evapotranspiration is higher than 0.5 in 84% of the study catchments; while the runoff is 87%. This paper validates catchments' hedging strategy on evapotranspiration for climate seasonality and shows its potential application for seasonal water balance, which is valuable for water resources planning and management.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichterman, Michael F.; Sun, Ke; Hu, Shu

Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation aremore » unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.« less

Density Functional Theory Simulations of Water Adsorption and Activation on the (-201) β-Ga2 O3 Surface.

PubMed

Anvari, Roozbeh; Spagnoli, Dino; Parish, Giacinta; Nener, Brett

2018-03-09

Density functional theory calculations are used to study the molecular and dissociative adsorption of water on the (-201) β-Ga 2 O 3 surface. The effect of adsorption of different water-like species on the geometry, binding energies, vibrational spectra and the electronic structure of the surface are discussed. The study shows that although the hydrogen evolution reaction requires a small amount of energy to become energetically favourable, the over potential for activating the oxygen evolution reaction is quite high. The results of our calculations provide insight as to why a high voltage is required in experiments to activate the water-splitting reaction, whereas previous studies of gallium oxide predicted very low activation energies for other energetically more favourable facets. Application of this work to studies of GaN-based chemical sensors with gallium oxide surfaces shows that it is possible to select the gate bias so that the sensors are not influenced by water-splitting reactions. It was also found that in the region where water splitting does not occur, the surface can exist in two states, that is, water or hydroxyl terminated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Why the different responses between single and split nitrogen applications?

USDA-ARS?s Scientific Manuscript database

Split- opposed to single-nitrogen applications may improve corn (Zea mays L.) production, N use efficiency, and lessen environmental impacts due to fertilization. However, there has been an inconsistent response of yield, plant nitrogen (N) uptake, and residual soil nitrates (RSN) when comparing sin...

Split and Splice Approach for Highly Selective Targeting of Human NSCLC Tumors

DTIC Science & Technology

2014-10-01

development and implementation of the “split-and- spice ” approach required optimization of many independent parameters, which were addressed in parallel...verify the feasibility of the “split and splice” approach for targeting human NSCLC tumor cell lines in culture and prepare the optimized toxins for...for cultured cells (months 2- 8). 2B. To test the efficiency of cell targeting by the toxin variants reconstituted in vitro (months 3-6). 2C. To

Highly efficient and robust molecular ruthenium catalysts for water oxidation.

PubMed

Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S G; Sun, Licheng

2012-09-25

Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H(2) driven by solar radiation (H(2)O + hν → 1/2O(2) + H(2)). The oxidation of water (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) → H(2)), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L(2)] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce(IV)-driven [Ce(IV) = Ce(NH(4))(2)(NO(3))(6)] water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dernotte, Jeremie; Dec, John E.; Ji, Chunsheng

A detailed understanding of the various factors affecting the trends in gross-indicated thermal efficiency with changes in key operating parameters has been carried out, applied to a one-liter displacement single-cylinder boosted Low-Temperature Gasoline Combustion (LTGC) engine. This work systematically investigates how the supplied fuel energy splits into the following four energy pathways: gross-indicated thermal efficiency, combustion inefficiency, heat transfer and exhaust losses, and how this split changes with operating conditions. Additional analysis is performed to determine the influence of variations in the ratio of specific heat capacities (γ) and the effective expansion ratio, related to the combustion-phasing retard (CA50), onmore » the energy split. Heat transfer and exhaust losses are computed using multiple standard cycle analysis techniques. Furthermore, the various methods are evaluated in order to validate the trends.« less

75 FR 45148 - Buy American Exceptions Under the American Recovery and Reinvestment Act of 2009

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-02

... Homes and mini-split ductless Heating, Ventilation and Air Conditioning (HVAC) systems at the Mary... that the relevant manufactured goods (tankless water heaters and mini-split ductless HVAC systems) are...

Accurate determination of the charge transfer efficiency of photoanodes for solar water splitting.

PubMed

Klotz, Dino; Grave, Daniel A; Rothschild, Avner

2017-08-09

The oxygen evolution reaction (OER) at the surface of semiconductor photoanodes is critical for photoelectrochemical water splitting. This reaction involves photo-generated holes that oxidize water via charge transfer at the photoanode/electrolyte interface. However, a certain fraction of the holes that reach the surface recombine with electrons from the conduction band, giving rise to the surface recombination loss. The charge transfer efficiency, η t , defined as the ratio between the flux of holes that contribute to the water oxidation reaction and the total flux of holes that reach the surface, is an important parameter that helps to distinguish between bulk and surface recombination losses. However, accurate determination of η t by conventional voltammetry measurements is complicated because only the total current is measured and it is difficult to discern between different contributions to the current. Chopped light measurement (CLM) and hole scavenger measurement (HSM) techniques are widely employed to determine η t , but they often lead to errors resulting from instrumental as well as fundamental limitations. Intensity modulated photocurrent spectroscopy (IMPS) is better suited for accurate determination of η t because it provides direct information on both the total photocurrent and the surface recombination current. However, careful analysis of IMPS measurements at different light intensities is required to account for nonlinear effects. This work compares the η t values obtained by these methods using heteroepitaxial thin-film hematite photoanodes as a case study. We show that a wide spread of η t values is obtained by different analysis methods, and even within the same method different values may be obtained depending on instrumental and experimental conditions such as the light source and light intensity. Statistical analysis of the results obtained for our model hematite photoanode show good correlation between different methods for measurements carried out with the same light source, light intensity and potential. However, there is a considerable spread in the results obtained by different methods. For accurate determination of η t , we recommend IMPS measurements in operando with a bias light intensity such that the irradiance is as close as possible to the AM1.5 Global solar spectrum.

Enhancing long-term photostability of BiVO4 photoanodes for solar water splitting by tuning electrolyte composition

NASA Astrophysics Data System (ADS)

Lee, Dong Ki; Choi, Kyoung-Shin

2018-01-01

As the performance of photoelectrodes used for solar water splitting continues to improve, enhancing the long-term stability of the photoelectrodes becomes an increasingly crucial issue. In this study, we report that tuning the composition of the electrolyte can be used as a strategy to suppress photocorrosion during solar water splitting. Anodic photocorrosion of BiVO4 photoanodes involves the loss of V5+ from the BiVO4 lattice by dissolution. We demonstrate that the use of a V5+-saturated electrolyte, which inhibits the photooxidation-coupled dissolution of BiVO4, can serve as a simple yet effective method to suppress anodic photocorrosion of BiVO4. The V5+ species in the solution can also incorporate into the FeOOH/NiOOH oxygen-evolution catalyst layer present on the BiVO4 surface during water oxidation, further enhancing water-oxidation kinetics. The effect of the V5+ species in the electrolyte on both the long-term photostability of BiVO4 and the performance of the FeOOH/NiOOH oxygen-evolution catalyst layer is systematically elucidated.

Comparative studies on different nanofiber photocatalysts for water splitting

NASA Astrophysics Data System (ADS)

Alharbi, Abdulaziz; Alarifi, Ibrahim M.; Khan, Waseem S.; Asmatulu, Ramazan

2016-04-01

Water splitting using photocatalyst has become a topic of recent investigation since it has the potential of producing hydrogen for clean energy from sunlight. An extensive number of solid photocatalysts have been studied for overall water splitting in recent years. In this study, two methods were employed to synthesize two different photocatalysts for water splitting. The first method describes the synthesis of nickel oxide-loaded strontium titanate (NiO-SrTiO3) particles on electrospun polyacrylonitrile (PAN) nanofibers incorporated with graphene nanoplatelets for water splitting. The electrospun PAN fibers were first oxidized at 270°C for two hours and subsequently immersed in a solution containing ethanol, titanium (IV)-isopropoxide [C12H28O4Ti] and strontium nitrate [Sr(NO3)2]. This solution was then treated with NiO nanoparticles dispersed in toluene. The surface treated PAN fibers were annealed at 600°C in air for 1 hour to transform fibers into a crystalline form for improved photocatalyst performance. In the second method, coaxial electrospinning process was used to produce core/shell strontium titanate/nickel oxide (SrTiO3-NiO) nanofibers. In coaxial method, poly (vinyl pyrrolidone) (PVP) was dissolved in deionized (DI) water, and then titanium (IV) isopropoxide [C12H28O4Ti] and strontium nitrate [Sr(NO3)2] were added into the solution to form the inner (core) layer. For outer (shell) solution, polyacrylonitrile (PAN) polymer was dissolved in dimethylformamide (DMF) at a weight ratio of 10:90 and then nickel oxide was mixed with the solution. Ultraviolet (UV) spectrophotometry and static contact angle measurement techniques were employed to characterize the structural properties of photocatalysts produced by both methods and a comparison was made between the two photocatalysts. The morphology and diameter of the nanofibers were observed by scanning electron microscopy (SEM). The structure and crystallinity of the calcined nanofibers were also observed by means of X-ray diffraction (XRD).

Land surface temperature measurements from EOS MODIS data

NASA Technical Reports Server (NTRS)

Wan, Zhengming

1994-01-01

A generalized split-window method for retrieving land-surface temperature (LST) from AVHRR and MODIS data has been developed. Accurate radiative transfer simulations show that the coefficients in the split-window algorithm for LST must depend on the viewing angle, if we are to achieve a LST accuracy of about 1 K for the whole scan swath range (+/-55.4 deg and +/-55 deg from nadir for AVHRR and MODIS, respectively) and for the ranges of surface temperature and atmospheric conditions over land, which are much wider than those over oceans. We obtain these coefficients from regression analysis of radiative transfer simulations, and we analyze sensitivity and error by using results from systematic radiative transfer simulations over wide ranges of surface temperatures and emissivities, and atmospheric water vapor abundance and temperatures. Simulations indicated that as atmospheric column water vapor increases and viewing angle is larger than 45 deg it is necessary to optimize the split-window method by separating the ranges of the atmospheric column water vapor and lower boundary temperature, and the surface temperature into tractable sub-ranges. The atmospheric lower boundary temperature and (vertical) column water vapor values retrieved from HIRS/2 or MODIS atmospheric sounding channels can be used to determine the range where the optimum coefficients of the split-window method are given. This new LST algorithm not only retrieves LST more accurately but also is less sensitive than viewing-angle independent LST algorithms to the uncertainty in the band emissivities of the land-surface in the split-window and to the instrument noise.

Choice of implicit and explicit operators for the upwind differencing method

NASA Technical Reports Server (NTRS)

Liou, Meng-Sing; Vanleer, Bram

1988-01-01

The flux-vector and flux-difference splittings of Steger-Warming, van Leer and Roe are tested in all possible combinations on the implicit and explicit operators that can be distinguished in implicit relaxation methods for the steady Euler and Navier-Stokes equations. The tests include one-dimensional inviscid nozzle flow, and two-dimensional inviscid and viscous shock reflection. Roe's splitting, as anticipated, is found to uniformly yield the most accurate results. On the other hand, an approximate Roe splitting of the implicit operator (the complete Roe splitting is too complicated for practical use) proves to be the least robust with regard to convergence to the steady state. In this respect, the Steger-Warming splitting is the most robust; it leads to convergence when combined with any of the splittings in the explicit operator, although not necessarily in the most efficient way.

Highly Efficient Photocatalytic H2 Evolution from Water using Visible Light and Structure-Controlled Graphitic Carbon Nitride**

PubMed Central

Martin, David James; Qiu, Kaipei; Shevlin, Stephen Andrew; Handoko, Albertus Denny; Chen, Xiaowei; Guo, Zhengxiao; Tang, Junwang

2014-01-01

The major challenge of photocatalytic water splitting, the prototypical reaction for the direct production of hydrogen by using solar energy, is to develop low-cost yet highly efficient and stable semiconductor photocatalysts. Herein, an effective strategy for synthesizing extremely active graphitic carbon nitride (g-C3N4) from a low-cost precursor, urea, is reported. The g-C3N4 exhibits an extraordinary hydrogen-evolution rate (ca. 20 000 μmol h−1 g−1 under full arc), which leads to a high turnover number (TON) of over 641 after 6 h. The reaction proceeds for more than 30 h without activity loss and results in an internal quantum yield of 26.5 % under visible light, which is nearly an order of magnitude higher than that observed for any other existing g-C3N4 photocatalysts. Furthermore, it was found by experimental analysis and DFT calculations that as the degree of polymerization increases and the proton concentration decreases, the hydrogen-evolution rate is significantly enhanced. PMID:25045013

3D architecture constructed via the confined growth of MoS2 nanosheets in nanoporous carbon derived from metal-organic frameworks for efficient hydrogen production.

PubMed

Liu, Yun; Zhou, Xiaoli; Ding, Tao; Wang, Chunde; Yang, Qing

2015-11-21

The design and synthesis of robust, high-performance and low-cost three-dimensional (3D) hierarchical structured materials for the electrochemical reduction of water to generate hydrogen is of great significance for practical water splitting applications. In this study, we develop an in situ space-confined method to synthesize an MoS2-based 3D hierarchical structure, in which the MoS2 nanosheets grow in the confined nanopores of metal-organic frameworks (MOFs)-derived 3D carbons as electrocatalysts for efficient hydrogen production. Benefiting from its unique structure, which has more exposed active sites and enhanced conductivity, the as-prepared MoS2/3D nanoporous carbon (3D-NPC) composite exhibits remarkable electrocatalytic activity for the hydrogen evolution reaction (HER) with a small onset overpotential of ∼0.16 V, large cathodic currents, small Tafel slope of 51 mV per decade and good durability. We anticipate that this in situ confined growth provides new insights into the construction of high performance catalysts for energy storage and conversion.

V-Assembly Dual-Head Efficient Resonator (VADER) for Remote Sensing Applications

NASA Technical Reports Server (NTRS)

Coyle, D. Barry; Kay, Richard B.; Stysley, Paul R.; Clark, Greg; Poulios, Demetrios; Frederickson, Robert; Blalock, Gordon; Arnold, Ed; Cory, Ken

2011-01-01

The V-Assembly Dual-head Efficient Resonator (VADER) is a diode pumped, Nd:YAG, Q-switched, positive branch unstable resonator that employs a split laser gain module designed for optimal efficiency and thermal lensing compensation.

Measuring and modeling three-dimensional water uptake of a growing faba bean (Vicia faba) within a soil column

NASA Astrophysics Data System (ADS)

Huber, Katrin; Koebernick, Nicolai; Kerkhofs, Elien; Vanderborght, Jan; Javaux, Mathieu; Vetterlein, Doris; Vereecken, Harry

2014-05-01

A faba bean was grown in a column filled with a sandy soil, which was initially close to saturation and then subjected to a single drying cycle of 30 days. The column was divided in four hydraulically separated compartments using horizontal paraffin layers. Paraffin is impermeable to water but penetrable by roots. Thus by growing deeper, the roots can reach compartments that still contain water. The root architecture was measured every second day by X-ray CT. Transpiration rate, soil matric potential in four different depths, and leaf area were measured continously during the experiment. To investigate the influence of the partitioning of available soil water in the soil column on water uptake, we used R-SWMS, a fully coupled root and soil water model [1]. We compared a scenario with and without the split layers and investigated the influence on root xylem pressure. The detailed three-dimensional root architecture was obtained by reconstructing binarized root images manually with a virtual reality system, located at the Juelich Supercomputing Centre [2]. To verify the properties of the root system, we compared total root lengths, root length density distributions and root surface with estimations derived from Minkowski functionals [3]. In a next step, knowing the change of root architecture in time, we could allocate an age to each root segment and use this information to define age dependent root hydraulic properties that are required to simulate water uptake for the growing root system. The scenario with the split layers showed locally much lower pressures than the scenario without splits. Redistribution of water within the unrestricted soil column led to a more uniform distribution of water uptake and lowers the water stress in the plant. However, comparison of simulated and measured pressure heads with tensiometers suggested that the paraffin layers were not perfectly hydraulically isolating the different soil layers. We could show compensation efficiency of water uptake by the roots in the lower and wetter compartments. By comparing transpiration rates of experiments with and without additional paraffin layers, we were able to quantify restrictions of plant growth to available soil water. [1] Javaux, M., T. Schröder, J. Vanderborght, and H. Vereecken (2008), Use of a Three-Dimensional Detailed Modeling Approach for Predicting Root Water Uptake, Vadose Zone Journal, 7(3), 1079-1079. [2] Stingaciu, L., H. Schulz, A. Pohlmeier, S. Behnke, H. Zilken, M. Javaux, H. Vereecken (2013), In Situ Root System Architecture Extraction from Magnetic Resonance Imaging for Water Uptake Modeling, Vadose Zone Journal, 12(1). [3] Koebernick, N., U. Weller, K. Huber, S. Schlüter, H.-J. Vogel, R. Jahn; H. Vereecken, D. Vetterlein, In situ visualisation and quantification of root-system architecture and growth with X-ray CT, Manuscript submitted for publication.

Novel Split Chest Tube Improves Post-Surgical Thoracic Drainage

PubMed Central

Olivencia-Yurvati, Albert H; Cherry, Brandon H; Gurji, Hunaid A; White, Daniel W; Newton, J Tyler; Scott, Gary F; Hoxha, Besim; Gourlay, Terence; Mallet, Robert T

2014-01-01

Objective Conventional, separate mediastinal and pleural tubes are often inefficient at draining thoracic effusions. Description We developed a Y-shaped chest tube with split ends that divide within the thoracic cavity, permitting separate intrathoracic placement and requiring a single exit port. In this study, thoracic drainage by the split drain vs. that of separate drains was tested. Methods After sternotomy, pericardiotomy, and left pleurotomy, pigs were fitted with separate chest drains (n=10) or a split tube prototype (n=9) with internal openings positioned in the mediastinum and in the costo-diaphragmatic recess. Separate series of experiments were conducted to test drainage of D5W or 0.58 M sucrose, an aqueous solution with viscosity approximating that of plasma. One litre of fluid was infused into the thorax, and suction was applied at −20 cm H2O for 30 min. Results When D5W was infused, the split drain left a residual volume of 53 ± 99 ml (mean value ± SD) vs. 148 ± 120 for the separate drain (P=0.007), representing a drainage efficiency (i.e. drained vol/[drained + residual vol]) of 95 ± 10% vs. 86 ± 12% for the separate drains (P = 0.011). In the second series, the split drain evacuated more 0.58 M sucrose in the first minute (967 ± 129 ml) than the separate drains (680 ± 192 ml, P<0.001). By 30 min, the split drain evacuated a similar volume of sucrose vs. the conventional drain (1089 ± 72 vs. 1056 ± 78 ml; P = 0.5). Residual volume tended to be lower (25 ± 10 vs. 62 ± 72 ml; P = 0.128) and drainage efficiency tended to be higher (98 ± 1 vs. 95 ± 6%; P = 0.111) with the split drain vs. conventional separate drains. Conclusion The split chest tube drained the thoracic cavity at least as effectively as conventional separate tubes. This new device could potentially alleviate postoperative complications. PMID:25478289

Novel Split Chest Tube Improves Post-Surgical Thoracic Drainage.

PubMed

Olivencia-Yurvati, Albert H; Cherry, Brandon H; Gurji, Hunaid A; White, Daniel W; Newton, J Tyler; Scott, Gary F; Hoxha, Besim; Gourlay, Terence; Mallet, Robert T

2014-01-01

Conventional, separate mediastinal and pleural tubes are often inefficient at draining thoracic effusions. We developed a Y-shaped chest tube with split ends that divide within the thoracic cavity, permitting separate intrathoracic placement and requiring a single exit port. In this study, thoracic drainage by the split drain vs. that of separate drains was tested. After sternotomy, pericardiotomy, and left pleurotomy, pigs were fitted with separate chest drains (n=10) or a split tube prototype (n=9) with internal openings positioned in the mediastinum and in the costo-diaphragmatic recess. Separate series of experiments were conducted to test drainage of D5W or 0.58 M sucrose, an aqueous solution with viscosity approximating that of plasma. One litre of fluid was infused into the thorax, and suction was applied at -20 cm H2O for 30 min. When D5W was infused, the split drain left a residual volume of 53 ± 99 ml (mean value ± SD) vs. 148 ± 120 for the separate drain (P=0.007), representing a drainage efficiency (i.e. drained vol/[drained + residual vol]) of 95 ± 10% vs. 86 ± 12% for the separate drains (P = 0.011). In the second series, the split drain evacuated more 0.58 M sucrose in the first minute (967 ± 129 ml) than the separate drains (680 ± 192 ml, P<0.001). By 30 min, the split drain evacuated a similar volume of sucrose vs. the conventional drain (1089 ± 72 vs. 1056 ± 78 ml; P = 0.5). Residual volume tended to be lower (25 ± 10 vs. 62 ± 72 ml; P = 0.128) and drainage efficiency tended to be higher (98 ± 1 vs. 95 ± 6%; P = 0.111) with the split drain vs. conventional separate drains. The split chest tube drained the thoracic cavity at least as effectively as conventional separate tubes. This new device could potentially alleviate postoperative complications.