Catalytic activity and stability of oxides: The role of near-surface atomic structures and compositions

DOE PAGES

Feng, Zhenxing; Hong, Wesley T.; Fong, Dillon D.; ...

2016-05-05

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal$-$air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive andhave shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Here, detailed studies of the oxide surface atomicmore » structure and chemistry (e.g.,cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts.« less

TePtFe Nanotubes as High-Performing Bifunctional Electrocatalysts for the Oxygen Reduction Reaction and Hydrogen Evolution Reaction.

PubMed

Li, Wenqiang; Amiinu, Ibrahim Saana; Ye, Bei; Wang, Zhe; Zhu, Jiawei; Kou, Zongkui; Mu, Shichun

2018-04-25

Currently, a multicomponent platinum-based alloy has been applied as a promising electrocatalyst to improve catalysis and lower the usage of the noble metal platinum. Herein, a tellurium nanowire (NW)-derived ternary TePtFe nanotube (NT) electrocatalyst has been prepared by the Kirkendall effect. The TePtFe NT formed consists of small single-crystal nanoparticles and voids with an open-end and hollow structure. The TePtFe NT electrocatalyst presents an impressive catalytic activity and stability for both the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Its ORR specific activity and mass activity are 8.5 and 2.4 times, respectively, improved relative to those of commercial platinum catalysts. It is also impressive that, for the HER, a very low overpotential of 28.1 mV at 10 mA cm -2 can be achieved; this is lower than that of platinum (51.8 mV) catalysts in 0.1 m HClO 4 , and the activity is improved, even after 5000 cycles. This work reveals that TePtFe NTs can be employed as nanocatalysts with an impressive catalytic activity and stability for application in fuel cells and hydrogen production. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

2017-07-01

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

PubMed Central

Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

2017-01-01

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm−2 at 80 °C with a low platinum loading of 0.09 mgPt cm−2, corresponding to a platinum utilization of 0.13 gPt kW−1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction. PMID:28737170

Surface and Interface Engineering of Noble-Metal-Free Electrocatalysts for Efficient Energy Conversion Processes.

PubMed

Zhu, Yun Pei; Guo, Chunxian; Zheng, Yao; Qiao, Shi-Zhang

2017-04-18

Developing cost-effective and high-performance electrocatalysts for renewable energy conversion and storage is motivated by increasing concerns regarding global energy security and creating sustainable technologies dependent on inexpensive and abundant resources. Recent achievements in the design and synthesis of efficient non-precious-metal and even non-metal electrocatalysts make the replacement of noble metal counterparts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) with earth-abundant elements, for example, C, N, Fe, Mn, and Co, a realistic possibility. It has been found that surface atomic engineering (e.g., heteroatom-doping) and interface atomic or molecular engineering (e.g., interfacial bonding) can induce novel physicochemical properties and strong synergistic effects for electrocatalysts, providing new and efficient strategies to greatly enhance the catalytic activities. In this Account, we discuss recent progress in the design and fabrication of efficient electrocatalysts based on carbon materials, graphitic carbon nitride, and transition metal oxides or hydroxides for efficient ORR, OER, and HER through surface and interfacial atomic and molecular engineering. Atomic and molecular engineering of carbon materials through heteroatom doping with one or more elements of noticeably different electronegativities can maximally tailor their electronic structures and induce a synergistic effect to increase electrochemical activity. Nonetheless, the electrocatalytic performance of chemically modified carbonaceous materials remains inferior to that of their metallic counterparts, which is mainly due to the relatively limited amount of electrocatalytic active sites induced by heteroatom doping. Accordingly, coupling carbon substrates with other active electrocatalysts to produce composite structures can impart novel physicochemical properties, thereby boosting the electroactivity even further. Although the majority of carbon-based materials remain uncompetitive with state-of-the-art metal-based catalysts for the aforementioned catalytic processes, non-metal carbon hybrids have already shown performance that typically only conventional noble metals or transition metal materials can achieve. The idea of hybridized carbon-based catalysts possessing unique active surfaces and macro- or nanostructures is addressed herein. For metal-carbon couples, the incorporation of carbon can effectively compensate for the intrinsic deficiency in conductivity of the metallic components. Chemical modification of carbon frameworks, such as nitrogen doping, not only can change the electron-donor character, but also can introduce anchoring sites for immobilizing active metallic centers to form metal-nitrogen-carbon (M-N-C) species, which are thought to facilitate the electrocatalytic process. With thoughtful material design, control over the porosity of composites, the molecular architecture of active metal moieties and macromorphologies of the whole catalysts can be achieved, leading to a better understanding structure-activity relationships. We hope that we can offer new insight into material design, particularly the role of chemical composition and structural properties in electrochemical performance and reaction mechanisms.

Effect of atomic composition on the compressive strain and electrocatalytic activity of PtCoFe/sulfonated graphene

NASA Astrophysics Data System (ADS)

Lohrasbi, Elaheh; Javanbakht, Mehran; Mozaffari, Sayed Ahmad

2017-06-01

The aim of this work is improvement of the stability and durability of sulfonated graphene supported PtCoFe electrocatalyst (PtCoFe/SG) for application in proton exchange membrane fuel cells (PEMFCs). The durability investigation of PtCoFe/SG is evaluated by a repetitive potential cycling test. The compressive strain in the lattice of PtCoFe/SG towards the electrocatalytic oxygen reduction reaction is studied. The synthesized electrocatalysts are examined physically and electrochemically for their structure, morphology and electrocatalytic performance. It is shown that presence of SO3sbnd groups on the graphene cause better adsorption of PtCoFe nanoparticles on the support and increase stability of electrocatalysts. Also, it is shown that Co:Fe atomic ratio in the synthesized electrocatalysts plays important role in their electrocatalytic performance. In the optimum Co:Fe atomic ratio, the compressive strain goes through the ideal value of the binding energy; further increase in Co/Fe atomic fraction introduces the excessive compressive strain and the activity of electrocatalyst decreases. The electrocatalyst synthesized in the optimum conditions is utilized as cathode in PEMFC. The power density of the PEMFC in low metal loading (0.1 mg cm-2 Pt) reaches to a maximum of 530 mW cm-2 at 75 °C. It suggests that PtCoFe/SG with 7:3 Co:Fe atomic ratio promises to improve the power density of PEMFCs.

Particle size and support effects in electrocatalysis.

PubMed

Hayden, Brian E

2013-08-20

Researchers increasingly recognize that, as with standard supported heterogeneous catalysts, the activity and selectivity of supported metal electrocatalysts are influenced by particle size, particle structure, and catalyst support. Studies using model supported heterogeneous catalysts have provided information about these effects. Similarly, model electrochemical studies on supported metal electrocatalysts can provide insight into the factors determining catalytic activity. High-throughput methods for catalyst synthesis and screening can determine systematic trends in activity as a function of support and particle size with excellent statistical certainty. In this Account, we describe several such studies investigating methods for dispersing precious metals on both carbon and oxide supports, with particular emphasis on the prospects for the development of low-temperature fuel-cell electrocatalysts. One key finding is a decrease in catalytic activity with decreasing particle size independent of the support for both oxygen reduction and CO oxidation on supported gold and platinum. For these reactions, there appears to be an intrinsic particle size effect that results in a loss of activity at particle sizes below 2-3 nm. A titania support, however, also increases activity of gold particles in the electrooxidation of CO and in the reduction of oxygen, with an optimum at 3 nm particle size. This optimum may represent the superposition of competing effects: a titania-induced enhanced activity versus deactivation at small particle sizes. The titania support shows catalytic activity at potentials where carbon-supported and bulk-gold surfaces are normally oxidized and CO electrooxidation is poisoned. On the other hand, platinum on amorphous titania shows a different effect: the oxidation reduction reaction is strongly poisoned in the same particle size range. We correlated the influence of the titania support with titania-induced changes in the surface redox behavior of the platinum particles. For both supported gold and platinum particles in electrocatalysis, we observe parallels to the effects of particle size and support in the equivalent heterogeneous catalysts. Studies of model supported-metal electrocatalysts, performs efficiently using high throughput synthetic and screening methodologies, will lead to a better understanding of the mechanisms responsible for support and particle size effects in electrocatalysis, and will drive the development of more effective and robust catalysts in the future.

Pd-Pt loaded graphene aerogel on nickel foam composite as binder-free anode for a direct glucose fuel cell unit

NASA Astrophysics Data System (ADS)

Tsang, Chi Him A.; Leung, D. Y. C.

2017-09-01

Fabrication of electrocatalyst for direct glucose fuel cell (DGFC) operation involves destructive preparation methods with the use of stabilizer like binder, which may cause activity depreciation. Binder-free electrocatalytic electrode becomes a possible solution to the above problem. Binder-free bimetallic Pd-Pt loaded graphene aerogel on nickel foam plates with different Pd/Pt ratios (1:2.32, 1:1.62, and 1:0.98) are successfully fabricated through a green one-step mild reduction process producing a Pd-Pt/GO/nickel form plate (NFP) composite. Anode with the binder-free electrocatalysts exhibit a strong activity in a batch type DGFC unit under room temperature. The effects of glucose and KOH concentrations, and the Pd/Pt ratios of the electrocatalyst on the DGFC performance are also studied. Maximum power density output of 1.25 mW cm-2 is recorded with 0.5 M glucose/3 M KOH as the anodic fuel, and Pd1Pt0.98/GA/NFP as catalyst, which is the highest obtained so far among other types of electrocatalyst.

Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

2018-01-01

Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

Well-Defined Metal-O6 in Metal-Catecholates as a Novel Active Site for Oxygen Electroreduction.

PubMed

Liu, Xuan-He; Hu, Wei-Li; Jiang, Wen-Jie; Yang, Ya-Wen; Niu, Shuai; Sun, Bing; Wu, Jing; Hu, Jin-Song

2017-08-30

Metal-nitrogen coordination sites, M-N x (M = Fe, Co, Ni, etc.), have shown great potential to replace platinum group materials as electrocatalysts for oxygen reduction reaction (ORR). However, the real active site in M-N x is still vague to date due to their complicated structure and composition. It is therefore highly desirable but challenging to develop ORR catalysts with novel and clear active sites, which could meet the needs of comprehensive understanding of structure-function relationships and explore new cost-effective and efficient ORR electrocatalysts. Herein, well-defined M-O 6 coordination in metal-catecholates (M-CATs, M = Ni or Co) is discovered to be catalytically active for ORR via a four-electron-dominated pathway. In view of no pyrolysis involved and unambiguous crystalline structure of M-CATs, the M-O 6 octahedral coordination site with distinct structure is determined as a new type of active site for ORR. These findings extend the scope of metal-nonmetal coordination as an active site for ORR and pave a way for bottom-up design of novel electrocatalysts containing M-O 6 coordination.

Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution.

PubMed

Tung, Ching-Wei; Hsu, Ying-Ya; Shen, Yen-Ping; Zheng, Yixin; Chan, Ting-Shan; Sheu, Hwo-Shuenn; Cheng, Yuan-Chung; Chen, Hao Ming

2015-08-28

Electrochemically converting water into oxygen/hydrogen gas is ideal for high-density renewable energy storage in which robust electrocatalysts for efficient oxygen evolution play crucial roles. To date, however, electrocatalysts with long-term stability have remained elusive. Here we report that single-crystal Co3O4 nanocube underlay with a thin CoO layer results in a high-performance and high-stability electrocatalyst in oxygen evolution reaction. An in situ X-ray diffraction method is developed to observe a strong correlation between the initialization of the oxygen evolution and the formation of active metal oxyhydroxide phase. The lattice of skin layer adapts to the structure of the active phase, which enables a reversible facile structural change that facilitates the chemical reactions without breaking the scaffold of the electrocatalysts. The single-crystal nanocube electrode exhibits stable, continuous oxygen evolution for >1,000 h. This robust stability is attributed to the complementary nature of defect-free single-crystal electrocatalyst and the reversible adapting layer.

New Electrocatalysts for Direct Oxidation of Organic Fuels

DTIC Science & Technology

2009-06-12

ambient temperature . [28,29] While 13C-NMR provides information on the nature of the adsorbate and the electronic environment at the active surface of...our study to unsupported electrocatalysts that are of greater interest for direct methanol and direct ethanol fuel cells. We have developed a new in...coverage, and type of surface site on the relative adsorption rate and electrooxidative activity of the electrocatalyst. Figure 2 shows sample

Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum-nickel hydroxide-graphene.

PubMed

Huang, Wenjing; Wang, Hongtao; Zhou, Jigang; Wang, Jian; Duchesne, Paul N; Muir, David; Zhang, Peng; Han, Na; Zhao, Feipeng; Zeng, Min; Zhong, Jun; Jin, Chuanhong; Li, Yanguang; Lee, Shuit-Tong; Dai, Hongjie

2015-11-25

Active and durable electrocatalysts for methanol oxidation reaction are of critical importance to the commercial viability of direct methanol fuel cell technology. Unfortunately, current methanol oxidation electrocatalysts fall far short of expectations and suffer from rapid activity degradation. Here we report platinum-nickel hydroxide-graphene ternary hybrids as a possible solution to this long-standing issue. The incorporation of highly defective nickel hydroxide nanostructures is believed to play the decisive role in promoting the dissociative adsorption of water molecules and subsequent oxidative removal of carbonaceous poison on neighbouring platinum sites. As a result, the ternary hybrids exhibit exceptional activity and durability towards efficient methanol oxidation reaction. Under periodic reactivations, the hybrids can endure at least 500,000 s with negligible activity loss, which is, to the best of our knowledge, two to three orders of magnitude longer than all available electrocatalysts.

Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum–nickel hydroxide–graphene

PubMed Central

Huang, Wenjing; Wang, Hongtao; Zhou, Jigang; Wang, Jian; Duchesne, Paul N.; Muir, David; Zhang, Peng; Han, Na; Zhao, Feipeng; Zeng, Min; Zhong, Jun; Jin, Chuanhong; Li, Yanguang; Lee, Shuit-Tong; Dai, Hongjie

2015-01-01

Active and durable electrocatalysts for methanol oxidation reaction are of critical importance to the commercial viability of direct methanol fuel cell technology. Unfortunately, current methanol oxidation electrocatalysts fall far short of expectations and suffer from rapid activity degradation. Here we report platinum–nickel hydroxide–graphene ternary hybrids as a possible solution to this long-standing issue. The incorporation of highly defective nickel hydroxide nanostructures is believed to play the decisive role in promoting the dissociative adsorption of water molecules and subsequent oxidative removal of carbonaceous poison on neighbouring platinum sites. As a result, the ternary hybrids exhibit exceptional activity and durability towards efficient methanol oxidation reaction. Under periodic reactivations, the hybrids can endure at least 500,000 s with negligible activity loss, which is, to the best of our knowledge, two to three orders of magnitude longer than all available electrocatalysts. PMID:26602295

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

DOE PAGES

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh; ...

2017-07-27

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge to produce hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y 2Ru 2O 7-δ) electrocatalyst that has significantly enhanced performance toward OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1 M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y 2Ru 2O 7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band centermore » energy for the overlap between Ru 4d and O 2p orbitals and is therefore more stable Ru–O bond than RuO 2, highlighting the effect of yttrium on the enhancement in stability. Finally, the Y 2Ru 2O 7-δ pyrochlore is also free of expensive iridium metal and thus is a cost-effective candidate for practical applications.« less

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

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

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge for the production of hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y2Ru2O7-δ) electrocatalyst that has significantly enhanced performance towards OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1-M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y2Ru2O7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band center energy for the overlap betweenmore » Ru 4d and O 2p orbitals and therefore more stable Ru-O bond than RuO2, highlighting the effect of yttrium on the enhancement in stability. The Y2Ru2O7-δ pyrochlore is also free of expensive iridium metal, thus a cost-effective candidate for practical applications.« less

High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media

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

Kim, Jaemin; Shih, Pei-Chieh; Tsao, Kai-Chieh

Development of acid-stable electrocatalysts with low overpotential for oxygen evolution reaction (OER) is a major challenge to produce hydrogen directly from water. We report in this paper a pyrochlore yttrium ruthenate (Y 2Ru 2O 7-δ) electrocatalyst that has significantly enhanced performance toward OER in acid media over the best-known catalysts, with an onset overpotential of 190 mV and high stability in 0.1 M perchloric acid solution. X-ray absorption near-edge structure (XANES) indicates Y 2Ru 2O 7-δ electrocatalyst had a low valence state that favors the high OER activity. Density functional theory (DFT) calculation shows this pyrochlore has lower band centermore » energy for the overlap between Ru 4d and O 2p orbitals and is therefore more stable Ru–O bond than RuO 2, highlighting the effect of yttrium on the enhancement in stability. Finally, the Y 2Ru 2O 7-δ pyrochlore is also free of expensive iridium metal and thus is a cost-effective candidate for practical applications.« less

High performance platinum single atom electrocatalyst for oxygen reduction reaction

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

Liu, Jing; Jiao, Menggai; Lu, Lanlu

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm –2 at 80 °C with a low platinum loading of 0.09 mgPt cm –2, corresponding to a platinum utilization of 0.13 gPt kWmore » –1 in the fuel cell. Good fuel cell durability is also observed. As a result, theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.« less

High performance platinum single atom electrocatalyst for oxygen reduction reaction

DOE PAGES

Liu, Jing; Jiao, Menggai; Lu, Lanlu; ...

2017-07-24

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm –2 at 80 °C with a low platinum loading of 0.09 mgPt cm –2, corresponding to a platinum utilization of 0.13 gPt kWmore » –1 in the fuel cell. Good fuel cell durability is also observed. As a result, theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.« less

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum.

PubMed

Yang, Zehui; Nakashima, Naotoshi

2015-07-20

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2'-(2,6-pyridine)-5,5'-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance.

PtRu nanoparticles embedded in nitrogen doped carbon with highly stable CO tolerance and durability

NASA Astrophysics Data System (ADS)

Ling, Ying; Yang, Zehui; Yang, Jun; Zhang, Yunfeng; Zhang, Quan; Yu, Xinxin; Cai, Weiwei

2018-02-01

As is well known, the lower durability and sluggish methanol oxidation reaction (MOR) of PtRu alloy electrocatalyst blocks the commercialization of direct methanol fuel cells (DMFCs). Here, we design a new PtRu electrocatalyst, with highly stable CO tolerance and durability, in which the PtRu nanoparticles are embedded in nitrogen doped carbon layers derived from carbonization of poly(vinyl pyrrolidone). The newly fabricated electrocatalyst exhibits no loss in electrochemical surface area (ECSA) and MOR activity after potential cycling from 0.6-1.0 V versus reversible hydrogen electrode, while commercial CB/PtRu retains only 50% of its initial ECSA. Meanwhile, due to the same protective layers, the Ru dissolution is decelerated, resulting in stable CO tolerance. Methanol oxidation reaction (MOR) testing indicates that the activity of newly fabricated electrocatalyst is two times higher than that of commercial CB/PtRu, and the fuel cell performance of the embedded PtRu electrocatalyst was comparable to that of commercial CB/PtRu. The embedded PtRu electrocatalyst is applicable in real DMFC operation. This study offers important and useful information for the design and fabrication of durable and CO tolerant electrocatalysts.

Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2.

PubMed

Miner, Elise M; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

2016-03-08

Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.

Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2

PubMed Central

Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dincă, Mircea

2016-01-01

Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units. Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. Such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications. PMID:26952523

Electrochemical oxygen reduction catalysed by Ni 3(hexaiminotriphenylene) 2

DOE PAGES

Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; ...

2016-03-08

Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni 3(HITP) 2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni 3(HITP) 2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N 4 sites are structurally reminiscent of the highly active and widely studied non-platinum groupmore » metal electrocatalysts containing M-N 4 units. Ni 3(HITP) 2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. As a result, such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.« less

Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

NASA Astrophysics Data System (ADS)

Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

2016-09-01

We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

An in situ vapour phase hydrothermal surface doping approach for fabrication of high performance Co3O4 electrocatalysts with an exceptionally high S-doped active surface.

PubMed

Tan, Zhijin; Liu, Porun; Zhang, Haimin; Wang, Yun; Al-Mamun, Mohammad; Yang, Hua Gui; Wang, Dan; Tang, Zhiyong; Zhao, Huijun

2015-04-04

A facile in situ vapour phase hydrothermal (VPH) surface doping approach has been developed for fabrication of high performance S-doped Co3O4 electrocatalysts with an unprecedentedly high surface S content (>47%). The demonstrated VPH doping approach could be useful for enrichment of surface active sites for other metal oxide electrocatalysts.

Durability enhancement of intermetallics electrocatalysts via N-anchor effect for fuel cells.

PubMed

Li, Xiang; An, Li; Chen, Xin; Zhang, Nanlin; Xia, Dingguo; Huang, Weifeng; Chu, Wangsheng; Wu, Ziyu

2013-11-18

Insufficient durability and catalytic activity of oxygen reduction reaction (ORR) electrocatalyst are key issues that have to be solved for the practical application of low temperature fuel cell. This paper introduces a new catalyst design strategy using N-anchor to promote the corrosion resistance of electrocatalyst. The as-synthesized N-Pt3Fe1/C shows a high electrocatalytic activity and a superior durability towards ORR. The kinetic current density of N-Pt3Fe1/C as normalized by ECSA is still as high as 0.145 mA cm(-2) and only 7% loss after 20,000 potential cycles from 0.6 to 1.2 V (vs. NHE) in O2-bubbling perchloric acid solution, whereas Pt3Fe1/C shows 49% loss under the same tests. The N-anchor approach offers novel opportunities for the development of ORR catalyst with excellent electrochemical properties.

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Pagliaro, P.

1980-01-01

Results are presented for hydrogen oxidation and hydrogen oxidation poisoned by carbon monoxide at levels between 0 and 30%. Due to the high activities that are now being observed for our platinum based electrocatalysts, the hydrogen concentrations were reduced to 10% levels in the gas supplies. Perturbation techniques were used to determine that a mechanism for the efficient operation of our porous gas diffusion electrodes is diffusion of the carbon monoxide out of the electrode structure through the electrolyte film on the electro-catalyst. A survey of the literature on platinum group materials (PGM) was carried out so that an identification of successful electrocatalysts could be made. Two PGM electrocatalysts were prepared and performance data for hydrogen oxidation in hot phosphoric acid in the presence of high carbon monoxide concentrations showed that they matched the best platinum on carbon electrocatalysts but with an electrocatalyst cost that was half of the platinum catalyst cost.

From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

2017-07-01

Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

MnMoO4 nanosheet array: an efficient electrocatalyst for hydrogen evolution reaction with enhanced activity over a wide pH range.

PubMed

Wen, Lulu; Sun, Yiqiang; Zhang, Tao; Bai, Yu; Li, Xinyang; Lyu, Xianjun; Cai, Weiping; Li, Yue

2018-08-17

We report the preparation of MnMoO 4 nanosheet array on nickel foam (MnMoO 4 NSA/NF) as an excellent 3D hydrogen evolution reaction (HER) electrocatalyst with good catalytic performance applied under basic, acidic and neutral conditions. In 0.5 M H 2 SO 4 , this MnMoO 4 NSA/NF electrode needs an overpotential of 89 mV to drive current densities of 10 mA cm -2 , to achieve the same current density, it demands overpotentials of 105 mV in 1.0 M KOH, 161 mV in 1.0 M PBS (pH = 7), respectively. After continuous CV scanning for 1000 cycles under different pH conditions, it also demonstrates an excellent stability with ignorable activity decrease. Such preeminent HER performance may be derived from the synergistic effect between manganese (Mn) and molybdenum (Mo) atoms, exposure of more active sites on the nanosheets and effective electron transport along the nanosheets. This MnMoO 4 NSA/NF electrocatalyst provides us a highly efficient material for water splitting devices for industrial hydrogen production.

A unified model for surface electrocatalysis based on observations with enzymes.

PubMed

Hexter, Suzannah V; Esterle, Thomas F; Armstrong, Fraser A

2014-06-28

Despite being so large, many enzymes are not only excellent electrocatalysts - making possible chemical transformations under almost reversible conditions - but they also facilitate our understanding of electrocatalysis by allowing complex processes to be dissected systematically. The electrocatalytic voltammograms obtained for enzymes attached to an electrode expose fundamental aspects of electrocatalysis that can be addressed in ways that are not available to conventional molecular or surface electrocatalysts. The roles of individual components, each characterisable by diffraction or spectroscopy, can be tested and optimised by genetic engineering. Importantly, unlike small-molecule electrocatalysts (RMM < 1000) that are structurally well-defined but invariably altered by being attached to a surface, the enzyme is a giant, multi-component assembly in which the active site is buried and relatively insensitive to the presence of the electrode and solvent interface. A central assertion is that for a given driving force (electrode potential) a true catalyst has no influence on the direction of the reaction; consequently, 'catalytic bias', i.e. the common observation that an enzyme or indeed any electrocatalyst operates preferentially in one direction, must arise from secondary effects beyond the elementary catalytic cycle. This Perspective highlights and extends a general model for electrocatalysis by surface-confined enzymes, and explains how two secondary effects control the bias: (i) the electrode potential at which electrons enter or leave the catalytic cycle; (ii) potential-dependent interconversions between states of the catalyst differing in catalytic activity due to changes in the composition and arrangements of atoms. The model, which is easily applied to enzymes that have been studied recently, highlights important considerations for understanding and developing surface-confined electrocatalysts.

A simple preparation of very high methanol tolerant cathode electrocatalyst for direct methanol fuel cell based on polymer-coated carbon nanotube/platinum

PubMed Central

Yang, Zehui; Nakashima, Naotoshi

2015-01-01

The development of a durable and methanol tolerant electrocatalyst with a high oxygen reduction reaction activity is highly important for the cathode side of direct methanol fuel cells. Here, we describe a simple and novel methodology to fabricate a practically applicable electrocatalyst with a high methanol tolerance based on poly[2,2′-(2,6-pyridine)-5,5′-bibenzimidazole]-wrapped multi-walled carbon nanotubes, on which Pt nanoparticles have been deposited, then coated with poly(vinylphosphonic acid) (PVPA). The polymer coated electrocatalyst showed an ~3.3 times higher oxygen reduction reaction activity compared to that of the commercial CB/Pt and methanol tolerance in the presence of methanol to the electrolyte due to a 50% decreased methanol adsorption on the Pt after coating with the PVPA. Meanwhile, the peroxide generation of the PVPA coated electrocatalyst was as low as 0.8% with 2 M methanol added to the electrolyte, which was much lower than those of the non-PVPA-coated electrocatalyst (7.5%) and conventional CB/Pt (20.5%). Such a high methanol tolerance is very important for the design of a direct methanol fuel cell cathode electrocatalyst with a high performance. PMID:26192397

Investigating the effects of proton exchange membrane fuel cell conditions on carbon supported platinum electrocatalyst composition and performance

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

Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen

2011-12-01

Changes that carbon-supported platinum electrocatalysts undergo in a proton exchange membrane fuel cell environment were simulated by ex situ heat treatment of catalyst powder samples at 150 C and 100% relative humidity. In order to study modifications that are introduced to chemistry, morphology, and performance of electrocatalysts, XPS, HREELS and three-electrode rotating disk electrode experiments were performed. Before heat treatment, graphitic content varied by 20% among samples with different types of carbon supports, with distinct differences between bulk and surface compositions within each sample. Following the aging protocol, the bulk and surface chemistry of the samples were similar, with graphitemore » content increasing or remaining constant and Pt-carbide decreasing for all samples. From the correlation of changes in chemical composition and losses in performance of the electrocatalysts, we conclude that relative distribution of Pt particles on graphitic and amorphous carbon is as important for electrocatalytic activity as the absolute amount of graphitic carbon present« less

Pt-Ru/CeO2/carbon nanotube nanocomposites: an efficient electrocatalyst for direct methanol fuel cells.

PubMed

Sun, Zhenyu; Wang, Xiang; Liu, Zhimin; Zhang, Hongye; Yu, Ping; Mao, Lanqun

2010-07-20

Pt-Ru/CeO(2)/multiwalled carbon nanotube (MWNT) electrocatalysts were prepared using a rapid sonication-facilitated deposition method and were characterized by X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS), and voltammetry. Morphological characterization by TEM revealed that CeO(2) nanoparticles (NPs) were in intimate contact with Pt-Ru NPs, and both were highly dispersed on the exteriors of nanotubes with a small size and a very narrow size distribution. Compared with the Pt-Ru/MWNT and Pt/MWNT electrocatalysts, the as-prepared Pt-Ru/CeO(2)/MWNT exhibited a significantly improved electrochemically active surface area (ECSA) and a remarkably enhanced activity toward methanol oxidation. The effects of the Pt-Ru loading and the Pt-to-Ru molar ratio on the electrocatalytic activity of Pt-Ru/CeO(2)/MWNT for methanol oxidation were investigated. We found that a maximum activity toward methanol oxidation reached at the 10 wt % of Pt-Ru loading and 1:1 of Pt-to-Ru ratio. Moreover, the role of CeO(2) in the catalysts for the enhancement of methanol oxidation was discussed in terms of both bifunctional mechanism and electronic effects.

Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

NASA Astrophysics Data System (ADS)

Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang

2017-05-01

Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm-2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers.

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.

Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

2016-02-01

In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

Self-assembled platinum nanoparticles on sulfonic acid-grafted graphene as effective electrocatalysts for methanol oxidation in direct methanol fuel cells.

PubMed

Lu, Jinlin; Li, Yanhong; Li, Shengli; Jiang, San Ping

2016-02-15

In this article, sulfonic acid-grafted reduced graphene oxide (S-rGO) were synthesized using a one-pot method under mild conditions, and used as Pt catalyst supports to prepare Pt/S-rGO electrocatalysts through a self-assembly route. The structure, morphologies and physicochemical properties of S-rGO were examined in detail by techniques such as atomic force microscope (AFM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The S-rGO nanosheets show excellent solubility and stability in water and the average particle size of Pt nanoparticles supported on S-rGO is ~3.8 nm with symmetrical and uniform distribution. The electrocatalytic properties of Pt/S-rGO were investigated for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). In comparison to Pt supported on high surface area Vulcan XC-72 carbon (Pt/VC) and Pt/rGO, the Pt/S-rGO electrocatalyst exhibits a much higher electrocatalytic activity, faster reaction kinetics and a better stability. The results indicate that Pt/S-rGO is a promising and effective electrocatalyst for MOR of DMFCs.

Hollow core-shell structured Ni-Sn@C nanoparticles: a novel electrocatalyst for the hydrogen evolution reaction.

PubMed

Lang, Leiming; Shi, Yi; Wang, Jiong; Wang, Feng-Bin; Xia, Xing-Hua

2015-05-06

Pt-free electrocatalysts with high activity and low cost are highly pursued for hydrogen production by electrochemically splitting water. Ni-based alloy catalysts are potential candidates for the hydrogen evolution reaction (HER) and have been studied extensively. Here, we synthesized novel hollow core-shell structure Ni-Sn@C nanoparticles (NPs) by sol-gel, chemical vapor deposition, and etching processes. The prepared electrocatalysts with porous hollow carbon layers have a high conductivity and large active area, which exhibit good electrocatalytic activity toward HER. The Tafel slope of ∼35 millivolts per decade measured in acidic solution for Ni-Sn@C NPs is the smallest one to date for the Ni-Sn alloy catalysts, and exceeds those of the most non-noble metal catalysts, indicating a possible Volmer-Heyrovsky reaction mechanism. The synthetic method can be extended to prepare other hollow core-shell structure electrocatalysts for low-temperature fuel cells.

Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

2015-09-01

Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

Onion-derived N, S self-doped carbon materials as highly efficient metal-free electrocatalysts for the oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Yang, Shuting; Mao, Xinxin; Cao, Zhaoxia; Yin, Yanhong; Wang, Zhichao; Shi, Mengjiao; Dong, Hongyu

2018-01-01

Onion-derived nitrogen, sulfur self-doped nanoporous carbon spheres (NSC) as efficient metal-free electrocatalyst were synthesized via a facile hydrothermal and subsequent pyrolysis process. The typical NSC with a high BET specific surface area of 1558 m2 g-1, contains 6.23 at.% N and 0.36 at.% S, and possesses high concentration of pyridinic and graphitic nitrogen species. Experimentally, the best performance was the NSC-A2 which showed excellent catalytic activity to oxygen reduction reaction via a 4 electron mechanism with an onset potential of 0.88 V (vs. RHE), and a superior stability comparable to commercial Pt/C catalyst. The high electrocatalytic activity is attributed to not only the synergistic effect of N and S dual doping in carbon and the sufficient active sites, but also its high BET specific surface area and suitable microporous structure. The results demonstrate that it is a simple and scalable approach for preparing efficient and low-cost carbon-based electrocatalysts for oxygen reduction reaction.

Controlling electrodeposited ultrathin amorphous Fe hydroxides film on V-doped nickel sulfide nanowires as efficient electrocatalyst for water oxidation

NASA Astrophysics Data System (ADS)

Shang, Xiao; Yan, Kai-Li; Lu, Shan-Shan; Dong, Bin; Gao, Wen-Kun; Chi, Jing-Qi; Liu, Zi-Zhang; Chai, Yong-Ming; Liu, Chen-Guang

2017-09-01

Developing cost-effective electrocatalysts with both high activity and stability remains challenging for oxygen evolution reaction (OER) in water electrolysis. Herein, based on V-doped nickel sulfide nanowire on nickel foam (NiVS/NF), we further conduct controllable electrodeposition of Fe hydroxides film on NiVS/NF (eFe/NiVS/NF) to further improve OER performance and stability. For comparison, ultrafast chemical deposition of Fe hydroxides on NiVS/NF (uFe/NiVS/NF) is also utilized. V-doping of NiVS/NF may introduce more active sites for OER, and nanowire structure can expose abundant active sites and facilitate mass transport. Both of the two depositions generate amorphous Fe hydroxides film covering on the surface of nanowires and lead to enhanced OER activities. Furthermore, electrodeposition strategy realizes uniform Fe hydroxides film on eFe/NiVS/NF confirmed by superior OER activity of eFe/NiVS/NF than uFe/NiVS/NF with relatively enhanced stability. The OER activity of eFe/NiVS/NF depends on various electrodepositon time, and the optimal time (15 s) is obtained with maximum OER activity. Therefore, the controllable electrodeposition of Fe may provide an efficient and simple strategy to enhance the OER properties of electrocatalysts.

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

A Pt-Co3O4-CD electrocatalyst with enhanced electrocatalytic performance and resistance to CO poisoning achieved by carbon dots and Co3O4 for direct methanol fuel cells.

PubMed

Sun, Yue; Zhou, Yunjie; Zhu, Cheng; Hu, Lulu; Han, Mumei; Wang, Aoqi; Huang, Hui; Liu, Yang; Kang, Zhenhui

2017-05-04

Highly efficient electrocatalysts remain huge challenges in direct methanol fuel cells (DMFCs). Here, a Pt-Co 3 O 4 -CDs/C composite was fabricated as an anode electrocatalyst with low Pt content (12 wt%) by using carbon dots (CDs) and Co 3 O 4 nanoparticles as building blocks. The Pt-Co 3 O 4 -CDs/C composite catalyst shows a significantly enhanced electrocatalytic activity (1393.3 mA mg -1 Pt), durability (over 4000 s) and CO-poisoning tolerance. The superior catalytic activity should be attributed to the synergistic effect of CDs, Pt and Co 3 O 4 . Furthermore, the Pt-Co 3 O 4 -CDs/C catalyst was integrated into a single cell, which exhibits a maximum power density of 45.6 mW cm -2 , 1.7 times the cell based on the commercial 20 wt% Pt/C catalyst.

Method for removing strongly adsorbed surfactants and capping agents from metal to facilitate their catalytic applications

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

Adzic, Radoslav R.; Gong, Kuanping; Cai, Yun

A method of synthesizing activated electrocatalyst, preferably having a morphology of a nanostructure, is disclosed. The method includes safely and efficiently removing surfactants and capping agents from the surface of the metal structures. With regard to metal nanoparticles, the method includes synthesis of nanoparticle(s) in polar or non-polar solution with surfactants or capping agents and subsequent activation by CO-adsorption-induced surfactant/capping agent desorption and electrochemical oxidation. The method produces activated macroparticle or nanoparticle electrocatalysts without damaging the surface of the electrocatalyst that includes breaking, increasing particle thickness or increasing the number of low coordination sites.

Electronic Modulation of Electrocatalytically Active Center of Cu7S4 Nanodisks by Cobalt-Doping for Highly Efficient Oxygen Evolution Reaction.

PubMed

Li, Qun; Wang, Xianfu; Tang, Kai; Wang, Mengfan; Wang, Chao; Yan, Chenglin

2017-12-26

Cu-based electrocatalysts have seldom been studied for water oxidation because of their inferior activity and poor stability regardless of their low cost and environmentally benign nature. Therefore, exploring an efficient way to improve the activity of Cu-based electrocatalysts is very important for their practical application. Modifying electronic structure of the electrocatalytically active center of electrocatalysts by metal doping to favor the electron transfer between catalyst active sites and electrode is an important approach to optimize hydrogen and oxygen species adsorption energy, thus leading to the enhanced intrinsic electrocatalytic activity. Herein, Co-doped Cu 7 S 4 nanodisks were synthesized and investigated as highly efficient electrocatalyst for oxygen evolution reaction (OER) due to the optimized electronic structure of the active center. Density-functional theory (DFT) calculations reveal that Co-engineered Cu 7 S 4 could accelerate electron transfer between Co and Cu sites, thus decrease the energy barriers of intermediates and products during OER, which are crucial for enhanced catalytic properties. As expected, Co-engineered Cu 7 S 4 nanodisks exhibit a low overpotential of 270 mV to achieve current density of 10 mA cm -2 as well as decreased Tafel slope and enhanced turnover frequencies as compared to bare Cu 7 S 4 . This discovery not only provides low-cost and efficient Cu-based electrocatalyst by Co doping, but also exhibits an in-depth insight into the mechanism of the enhanced OER properties.

An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.

PubMed

Gong, Ming; Li, Yanguang; Wang, Hailiang; Liang, Yongye; Wu, Justin Z; Zhou, Jigang; Wang, Jian; Regier, Tom; Wei, Fei; Dai, Hongjie

2013-06-12

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

DOE PAGES

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao; ...

2016-08-30

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

Inhibition of tafel kinetics for electrolytic hydrogen evolution on isolated micron scale electrocatalysts on semiconductor interfaces

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

Coridan, Robert H.; Schichtl, Zebulon G.; Sun, Tao

Semiconductor-liquid junctions are ubiquitous in photoelectrochemical approaches for solar-to-fuels energy conversion. Electrocatalysts are added to the interface to improve catalytic efficiency, but they can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. This balance is more complicated when gas products are evolved, like hydrogen on water splitting electrodes. Discrete catalysts can be blocked by the gas liquid-solid boundary of a bubble stuck to the surface. Here, we study the kinetics of hydrogen evolution on semiconductor electrodes fabricated with an isolated, micronscale platinum electrocatalyst pad. Movies of in operando bubblemore » evolution were recorded with synchrotron-based high-speed x-ray phase-contrast imaging in a compatible electrochemical cell. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas-liquid boundary through the sequence of images in the movie. As a result, the effect of pad size on the catalytic currents and the issues with reactant transport can be inferred from these dynamics.« less

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

In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe2+ induction as an efficient and stable electrocatalyst for water oxidation.

PubMed

Xing, Jiale; Guo, Kailu; Zou, Zehua; Cai, Minmin; Du, Jing; Xu, Cailing

2018-06-06

Well-ordered NiFe-MOF-74 is in situ grown on Ni foam by the induction of Fe2+ and directly used as an OER electrocatalyst. Benefited from the intrinsic open porous structure of MOF-74, the in situ formed MOF arrays and the synergistic effect of Ni and Fe, outstanding water oxidation activity is obtained in alkaline electrolytes with an overpotential of 223 mV at 10 mA cm-2.

In situ probing of the active site geometry of ultrathin nanowires for the oxygen reduction reaction

DOE PAGES

Liu, Haiqing; Wong, Stanislaus S.; An, Wei; ...

2015-09-24

To create truly effective electrocatalysts for the cathodic reaction governing proton exchange membrane fuel cells (PEMFC), namely the oxygen reduction reaction (ORR), necessitates an accurate and detailed structural understanding of these electrocatalysts, especially at the nanoscale, and to precisely correlate that structure with demonstrable performance enhancement. To address this key issue, we have combined and interwoven theoretical calculations with experimental, spectroscopic observations in order to acquire useful structural insights into the active site geometry with implications for designing optimized nanoscale electrocatalysts with rationally predicted properties. Specifically, we have probed ultrathin (~2 nm) core–shell Pt~Pd 9Au nanowires, which have been previouslymore » shown to be excellent candidates for ORR in terms of both activity and long-term stability, from the complementary perspectives of both DFT calculations and X-ray absorption spectroscopy (XAS). The combination and correlation of data from both experimental and theoretical studies has revealed for the first time that the catalytically active structure of our ternary nanowires can actually be ascribed to a PtAu~Pd configuration, comprising a PtAu binary shell and a pure inner Pd core. Moreover, we have plausibly attributed the resulting structure to a specific synthesis step, namely the Cu underpotential deposition (UPD) followed by galvanic replacement with Pt. Thus, the fundamental insights gained into the performance of our ultrathin nanowires from our demonstrated approach will likely guide future directed efforts aimed at broadly improving upon the durability and stability of nanoscale electrocatalysts in general.« less

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hochmuth, J.; Pagliaro, P.

1981-01-01

The highest performance fuel cell cathode electrocatalyst combination ever observed gives 755 mV vs hydrogen at 100 ASF on air at 180 C and shows a potential improvement to 775 mV vs hydrogen for better electrode structures. A pressurized fuel cell (UTC at 5 atm) would then give 805 mV at 320 ASF and 180 C. Another activity diagnostic is the performance of this electrocatalyst on oxygen at 900 mV vs hydrogen. The value for electrocatalyst is 44 mA per milligram of platinum and is projected to reach 60 mA per milligram of platinum with improved electrode structures. Since the electrocatalyst surface area and the electrode structure are not yet optimized there is considerable room for performance enhancement beyond these values, especially at higher temperatures.

Influence of support material on the electrocatalytic activity of nickel oxide nanoparticles for urea electro-oxidation reaction.

PubMed

Abdel Hameed, R M; Medany, Shymaa S

2018-03-01

Nickel oxide nanoparticles were deposited on different carbon supports including activated Vulcan XC-72R carbon black (NiO/AC), multi-walled carbon nanotubes (NiO/MWCNTs), graphene (NiO/Gr) and graphite (NiO/Gt) through precipitation step followed by calcination at 400 °C. To determine the crystalline structure and morphology of prepared electrocatalysts, X-ray diffraction (XRD) and transmission electron microscopy (TEM) were employed. The electrocatalytic activity of NiO/carbon support electrocatalysts was investigated towards urea electro-oxidation reaction in NaOH solution using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. Urea oxidation peak current density was increased in the following order: NiO/AC < NiO/MWCNTs < NiO/Gr < NiO/Gt. Chronoamperometry test also showed an increased steady state oxidation current density for NiO/Gt in comparison to other electrocatalysts. The increased activity and stability of NiO/Gt electrocatalyst encourage the application of graphite as an efficient and cost-saving support to carry metal nanoparticles for urea electro-oxidation reaction. Copyright © 2017 Elsevier Inc. All rights reserved.

An Operando Investigation of (Ni–Fe–Co–Ce)O x System as Highly Efficient Electrocatalyst for Oxygen Evolution Reaction

DOE PAGES

Favaro, Marco; Drisdell, Walter S.; Marcus, Matthew A.; ...

2016-12-27

The oxygen evolution reaction (OER) is a critical component of industrial processes such as electrowinning of metals and the chlor-alkali process. It also plays a central role in the development of a renewable energy field for generation a solar fuels by providing both the protons and electrons needed to generate fuels such as H 2 or reduced hydrocarbons from CO 2. To improve these processes, it is necessary to expand the fundamental understanding of catalytically active species at low overpotential, which will further the development of electrocatalysts with high activity and durability. In this context, performing experimental investigations of themore » electrocatalysts under realistic working regimes (i.e., under operando conditions) is of crucial importance. In this paper, we study a highly active quinary transition-metal-oxide-based OER electrocatalyst by means of operando ambient-pressure X-ray photoelectron spectroscopy and X-ray absorption spectroscopy performed at the solid/liquid interface. We observe that the catalyst undergoes a clear chemical-structural evolution as a function of the applied potential with Ni, Fe, and Co oxyhydroxides comprising the active catalytic species. Finally, while CeO 2 is redox inactive under catalytic conditions, its influence on the redox processes of the transition metals boosts the catalytic activity at low overpotentials, introducing an important design principle for the optimization of electrocatalysts and tailoring of high-performance materials.« less

Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap

PubMed Central

Karunagaran, Ramesh; Coghlan, Campbell; Gulati, Karan; Tung, Tran Thanh; Doonan, Christian

2018-01-01

Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas) into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR) in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF) and carbon microspheres (N-CMS) synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism. PMID:29382103

Green Synthesis of Three-Dimensional Hybrid N-Doped ORR Electro-Catalysts Derived from Apricot Sap.

PubMed

Karunagaran, Ramesh; Coghlan, Campbell; Shearer, Cameron; Tran, Diana; Gulati, Karan; Tung, Tran Thanh; Doonan, Christian; Losic, Dusan

2018-01-28

Rapid depletion of fossil fuel and increased energy demand has initiated a need for an alternative energy source to cater for the growing energy demand. Fuel cells are an enabling technology for the conversion of sustainable energy carriers (e.g., renewable hydrogen or bio-gas) into electrical power and heat. However, the hazardous raw materials and complicated experimental procedures used to produce electro-catalysts for the oxygen reduction reaction (ORR) in fuel cells has been a concern for the effective implementation of these catalysts. Therefore, environmentally friendly and low-cost oxygen reduction electro-catalysts synthesised from natural products are considered as an attractive alternative to currently used synthetic materials involving hazardous chemicals and waste. Herein, we describe a unique integrated oxygen reduction three-dimensional composite catalyst containing both nitrogen-doped carbon fibers (N-CF) and carbon microspheres (N-CMS) synthesised from apricot sap from an apricot tree. The synthesis was carried out via three-step process, including apricot sap resin preparation, hydrothermal treatment, and pyrolysis with a nitrogen precursor. The nitrogen-doped electro-catalysts synthesised were characterised by SEM, TEM, XRD, Raman, and BET techniques followed by electro-chemical testing for ORR catalysis activity. The obtained catalyst material shows high catalytic activity for ORR in the basic medium by facilitating the reaction via a four-electron transfer mechanism.

Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching.

PubMed

Han, Lijuan; Tang, Pengyi; Reyes-Carmona, Álvaro; Rodríguez-García, Bárbara; Torréns, Mabel; Morante, Joan Ramon; Arbiol, Jordi; Galan-Mascaros, Jose Ramon

2016-12-14

The development of upscalable oxygen evolving electrocatalysts from earth-abundant metals able to operate in neutral or acidic environments and low overpotentials remains a fundamental challenge for the realization of artificial photosynthesis. In this study, we report a highly active phase of heterobimetallic cyanide-bridged electrocatalysts able to promote water oxidation under neutral, basic (pH < 13), and acidic conditions (pH > 1). Cobalt-iron Prussian blue-type thin films, formed by chemical etching of Co(OH) 1.0 (CO 3 ) 0.5 ·nH 2 O nanocrystals, yield a dramatic enhancement of the catalytic performance toward oxygen production, when compared with previous reports for analogous materials. Electrochemical, spectroscopic, and structural studies confirm the excellent performance, stability, and corrosion resistance, even when compared with state-of-the-art metal oxide catalysts under moderate overpotentials and in a remarkably large pH range, including acid media where most cost-effective water oxidation catalysts are not useful. The origin of the superior electrocatalytic activity toward water oxidation appears to be in the optimized interfacial matching between catalyst and electrode surface obtained through this fabrication method.

N-doped graphene coupled with Co nanoparticles as an efficient electrocatalyst for oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Zhang, Geng; Lu, Wangting; Cao, Feifei; Xiao, Zhidong; Zheng, Xinsheng

2016-01-01

Development of low-cost and highly efficient electrocatalysts for oxygen reduction reaction (ORR) is still a great challenge for the large-scale application of fuel cells and metal-air batteries. Herein, a noble metal-free ORR electrocatalyst in the form of N-doped graphene coupled with part of Co nanoparticles encased in N-doped graphitic shells (named as SUCo-0.03-800) is prepared by facile one-step pyrolysis of the mixture of sucrose, urea and cobalt nitrate. The novel structure is confirmed by High Resolution-TEM, XRD, XPS and Raman spectroscopy. SUCo-0.03-800 presents comparable ORR catalytic activity to commercial Pt/C catalyst with a dominating four-electron pathway under alkaline conditions, and both of its mass activity and volume activity also outperform Co-free N-doped graphene and other Co/N-C hybrids with higher Co content, which may probably be ascribed to the high specific surface area, novel structure and synergistic effect between encased Co nanoparticles and N-doped graphitic shell. Additionally, SUCo-0.03-800 also shows outstanding stability and improved selectivity towards ORR, making it a promising alternative to Pt with potential application in fuel cells and metal-air batteries.

Tin-oxide-coated single-walled carbon nanotube bundles supporting platinum electrocatalysts for direct ethanol fuel cells.

PubMed

Hsu, Ryan S; Higgins, Drew; Chen, Zhongwei

2010-04-23

Novel tin-oxide (SnO(2))-coated single-walled carbon nanotube (SWNT) bundles supporting platinum (Pt) electrocatalysts for ethanol oxidation were developed for direct ethanol fuel cells. SnO(2)-coated SWNT (SnO(2)-SWNT) bundles were synthesized by a simple chemical-solution route. SnO(2)-SWNT bundles supporting Pt (Pt/SnO(2)-SWNTs) electrocatalysts and SWNT-supported Pt (Pt/SWNT) electrocatalysts were prepared by an ethylene glycol reduction method. The catalysts were physically characterized using TGA, XRD and TEM and electrochemically evaluated through cyclic voltammetry experiments. The Pt/SnO(2)-SWNTs showed greatly enhanced electrocatalytic activity for ethanol oxidation in acid medium, compared to the Pt/SWNT. The optimal SnO(2) loading of Pt/SnO(2)-SWNT catalysts with respect to specific catalytic activity for ethanol oxidation was also investigated.

Design Principles for Covalent Organic Frameworks as Efficient Electrocatalysts in Clean Energy Conversion and Green Oxidizer Production.

PubMed

Lin, Chun-Yu; Zhang, Lipeng; Zhao, Zhenghang; Xia, Zhenhai

2017-05-01

Covalent organic frameworks (COFs), an emerging class of framework materials linked by covalent bonds, hold potential for various applications such as efficient electrocatalysts, photovoltaics, and sensors. To rationally design COF-based electrocatalysts for oxygen reduction and evolution reactions in fuel cells and metal-air batteries, activity descriptors, derived from orbital energy and bonding structures, are identified with the first-principle calculations for the COFs, which correlate COF structures with their catalytic activities. The calculations also predict that alkaline-earth metal-porphyrin COFs could catalyze the direct production of H 2 O 2 , a green oxidizer and an energy carrier. These predictions are supported by experimental data, and the design principles derived from the descriptors provide an approach for rational design of new electrocatalysts for both clean energy conversion and green oxidizer production. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of Pd/PANI/Pd sandwich-structured nanotube array catalysts with special shape effects and synergistic effects for ethanol electrooxidation.

PubMed

Wang, An-Liang; Xu, Han; Feng, Jin-Xian; Ding, Liang-Xin; Tong, Ye-Xiang; Li, Gao-Ren

2013-07-24

Low cost, high activity, and long-term durability are the main requirements for commercializing fuel cell electrocatalysts. Despite tremendous efforts, developing non-Pt anode electrocatalysts with high activity and long-term durability at low cost remains a significant technical challenge. Here we report a new type of hybrid Pd/PANI/Pd sandwich-structured nanotube array (SNTA) to exploit shape effects and synergistic effects of Pd-PANI composites for the oxidation of small organic molecules for direct alcohol fuel cells. These synthesized Pd/PANI/Pd SNTAs exhibit significantly improved electrocatalytic activity and durability compared with Pd NTAs and commercial Pd/C catalysts. The unique SNTAs provide fast transport and short diffusion paths for electroactive species and high utilization rate of catalysts. Besides the merits of nanotube arrays, the improved electrocatalytic activity and durability are especially attributed to the special Pd/PANI/Pd sandwich-like nanostructures, which results in electron delocalization between Pd d orbitals and PANI π-conjugated ligands and in electron transfer from Pd to PANI.

Confined Molybdenum Phosphide in P-Doped Porous Carbon as Efficient Electrocatalysts for Hydrogen Evolution.

PubMed

Li, Ji-Sen; Zhang, Shuai; Sha, Jing-Quan; Wang, Hao; Liu, Ming-Zhu; Kong, Ling-Xin; Liu, Guo-Dong

2018-05-09

Highly efficient electrocatalysts for hydrogen evolution reactions (HER) are crucial for electrochemical water splitting, where high-cost and low-abundance Pt-based materials are the benchmark catalysts for HER. Herein, we report the fabrication of MoP nanoparticles confined in P-doped porous carbon (MoP@PC) via a metal-organic framework-assisted route for the first time. Remarkably, due to the synergistic effects of MoP nanocrystals, P dopant, and porous carbon, the resulting MoP@PC composite exhibits superior HER catalytic activity with an onset overpotential of 97 mV, a Tafel slope of 59.3 mV dec -1 , and good long-term durability, which compares to those of most reported MoP-based HER catalysts. Most importantly, the work opens a new route in the development of high-performance nonprecious HER electrocatalysts derived from MOFs.

Protic ionic liquid modified electrocatalyst enables robust anode under cell reversal condition

NASA Astrophysics Data System (ADS)

Zhu, Zhengyu; Yan, Xiaocong; Tang, Haolin; Cai, Haopeng; Pan, Mu; Zhang, Haining; Luo, Jiangshui

2017-05-01

Pt/C has been commercially used as anode electrocatalyst for fuel cells but generally exhibits limited durability under conditions of fuel starvation and subsequent cell reversal. Herein we report an improved scaffold concept to simultaneously stabilize the catalyst against particle growth and reduce the adverse effects of cell reversal by modifying Pt/C with suitable protic ionic liquids (PILs). The modified Pt/C catalysts show enhanced cell reversal tolerance because of their high activity towards oxygen evolution reaction (OER), up to 300 mV lower overpotential compared to the unmodified Pt/C. Moreover, the PIL modified catalysts show better resistance to the loss of electrochemical surface area (ECSA) under simulated cell reversal conditions. The results indicate that modification of Pt/C catalysts with PILs is a promising strategy to enhance the stability and durability of electrocatalysts in fuel cell applications with the risk of frequent fuel starvation events, such as automotive fuel cells.

Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Zhang, Jie; Chen, Jinwei; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin

2016-12-01

This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe3C and Co3C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe3C, and Co3C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

High-Efficiency Co/CoxSy@S,N-Codoped Porous Carbon Electrocatalysts Fabricated from Controllably Grown Sulfur- and Nitrogen-Including Cobalt-Based MOFs for Rechargeable Zinc-Air Batteries.

PubMed

Liu, Shengwen; Zhang, Xian; Wang, Guozhong; Zhang, Yunxia; Zhang, Haimin

2017-10-04

Developing bifunctional oxygen electrocatalysts with superior catalytic activities of oxygen reduction reaction (ORR) and oxygen revolution reaction (OER) is crucial to their practical energy storage and conversion applications. In this work, we report the fabrication of Co/Co x S y @S,N-codoped porous carbon structures with various morphologies, specific surface areas, and pore structures, derived from controllably grown Co-based metal-organic frameworks with S- and N-containing organic ligands (thiophene-2,5-dicarboxylate, Tdc; and 4,4'-bipyridine, bpy) utilizing solvent effect (e.g., water and methanol) under room temperature and hydrothermal conditions. The results demonstrate that Co/Co x S y @S,N-codoped carbon fibers fabricated at a pyrolytic temperature of 800 °C (Co/Co x S y @SNCF-800) from Co-MOFs fibers fabricated in methanol under hydrothermal conditions as electrocatalysts exhibit superior bifunctional ORR and OER activities in alkaline media, endowing them as air cathodic catalysts in rechargeable zinc-air batteries with high power density and good durability.

Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof

DOEpatents

Adzic, Radoslav; Zhang, Junliang

2010-04-27

The invention relates to gold-coated particles useful as fuel cell electrocatalysts. The particles are composed of an electrocatalytically active core at least partially encapsulated by an outer shell of gold or gold alloy. The invention more particularly relates to such particles having a noble metal-containing core, and more particularly, a platinum or platinum alloy core. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

Synthesis and Catalytic Activity of Pt Monolayer on Pd Tetrahedral Nanocrystals with CO-adsorption-induced Removal of Surfactants

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

Gong K.; Vukmirovic M.B.; Ma C.

2011-11-01

We synthesized the Pt monolayer shell-Pd tetrahedral core electrocatalysts that are notable for their high activity and stable performance. A small number of low-coordination sites and defects, and high content of the (1 1 1)-oriented facets on Pd tetrahedron makes them a suitable support for a Pt monolayer to obtain an active O{sub 2} reduction reaction (ORR) electrocatalyst. The surfactants, used to control size and shape of Pd tetrahedral nanoparticles, are difficult to remove and cause adverse effects on the ORR. We describe a simple and noninvasive method to synthesize high-purity tetrahedral Pd nanocrystals (TH Pd) by combining a hydrothermalmore » route and CO adsorption-induced removal of surfactants. Poly(vinylpyrrolidone) (PVP), used as a protecting and reducing agent in hydrothermal reactions, is strongly bonded to the surface of the resulting nanocrystals. We demonstrate that PVP was displaced efficiently by adsorbed CO. A clean surface was achieved upon CO stripping at a high potential (1.0 V vs RHE). It played a decisive role in improving the activity of the Pt monolayer/TH Pd electrocatalyst for the ORR. Furthermore, the results demonstrate a versatile method for removal of surfactants from various nanoparticles that severely limited their applications.« less

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

DOE PAGES

Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph; ...

2017-05-08

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolyzers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using Density Functional Theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that aremore » tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. Finally, the results suggest design principles for a new class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.« less

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

NASA Astrophysics Data System (ADS)

Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph; Markovic, Nenad M.; Greeley, Jeffrey

2017-06-01

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolysers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using density functional theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that are tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. The results suggest design principles for this class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.

Facile synthesis of sewage sludge-derived in-situ multi-doped nanoporous carbon material for electrocatalytic oxygen reduction

NASA Astrophysics Data System (ADS)

Yuan, Shi-Jie; Dai, Xiao-Hu

2016-06-01

Developing efficient, low-cost, and stable carbon-based catalysts for oxygen reduction reaction (ORR) to replace the expensive platinum-based electrocatalysts remains a major challenge that hamper the practical application of fuel cells. Here, we report that N, Fe, and S co-doped nanoporous carbon material, derived via a facile one-step pyrolysis of sewage sludge, the major byproduct of wastewater treatment, can serve as an effective electrocatalyst for ORR. Except for the comparable catalytic activity with commercial 20% Pt/C via a nearly four-electron transfer pathway in both alkaline and acid medium, the as-synthesized co-doped electrocatalyst also exhibits excellent methanol crossover resistance and outstanding long-term operation stability. The organic compounds in sewage sludge act as the carbon source and the in-situ N and S dopant in the fabrication, while the inorganic compounds serve as the in-built template and the in-situ Fe dopant. Our protocol demonstrates a new approach in the economic and eco-friendly benign reuse of sewage sludge, and also provides a straightforward route for synthesizing excellent carbon-based electrocatalysts as promising candidates for ORR directly from a type of waste/pollution.

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

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

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.

We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu 1.5Mn 1.5O 4, identified by exploiting theoretical first principles calculations for ORR and OERmore » in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO 2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO 2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

Advancing semiconductor-electrocatalyst systems: application of surface transformation films and nanosphere lithography.

PubMed

Brinkert, Katharina; Richter, Matthias H; Akay, Ömer; Giersig, Michael; Fountaine, Katherine T; Lewerenz, Hans-Joachim

2018-05-24

Photoelectrochemical (PEC) cells offer the possibility of carbon-neutral solar fuel production through artificial photosynthesis. The pursued design involves technologically advanced III-V semiconductor absorbers coupled via an interfacial film to an electrocatalyst layer. These systems have been prepared by in situ surface transformations in electrochemical environments. High activity nanostructured electrocatalysts are required for an efficiently operating cell, optimized in their optical and electrical properties. We demonstrate that shadow nanosphere lithography (SNL) is an auspicious tool to systematically create three-dimensional electrocatalyst nanostructures on the semiconductor photoelectrode through controlling their morphology and optical properties. First results are demonstrated by means of the photoelectrochemical production of hydrogen on p-type InP photocathodes where hitherto applied photoelectrodeposition and SNL-deposited Rh electrocatalysts are compared based on their J-V and spectroscopic behavior. We show that smaller polystyrene particle masks achieve higher defect nanostructures of rhodium on the photoelectrode which leads to a higher catalytic activity and larger short circuit currents. Structural analyses including HRSEM and the analysis of the photoelectrode surface composition by using photoelectron spectroscopy support and complement the photoelectrochemical observations. The optical performance is further compared to theoretical models of the nanostructured photoelectrodes on light scattering and propagation.

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

DOE PAGES

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; ...

2016-07-06

We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu 1.5Mn 1.5O 4, identified by exploiting theoretical first principles calculations for ORR and OERmore » in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO 2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO 2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

PubMed Central

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

2016-01-01

Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

NASA Astrophysics Data System (ADS)

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

2016-07-01

Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts.

PubMed

Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S; Kumta, Prashant N

2016-07-06

Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

Amine-Modulated/Engineered Interfaces of NiMo Electrocatalysts for Improved Hydrogen Evolution Reaction in Alkaline Solutions.

PubMed

Gao, Wei; Gou, Wangyan; Zhou, Xuemei; Ho, Johnny C; Ma, Yuanyuan; Qu, Yongquan

2018-01-17

The interface between electrolytes and electrocatalysts would largely determine their corresponding activity and stability. Herein, modulating the surface characteristics of NiMo nanoparticles by various adsorbed amines gives the tunability on their interfacial properties and subsequently improves their catalytic performance for hydrogen evolution reaction (HER) in alkaline solutions. Diamines can significantly improve their HER activity by decreasing the charge-transfer resistance and modulating the electronic structures of interfacial active sites. Importantly, among various amines, ethylenediamine facilitates the HER activity of NiMo with a remarkable decrease of 268 mV in the overpotential to reach 10 mA cm -2 as compared with that of the unmodified NiMo in 1.0 M KOH. This method provides a novel strategy of regulating the interfacial properties to strengthen the catalytic performance of electrocatalysts.

Heteroatom (P, B, or S) incorporated NiFe-based nanocubes as efficient electrocatalysts for the oxygen evolution reaction

DOE PAGES

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

2018-03-21

Exploring low-cost and highly efficient electrocatalysts toward the oxygen evolution reaction (OER) is of significant importance, although facing great challenges for sustainable energy systems. In this study, amorphous NiFe-based porous nanocubes (Ni–Fe–O–P, Ni–Fe–O–B, and Ni–Fe–O–S) are successfully synthesized via simple and cost-effective one-step calcination of Ni–Fe based metal–organic frameworks (MOFs) and heteroatom containing molecules. The resulting three materials maintain a well-defined porous nanocube morphology with heteroatoms uniformly distributed in the structure. The unique porous structure can effectively provide more active sites and shorten the mass transport distance. Additionally, the introduction of P, B or S can tune the electronic structure,more » which is favorable for accelerating the charge transfer, and may lead to the formation of the higher average oxidative valence of Ni species during the OER process. Benefiting from the above desirable properties, all three materials exhibit excellent OER electrocatalytic activities and outstanding long-term stability in a home-made zinc air battery. Lastly, this work not only provides a general approach for the synthesis of highly efficient electrocatalysts based on earth-abundant elements but also highlights the potential prospects of MOFs in energy conversion and storage devices.« less

Heteroatom (P, B, or S) incorporated NiFe-based nanocubes as efficient electrocatalysts for the oxygen evolution reaction

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

Xuan, Cuijuan; Wang, Jie; Xia, Weiwei

Exploring low-cost and highly efficient electrocatalysts toward the oxygen evolution reaction (OER) is of significant importance, although facing great challenges for sustainable energy systems. In this study, amorphous NiFe-based porous nanocubes (Ni–Fe–O–P, Ni–Fe–O–B, and Ni–Fe–O–S) are successfully synthesized via simple and cost-effective one-step calcination of Ni–Fe based metal–organic frameworks (MOFs) and heteroatom containing molecules. The resulting three materials maintain a well-defined porous nanocube morphology with heteroatoms uniformly distributed in the structure. The unique porous structure can effectively provide more active sites and shorten the mass transport distance. Additionally, the introduction of P, B or S can tune the electronic structure,more » which is favorable for accelerating the charge transfer, and may lead to the formation of the higher average oxidative valence of Ni species during the OER process. Benefiting from the above desirable properties, all three materials exhibit excellent OER electrocatalytic activities and outstanding long-term stability in a home-made zinc air battery. Lastly, this work not only provides a general approach for the synthesis of highly efficient electrocatalysts based on earth-abundant elements but also highlights the potential prospects of MOFs in energy conversion and storage devices.« less

Ancient Chemistry "Pharaoh's Snakes" for Efficient Fe-/N-Doped Carbon Electrocatalysts.

PubMed

Ren, Guangyuan; Gao, Liangliang; Teng, Chao; Li, Yunan; Yang, Hequn; Shui, Jianglan; Lu, Xianyong; Zhu, Ying; Dai, Liming

2018-04-04

The method of fabricating nonprecious metal electrocatalysts with high activity and durability through a facile and eco-friendly procedure is of great significance to the development of low-cost fuel cells and metal-air batteries. Herein, we present that an ancient chemical reaction of "Pharaoh's snakes" can be a fast and convenient technique to prepare Fe-/N-doped carbon (Fe/N-C) nanosheet/nanotube electrocatalysts with sugar, soda, melamine, and iron nitrate as precursors. The resultant Fe/N-C catalyst has a hierarchically porous structure, a large surface area, and uniformly distributed active sites. The catalyst shows high electrocatalytic activities toward both the oxygen reduction reaction with a half-wave potential of 0.90 V (vs reversible hydrogen electrode) better than that of Pt/C and the oxygen evolution reaction with an overpotential of 0.46 V at the current density of 10 mA cm -2 comparable to that of RuO 2 . The activity and stability of the catalyst are also evaluated in primary and rechargeable Zn-air batteries. In both conditions, three-dimensional Fe/N-C exhibited performances superior to Pt/C. Our work demonstrates a success of utilizing an ancient science to make a state-of-the-art electrocatalyst.

Two-Dimensional MoS2 Confined Co(OH)2 Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes.

PubMed

Luo, Yuting; Li, Xu; Cai, Xingke; Zou, Xiaolong; Kang, Feiyu; Cheng, Hui-Ming; Liu, Bilu

2018-05-22

The development of abundant and cheap electrocatalysts for the hydrogen evolution reaction (HER) has attracted increasing attention over recent years. However, to achieve low-cost HER electrocatalysis, especially in alkaline media, is still a big challenge due to the sluggish water dissociation kinetics as well as the poor long-term stability of catalysts. In this paper we report the design and synthesis of a two-dimensional (2D) MoS 2 confined Co(OH) 2 nanoparticle electrocatalyst, which accelerates water dissociation and exhibits good durability in alkaline solutions, leading to significant improvement in HER performance. A two-step method was used to synthesize the electrocatalyst, starting with the lithium intercalation of exfoliated MoS 2 nanosheets followed by Co 2+ exchange in alkaline media to form MoS 2 intercalated with Co(OH) 2 nanoparticles (denoted Co-Ex-MoS 2 ), which was fully characterized by spectroscopic studies. Electrochemical tests indicated that the electrocatalyst exhibits superior HER activity and excellent stability, with an onset overpotential and Tafel slope as low as 15 mV and 53 mV dec -1 , respectively, which are among the best values reported so far for the Pt-free HER in alkaline media. Furthermore, density functional theory calculations show that the cojoint roles of Co(OH) 2 nanoparticles and MoS 2 nanosheets result in the excellent activity of the Co-Ex-MoS 2 electrocatalyst, and the good stability is attributed to the confinement of the Co(OH) 2 nanoparticles. This work provides an imporant strategy for designing HER electrocatalysts in alkaline solutions, and can, in principle, be expanded to other materials besides the Co(OH) 2 and MoS 2 used here.

Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction

NASA Astrophysics Data System (ADS)

Yang, Hong Bin; Hung, Sung-Fu; Liu, Song; Yuan, Kaidi; Miao, Shu; Zhang, Liping; Huang, Xiang; Wang, Hsin-Yi; Cai, Weizheng; Chen, Rong; Gao, Jiajian; Yang, Xiaofeng; Chen, Wei; Huang, Yanqiang; Chen, Hao Ming; Li, Chang Ming; Zhang, Tao; Liu, Bin

2018-02-01

Electrochemical reduction of CO2 to chemical fuel offers a promising strategy for managing the global carbon balance, but presents challenges for chemistry due to the lack of effective electrocatalyst. Here we report atomically dispersed nickel on nitrogenated graphene as an efficient and durable electrocatalyst for CO2 reduction. Based on operando X-ray absorption and photoelectron spectroscopy measurements, the monovalent Ni(i) atomic center with a d9 electronic configuration was identified as the catalytically active site. The single-Ni-atom catalyst exhibits high intrinsic CO2 reduction activity, reaching a specific current of 350 A gcatalyst-1 and turnover frequency of 14,800 h-1 at a mild overpotential of 0.61 V for CO conversion with 97% Faradaic efficiency. The catalyst maintained 98% of its initial activity after 100 h of continuous reaction at CO formation current densities as high as 22 mA cm-2.

Iron carbide encapsulated by porous carbon nitride as bifunctional electrocatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Wei, Liangqin; Sun, Hongdi; Yang, Tiantian; Deng, Shenzhen; Wu, Mingbo; Li, Zhongtao

2018-05-01

Herein, the study reports a facile and scale-up able strategy to synthesize metal organic frameworks (MOFs) Fe-7,7,8,8-Tetracyanoquinodimethane (Fe-TCNQ) as precursors to develop non-precious metal bifunctional electrocatalysts through a one-step hydrothermal route. Then, Fe3C/carbon nitride (Fe3C@CNx) core-shell structure composites are readily available through pyrolyzing Fe-TCNQ at reasonable temperature, during which hierarchical porous structures with multimodal porosity formed. Nitrogen doped porosity carbon layers can facilitate mass access to active sites and accelerate reaction. Consequently, the optimized catalyst exhibits superior oxygen reduction reaction (ORR) electrocatalytic activity and better catalytic activity for oxygen evolution reaction (OER) in alkaline medium than that of Pt/C, which can be attributed to the synergistic effect of strong coupling between Fe3C and nitrogen doped carbon shells, active sites Fe-NX, optimal level of nitrogen doping, and appropriate multimodal porosity.

Modified Graphene as Electrocatalyst towards Oxygen Reduction Reaction for Fuel Cells

NASA Astrophysics Data System (ADS)

Qazzazie, D.; Beckert, M.; Mülhaupt, R.; Yurchenko, O.; Urban, G.

2014-11-01

This paper reports modified graphene-based materials as metal-free electrocatalysts for oxygen reduction reaction (ORR) with outstanding electrocatalytic activity in alkaline conditions. Nitrogen-doped graphene samples are synthesized by a novel procedure. The defect density in the structure of the prepared materials is investigated by Raman spectroscopy. Further structural characterization by X-ray photoelectron spectroscopy reveals the successful nitrogen doping of graphene. The electrochemical characterization of graphene and nitrogen-doped graphene in 0.1 M KOH solution demonstrates the material's electrocatalytic activity towards ORR. For graphene an onset potential of - 0.175 V vs. Ag/AgCl reference electrode is determined, while for nitrogen-doped graphene the determined onset potential is - 0.160 V. Thus, the electrocatalytic activity of nitrogen-doped graphene towards ORR is enhanced which can be ascribed to the effect of nitrogen doping.

Structure-Activity Relationships for Pt-Free Metal Phosphide Hydrogen Evolution Electrocatalysts.

PubMed

Owens-Baird, Bryan; Kolen'ko, Yury V; Kovnir, Kirill

2018-05-23

In the field of renewable energy, the splitting of water into hydrogen and oxygen fuel gases using water electrolysis is a prominent topic. Traditionally, these catalytic processes have been performed by platinum-group metal catalysts, which are effective at promoting water electrolysis but expensive and rare. The search for an inexpensive and Earth-abundant catalyst has led to the development of 3d-transition-metal phosphides for the hydrogen evolution reaction. These catalysts have shown excellent activity and stability. In this review, we discuss the electronic and crystal structures of bulk and surface of selected Fe, Co, and Ni phosphides, and their relationships to the experimental catalytic activity. The various synthetic protocols towards the state-of-the-art transition metal phosphide electrocatalysts are also discussed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

DOE PAGES

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.; ...

2017-05-02

Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for the imminentmore » commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo - TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. Furthermore, the ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

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

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.

Abstract Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for themore » imminent commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo—TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. The ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Best Practices and Testing Protocols for Benchmarking ORR Activities of Fuel Cell Electrocatalysts Using Rotating Disk Electrode

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

Kocha, Shyam S.; Shinozaki, Kazuma; Zack, Jason W.

Thin-film-rotating disk electrodes (TF-RDEs) are the half-cell electrochemical system of choice for rapid screening of oxygen reduction reaction (ORR) activity of novel Pt supported on carbon black supports (Pt/C) electrocatalysts. It has been shown that the magnitude of the measured ORR activity and reproducibility are highly dependent on the system cleanliness, evaluation protocols, and operating conditions as well as ink formulation, composition, film drying, and the resultant film thickness and uniformity. Accurate benchmarks of baseline Pt/C catalysts evaluated using standardized protocols and best practices are necessary to expedite ultra-low-platinum group metal (PGM) catalyst development that is crucial for the imminentmore » commercialization of fuel cell vehicles. We report results of evaluation in three independent laboratories of Pt/C electrocatalysts provided by commercial fuel cell catalyst manufacturers (Johnson Matthey, Umicore, Tanaka Kikinzoku Kogyo - TKK). The studies were conducted using identical evaluation protocols/ink formulation/film fabrication albeit employing unique electrochemical cell designs specific to each laboratory. Furthermore, the ORR activities reported in this work provide a baseline and criteria for selection and scale-up of novel high activity ORR electrocatalysts for implementation in proton exchange membrane fuel cells (PEMFCs).« less

Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

PubMed

Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

2016-05-17

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±δ/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.

Monodisperse Ultrasmall Manganese-Doped Multimetallic Oxysulfide Nanoparticles as Highly Efficient Oxygen Reduction Electrocatalyst.

PubMed

Zhang, Yingying; Wang, Xiang; Hu, Dandan; Xue, Chaozhuang; Wang, Wei; Yang, Huajun; Li, Dongsheng; Wu, Tao

2018-04-25

The highly efficient and cheap non-Pt-based electrocatalysts such as transition-based catalysts prepared via facile methods for oxygen reduction reaction (ORR) are desirable for large-scale practical industry applications in energy conversion and storage systems. Herein, we report a straightforward top-down synthesis of monodisperse ultrasmall manganese-doped multimetallic (ZnGe) oxysulfide nanoparticles (NPs) as an efficient ORR electrocatalyst by simple ultrasonic treatment of the Mn-doped Zn-Ge-S chalcogenidometalate crystal precursors in H 2 O/EtOH for only 1 h at room temperature. Thus obtained ultrasmall monodisperse Mn-doped oxysulfide NPs with ultralow Mn loading level (3.92 wt %) not only exhibit comparable onset and half-wave potential (0.92 and 0.86 V vs reversible hydrogen electrode, respectively) to the commercial 20 wt % Pt/C but also exceptionally high metal mass activity (189 mA/mg at 0.8 V) and good methanol tolerance. A combination of transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and electrochemical analysis demonstrated that the homogenous distribution of a large amount of Mn(III) on the surface of NPs mainly accounts for the high ORR activity. We believe that this simple synthesis of Mn-doped multimetallic (ZnGe) oxysulfide NPs derived from chalcogenidometalates will open a new route to explore the utilization of discrete-cluster-based chalcogenidometalates as novel non-Pt electrocatalysts for energy applications and provide a facile way to realize the effective reduction of the amount of catalyst while keeping desired catalytic performances.

A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Xu, Jingjing; Lu, Shiyao; Chen, Xu; Wang, Jianan; Zhang, Bo; Zhang, Xinyu; Xiao, Chunhui; Ding, Shujiang

2017-12-01

Investigating low-cost and highly active electrocatalysts for oxygen reduction reactions (ORR) is of crucial importance for energy conversion and storage devices. Herein, we design and prepare mesoporous carbon supported nitrogen-doped carbon by pyrolysis of polyaniline coated on CMK-3. This electrocatalyst exhibits excellent performance towards ORR in alkaline media. The optimized nitrogen-doped mesoporous electrocatalyst show an onset potential (E onset) of 0.95 V (versus reversible hydrogen electrode (RHE)) and half-wave potential (E 1/2) of 0.83 V (versus RHE) in 0.1 M KOH. Furthermore, the as-prepared catalyst presents superior durability and methanol tolerance compared to commercial Pt/C indicating its potential applications in fuel cells and metal-air batteries.

Nanostructured electrocatalysts with tunable activity and selectivity

NASA Astrophysics Data System (ADS)

Mistry, Hemma; Varela, Ana Sofia; Kühl, Stefanie; Strasser, Peter; Cuenya, Beatriz Roldan

2016-04-01

The field of electrocatalysis has undergone tremendous advancement in the past few decades, in part owing to improvements in catalyst design at the nanoscale. These developments have been crucial for the realization of and improvement in alternative energy technologies based on electrochemical reactions such as fuel cells. Through the development of novel synthesis methods, characterization techniques and theoretical methods, rationally designed nanoscale electrocatalysts with tunable activity and selectivity have been achieved. This Review explores how nanostructures can be used to control electrochemical reactivity, focusing on three model reactions: O2 electroreduction, CO2 electroreduction and ethanol electrooxidation. The mechanisms behind nanoscale control of reactivity are discussed, such as the presence of low-coordinated sites or facets, strain, ligand effects and bifunctional effects in multimetallic materials. In particular, studies of how particle size, shape and composition in nanostructures can be used to tune reactivity are highlighted.

Electrocatalytic Metal-Organic Frameworks for Energy Applications.

PubMed

Downes, Courtney A; Marinescu, Smaranda C

2017-11-23

With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal-organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best-performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble-metal-based catalysts in commercial energy-converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy-related reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen reduction reaction (ORR) on mixed oxy-nitride non-noble catalyst: Ab-initio simulation, elaboration and characterization

NASA Astrophysics Data System (ADS)

Seifitokaldani, Ali

In this project, titanium oxy-nitride (TiOxN y) has been studied as a new non-noble electrocatalyst for the oxygen reduction reaction (ORR). A comprehensive comparison between four different sol-gel methods was carried out to evaluate the physicochemical and electrochemical properties of the produced electro-catalysts. Among them, a new urea-based sol-gel method (simply called U method) is introduced to prepare TiOxNy at a fairly low temperature and duration, with higher electro-catalytic activity for the ORR. The prepared electro-catalysts with different N/O ratios showed different properties from a less conductive behavior in oxygen-rich (low N/O ratio) materials to more conductive electro-catalyst behavior in nitrogen-rich (high N/O ratio) oxy-nitrides, respectively. Generally, electro-catalysts prepared by the U method had more titanium nitride in their structures than the electro-catalysts prepared by the other methods. Nevertheless, heat treatment had a key role in this phase transferring from having high oxide structure to high nitride structure. According to the elemental analysis done by energy dispersive spectroscopy (EDS), nitrogen percentage in the bulk material increased from 9 to 24 percent by increasing the temperature from 700 to 1100 °C, while the oxygen percentage was decreasing inversely. In addition, based on the X-ray diffraction (XRD) data, in the case of U method, the TiN characteristic peaks were obvious, even at lower temperatures. Increasing the temperature also made the peaks much sharper indicating the growth of the crystallite size. The calculated crystallite size showed the crystallite size of samples prepared by U method (20 to 40 nm) was almost in the same range of the TiN crystallite size, but the crystallite size of the samples prepared by the other sol-gel methods (40 to 60 nm) was in the same range of the TiO2 crystallite size. Scanning electron microscopy (SEM) and B.E.T. surface area analyzer were used to evaluate the particle size and surface area of different samples, respectively. They indicated a smaller particle size and a higher surface area in the electro-catalysts produced by the U method. Besides the aforementioned physicochemical characterizations, cyclic voltammetry (CV), polarization, and electrochemical impedance spectroscopy (EIS) were used to evaluate the electrochemical properties of the electro-catalysts. Obtained Tafel slope, exchange current density and onset potential revealed that the electro-catalyst prepared by the U method which was annealed at 1100 °C, had the best electro-catalytic activity among all other samples with Tafel slope of -203 mV/decade, exchange current density around 4E-04 mA/mg and the onset potential close to 0.8 volt vs. NHE (normal hydrogen electrode). EIS measurements also supported this assertion through revealing the highest specific capacitance (˜ 3.3 F/g). This result was in agreement with the highest B.E.T. surface area and the lowest charge transfer resistance exhibited by this electro-catalyst among the other samples. Stability is one of the determinant factors in selecting an electro-catalyst for the ORR. In this regard, ICP-TOF-MS was used to evaluate the chemical stability of the prepared electro-catalysts under corrosive acidic environment, by measuring the concentration of the dissolved titanium after a certain time. Heretofore, measuring the dissolved metal concentration by ICP-TOF-MS was done just to evaluate its chemical stability. However, in this project this technique was also used during the CV, to evaluate the electro-catalyst's electrochemical stability as well, which is more realistic and similar to the PEMFC's working condition. Stability of the best electrocatalyst with the highest catalytic activity (prepared by the U method) was better than the commercially used Pt/C electro-catalyst, both chemically and electrochemically. Electrochemical stability of the prepared electro-catalysts has also been studied at a high oxidizing potential (more than 2 volts vs. NHE). X-ray Photoelectron Spectroscopy (XPS) showed that the nitrogen amount on the surface of the electro-catalyst decreased from 11 % before the oxidation to 5 % after the oxidation, whereas the catalytic activity for the ORR decreased after the oxidation. Thus, decreasing the titanium nitride's amount in the titanium oxy-nitride surface reduced its catalytic activity. In the second phase of this project, electro-catalytic activity of the titanium nitride for the ORR was investigated via a density functional theory (DFT) computation. To the best of our knowledge, there is no theoretical and computational quantum chemistry study of the transition metal's nitride as the electro-catalyst in PEM fuel cells. ORR was considered to take place in three different sequential steps namely oxygen adsorption, hydroxide production and water desorption. Based on the XRD results, TiN(111) and TiN(200) were considered as the two major facets of the TiN. Simulation was done by the Vienna ab initio Simulation Package (VASP) based on the Plane-Wave basis sets and periodic boundary condition, while the PBE exchangecorrelational functional was used to describe the interactions among electrons. Comparing the adsorption energies proved existence of a strong dissociative adsorption of oxygen on the TiN(111) regardless of the adsorption sites. However, because of a relatively strong OH adsorption, TiN(111) loses the active sites to proceed the ORR, while on the TiN(200) surface, water production and desorption came about easily. Electron density of states (DOS) was obtained to calculate the d-band center and fractional filling in different situations. Considering two possible bridge and top adsorption sites on the TiN(200), these information indicated the hydroxide production and water desorption as the rate determining steps for the ORR in bridge and top sites, respectively. Therefore, it was shown that the TiN, specially TiN(200) had exhibited good electro-catalytic activity for the ORR. Losing this TiN amount from the titanium oxy-nitride's surface might be responsible for the decrease of the electro-catalytic activity of the titanium oxy-nitride for the ORR.

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

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

Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.

2017-03-06

NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast,more » absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.« less

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry.

PubMed

Goldsmith, Zachary K; Harshan, Aparna K; Gerken, James B; Vörös, Márton; Galli, Giulia; Stahl, Shannon S; Hammes-Schiffer, Sharon

2017-03-21

NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni 2+ to Ni 3+ , followed by oxidation to a mixed Ni 3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fe-doped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe 4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixed-metal oxidation states in heterogeneous catalysts.

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

PubMed Central

Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.; Galli, Giulia; Stahl, Shannon S.

2017-01-01

NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni2+ to Ni3+, followed by oxidation to a mixed Ni3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fe-doped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixed-metal oxidation states in heterogeneous catalysts. PMID:28265083

Effect of Chloride Anions on the Synthesis and Enhanced Catalytic Activity of Silver Nanocoral Electrodes for CO 2 Electroreduction

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

Hsieh, Yu-Chi; Senanayake, Sanjaya D.; Zhang, Yu

2015-09-04

Metallic silver (Ag) is known as an efficient electrocatalyst for the conversion of carbon dioxide (CO 2) to carbon monoxide (CO) in aqueous or nonaqueous electrolytes. However, polycrystalline silver electrocatalysts require significant overpotentials in order to achieve high selectivity toward CO 2 reduction, as compared to the side reaction of hydrogen evolution. Here we report a high-surface-area Ag nanocoral catalyst, fabricated by an oxidation–reduction method in the presence of chloride anions in an aqueous medium, for the electro-reduction of CO 2 to CO with a current efficiency of 95% at the low overpotential of 0.37 V and the current densitymore » of 2 mA cm –2. A lower limit of TOF of 0.4 s –1 and TON > 8.8 × 10 4 (over 72 h) was estimated for the Ag nanocoral catalyst at an overpotential of 0.49 V. The Ag nanocoral catalyst demonstrated a 32-fold enhancement in surface-area-normalized activity, at an overpotential of 0.49 V, as compared to Ag foil. We found that, in addition to the effect on nanomorphology, the adsorbed chloride anions play a critical role in the observed enhanced activity and selectivity of the Ag nanocoral electrocatalyst toward CO 2 reduction. Synchrotron X-ray photoelectron spectroscopy (XPS) studies along with a series of control experiments suggest that the chloride anions, remaining adsorbed on the catalyst surface under electrocatalytic conditions, can effectively inhibit the side reaction of hydrogen evolution and enhance the catalytic performance for CO 2 reduction.« less

Ternary mixed metal Fe-doped NiCo2O4 nanowires as efficient electrocatalysts for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Yan, Kai-Li; Shang, Xiao; Li, Zhen; Dong, Bin; Li, Xiao; Gao, Wen-Kun; Chi, Jing-Qi; Chai, Yong-Ming; Liu, Chen-Guang

2017-09-01

Designing mixed metal oxides with unique nanostructures as efficient electrocatalysts for water electrolysis has been an attractive approach for the storage of renewable energies. The ternary mixed metal spinel oxides FexNi1-xCo2O4 (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, 1) have been synthesized by a facile hydrothermal approach and calcination treatment using nickel foam as substrate. Fe/Ni ratios have been proved to affect the nanostructures of FexNi1-xCo2O, which imply different intrinsic activity for oxygen evolution reaction (OER). SEM images show that Fe0.5Ni0.5Co2O4 has the uniform nanowires morphology with about 30 nm of the diameter and 200-300 nm of the length. The OER measurements show that Fe0.5Ni0.5Co2O4 exhibits the better electrocatalytic performances with lower overpotential of 350 mV at J = 10 mA cm-2. In addition, the smaller Tafel slope of 27 mV dec-1 than other samples with different Fe/Ni ratios for Fe0.5Ni0.5Co2O4 is obtained. The improved OER activity of Fe0.5Ni0.5Co2O4 may be attributed to the synergistic effects from ternary mixed metals especially Fe-doping and the uniform nanowires supported on NF. Therefore, synthesizing Fe-doped multi-metal oxides with novel nanostructures may be a promising strategy for excellent OER electrocatalysts and it also provides a facile way for the fabrication of high-activity ternary mixed metal oxides electrocatalysts.

Hierarchically structured graphene-carbon nanotube-cobalt hybrid electrocatalyst for seawater battery

NASA Astrophysics Data System (ADS)

Suh, Dong Hoon; Park, Sul Ki; Nakhanivej, Puritut; Kim, Youngsik; Hwang, Soo Min; Park, Ho Seok

2017-12-01

The design of cost-effective and highly active catalysts is a critical challenge. Inspired by the strong points of stability and conductivity of carbon nanotubes (CNTs), high catalytic activity of Co nanoparticles, and rapid ion diffusion and large accessible area of three-dimensional (3D) graphene, we demonstrate a novel strategy to construct a hierarchical hybrid structure consisting of Co/CoOx nanoparticles-incorporated CNT branches onto the 3D reduced graphene oxide (rGO) architecture. The surface-modified 3D rGO by steam activation process has a large surface area and abundant defect sites, which serve as active sites to uniformly grow Co/CoOx nanoparticles. Furthermore, the CNTs preserve their performance stably by encapsulating Co nanoparticles, while the uniformly decorated Co/CoOx nanoparticles exhibit superior electrocatalytic activity toward oxygen evolution/reduction reaction due to highly exposed active sites. Employing the hybrid particle electrocatalyst, the seawater battery operates stably at 0.01 mA cm-2 during 50 cycles, owing to the good electrocatalytic ability.

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.

Solvent effect in sonochemical synthesis of metal-alloy nanoparticles for use as electrocatalysts

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

Okoli, Celest U.; Kuttiyiel, Kurian A.; Cole, Jesse

Nanomaterials are now widely used in the fabrication of electrodes and electrocatalysts. In this paper, we report a sonochemical study of the synthesis of molybdenum and palladium alloy nanomaterials supported on functionalized carbon material in various solvents: hexadecane, ethanol, ethylene glycol, polyethylene glycol (PEG 400) and Ionic liquids (ILs). The objective was to identify simple and more environmentally friendly design and fabrication methods for nanomaterial synthesis that are suitable as electrocatalysts in electrochemical applications. The particles size and distribution of nanomaterials were compared on two different carbons as supports: activated carbon and multiwall carbon nanotubes (MWCNTs). The results show thatmore » carbon materials functionalized with ILs in ethanol/deionized water mixture solvent produced smaller particles sizes (3.00 ± 0.05 nm) with uniform distribution while in PEG 400, functionalized materials produced 4.00 ± 1 nm sized particles with uneven distribution (range). In hexadecane solvents with Polyvinylpyrrolidone (PVP) as capping ligands, large particle sizes (14.00 ± 1 nm) were produced with wide particle size distribution. Finally, the metal alloy nanoparticles produced in ILs without any external reducing agent have potential to exhibit a higher catalytic activity due to smaller particle size and uniform distribution.« less

Tension-Enhanced Hydrogen Evolution Reaction on Vanadium Disulfide Monolayer

NASA Astrophysics Data System (ADS)

Pan, Hui

2016-02-01

Water electrolysis is an efficient way for hydrogen production. Finding efficient, cheap, and eco-friendly electrocatalysts is essential to the development of this technology. In the work, we present a first-principles study on the effects of tension on the hydrogen evolution reaction of a novel electrocatalyst, vanadium disulfide (VS2) monolayer. Two electrocatalytic processes, individual and collective processes, are investigated. We show that the catalytic ability of VS2 monolayer at higher hydrogen coverage can be efficiently improved by escalating tension. We find that the individual process is easier to occur in a wide range of hydrogen coverage and the collective process is possible at a certain hydrogen coverage under the same tension. The best hydrogen evolution reaction with near-zero Gibbs free energy can be achieved by tuning tension. We further show that the change of catalytic activity with tension and hydrogen coverage is induced by the change of free carrier density around the Fermi level, that is, higher carrier density, better catalytic performance. It is expected that tension can be a simple way to improve the catalytic activity, leading to the design of novel electrocatalysts for efficient hydrogen production from water electrolysis.

Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

PubMed

Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

2016-05-01

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent effect in sonochemical synthesis of metal-alloy nanoparticles for use as electrocatalysts

DOE PAGES

Okoli, Celest U.; Kuttiyiel, Kurian A.; Cole, Jesse; ...

2017-10-03

Nanomaterials are now widely used in the fabrication of electrodes and electrocatalysts. In this paper, we report a sonochemical study of the synthesis of molybdenum and palladium alloy nanomaterials supported on functionalized carbon material in various solvents: hexadecane, ethanol, ethylene glycol, polyethylene glycol (PEG 400) and Ionic liquids (ILs). The objective was to identify simple and more environmentally friendly design and fabrication methods for nanomaterial synthesis that are suitable as electrocatalysts in electrochemical applications. The particles size and distribution of nanomaterials were compared on two different carbons as supports: activated carbon and multiwall carbon nanotubes (MWCNTs). The results show thatmore » carbon materials functionalized with ILs in ethanol/deionized water mixture solvent produced smaller particles sizes (3.00 ± 0.05 nm) with uniform distribution while in PEG 400, functionalized materials produced 4.00 ± 1 nm sized particles with uneven distribution (range). In hexadecane solvents with Polyvinylpyrrolidone (PVP) as capping ligands, large particle sizes (14.00 ± 1 nm) were produced with wide particle size distribution. Finally, the metal alloy nanoparticles produced in ILs without any external reducing agent have potential to exhibit a higher catalytic activity due to smaller particle size and uniform distribution.« less

Uranium electrocatalysis: The secret is in the ring

NASA Astrophysics Data System (ADS)

Mazzanti, Marinella

2018-03-01

An arene-anchored uranium complex has recently been shown to serve as efficient electrocatalyst for the conversion of water into dihydrogen. Now, the crucial role of the arene moiety in enabling catalytic activity -- unusual for uranium -- has been explored, providing important insight for the design of improved electrocatalysts.

Hollow structured carbon-supported nickel cobaltite nanoparticles as an efficient bifunctional electrocatalyst for the oxygen reduction and evolution reaction

DOE PAGES

Wang, Jie; Han, Lili; Lin, Ruoqian; ...

2016-01-05

Here, the exploration of efficient electrocatalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is essential for fuel cells and metal-air batteries. In this study, we developed 3D hollow-structured NiCo 2O 4/C nanoparticles with interconnected pores as bifunctional electrocatalysts, which are transformed from solid NiCo 2 alloy nanoparticles through the Kirkendall effect. The unique hollow structure of NiCo 2O 4 nanoparticles increases the number of active sites and improves contact with the electrolyte to result in excellent ORR and OER performances. In addition, the hollow-structured NiCo 2O 4/C nanoparticles exhibit superior long-term stability for both themore » ORR and OER compared to commercial Pt/C. The template- and surfactant-free synthetic strategy could be used for the low-cost and large-scale synthesis of hollow-structured materials, which would facilitate the screening of high-efficiency catalysts for energy conversion.« less

How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

PubMed

Bachmeier, Andreas; Wang, Vincent C C; Woolerton, Thomas W; Bell, Sophie; Fontecilla-Camps, Juan C; Can, Mehmet; Ragsdale, Stephen W; Chaudhary, Yatendra S; Armstrong, Fraser A

2013-10-09

The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

Oxygen electrodes for rechargeable alkaline fuel cells

NASA Technical Reports Server (NTRS)

Swette, Larry; Giner, Jose

1987-01-01

Electrocatalysts and supports for the positive electrode of moderate temperature single unit rechargeable alkaline fuel cells were investigated and developed. The electrocatalysts are defined as the material with a higher activity for the oxygen electrode reaction than the support. Advanced development will require that the materials be prepared in high surface area forms, and may also entail integration of various candidate materials. Eight candidate support materials and seven electrocatalysts were investigated. Of the 8 support, 3 materials meet the preliminary requirements in terms of electrical conductivity and stability. Emphasis is now on preparing in high surface area form and testing under more severe corrosion stress conditions. Of the 7 electrocatalysts prepared and evaluated, at least 5 materials remain as potential candidates. The major emphasis remains on preparation, physical characterization and electrochemical performance testing.

Monodispersed porous flowerlike PtAu nanocrystals as effective electrocatalysts for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shumin; Xu, Hui; Xiong, Zhiping; Zhang, Ke; Wang, Caiqin; Yan, Bo; Guo, Jun; Du, Yukou

2017-11-01

Designing and tuning the bimetallic nanoparticles with desirable morphology and structure can embody them with greatly enhanced electrocatalytic activity and stability towards liquid fuel oxidation. We herein reported a facile one-pot method for the controlled synthesis of monodispersed binary PtAu nanoflowers with abundant exposed surface area. Owing to its fantastic structure, synergistic and electronic effect, such as-prepared PtAu nanoflowers exhibited outstandingly high electrocatalytic activity with the mass activity of 6482 mA mg-1 towards ethanol oxidation, which is 28.3 times higher than that of commercial Pt/C (227 mA mg-1). More interesting, the present PtAu nanoflower catalysts are more stable for the ethanol oxidation reaction in the alkaline with lower current density decay and retained a much higher current density after successive CVs of 500 cycles than that of commercial Pt/C. This work may open a new way for maximizing the catalytic performance of electrocatalysts towards ethanol oxidation by synthesizing shape-controlled alloy nanoparticles with more surface active sites to enhance the performances of direct fuel cells reaction, chemical conversion, and beyond.

Pt skin coated hollow Ag-Pt bimetallic nanoparticles with high catalytic activity for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Fu, Tao; Huang, Jianxing; Lai, Shaobo; Zhang, Size; Fang, Jun; Zhao, Jinbao

2017-10-01

The catalytic activity and stability of electrocatalyst is critical for the commercialization of fuel cells, and recent reports reveal the great potential of the hollow structures with Pt skin coat for developing high-powered electrocatalysts due to their highly efficient utilization of the Pt atoms. Here, we provide a novel strategy to prepare the Pt skin coated hollow Ag-Pt structure (Ag-Pt@Pt) of ∼8 nm size at room temperature. As loaded on the graphene, the Ag-Pt@Pt exhibits a remarkable mass activity of 0.864 A/mgPt (at 0.9 V, vs. reversible hydrogen electrode (RHE)) towards oxygen reduction reaction (ORR), which is 5.30 times of the commercial Pt/C catalyst, and the Ag-Pt@Pt also shows a better stability during the ORR catalytic process. The mechanism of this significant enhancement can be attributed to the higher Pt utilization and the unique Pt on Ag-Pt surface structure, which is confirmed by the density functional theory (DFT) calculations and other characterization methods. In conclusion, this original work offers a low-cost and environment-friendly method to prepare a high active electrocatalyst with cheaper price, and this work also discloses the correlation between surface structures and ORR catalytic activity for the hollow structures with Pt skin coat, which can be instructive for designing novel advanced electrocatalysts for fuel cells.

Semiconductor-Electrocatalyst Interfaces: Theory, Experiment, and Applications in Photoelectrochemical Water Splitting.

PubMed

Nellist, Michael R; Laskowski, Forrest A L; Lin, Fuding; Mills, Thomas J; Boettcher, Shannon W

2016-04-19

Light-absorbing semiconductor electrodes coated with electrocatalysts are key components of photoelectrochemical energy conversion and storage systems. Efforts to optimize these systems have been slowed by an inadequate understanding of the semiconductor-electrocatalyst (sem|cat) interface. The sem|cat interface is important because it separates and collects photoexcited charge carriers from the semiconductor. The photovoltage generated by the interface drives "uphill" photochemical reactions, such as water splitting to form hydrogen fuel. Here we describe efforts to understand the microscopic processes and materials parameters governing interfacial electron transfer between light-absorbing semiconductors, electrocatalysts, and solution. We highlight the properties of transition-metal oxyhydroxide electrocatalysts, such as Ni(Fe)OOH, because they are the fastest oxygen-evolution catalysts known in alkaline media and are (typically) permeable to electrolyte. We describe the physics that govern the charge-transfer kinetics for different interface types, and show how numerical simulations can explain the response of composite systems. Emphasis is placed on "limiting" behavior. Electrocatalysts that are permeable to electrolyte form "adaptive" junctions where the interface energetics change during operation as charge accumulates in the catalyst, but is screened locally by electrolyte ions. Electrocatalysts that are dense, and thus impermeable to electrolyte, form buried junctions where the interface physics are unchanged during operation. Experiments to directly measure the interface behavior and test the theory/simulations are challenging because conventional photoelectrochemical techniques do not measure the electrocatalyst potential during operation. We developed dual-working-electrode (DWE) photoelectrochemistry to address this limitation. A second electrode is attached to the catalyst layer to sense or control current/voltage independent from that of the semiconductor back ohmic contact. Consistent with simulations, electrolyte-permeable, redox-active catalysts such as Ni(Fe)OOH form "adaptive" junctions where the effective barrier height for electron exchange depends on the potential of the catalyst. This is in contrast to sem|cat interfaces with dense electrolyte-impermeable catalysts, such as nanocrystalline IrOx, that behave like solid-state buried (Schottky-like) junctions. These results elucidate a design principle for catalyzed photoelectrodes. The buried heterojunctions formed by dense catalysts are often limited by Fermi-level pinning and low photovoltages. Catalysts deposited by "soft" methods, such as electrodeposition, form adaptive junctions that tend to provide larger photovoltages and efficiencies. We also preview efforts to improve theory/simulations to account for the presence of surface states and discuss the prospect of carrier-selective catalyst contacts.

Preparation method of Ni@Pt/C nanocatalyst affects the performance of direct borohydride-hydrogen peroxide fuel cell: Improved power density and increased catalytic oxidation of borohydride.

PubMed

Hosseini, Mir Ghasem; Mahmoodi, Raana

2017-08-15

The Ni@Pt/C electrocatalysts were synthesized using two different methods: with sodium dodecyl sulfate (SDS) and without SDS. The metal loading in synthesized nanocatalysts was 20wt% and the molar ratio of Ni: Pt was 1:1. The structural characterizations of Ni@Pt/C electrocatalysts were investigated by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HR-TEM). The electrocatalytic activity of Ni@Pt/C electrocatalysts toward BH 4 - oxidation in alkaline medium was studied by means of cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The results showed that Ni@Pt/C electrocatalyst synthesized without SDS has superior catalytic activity toward borohydride oxidation (22016.92Ag Pt -1 ) in comparison with a catalyst prepared in the presence of SDS (17766.15Ag Pt -1 ) in NaBH 4 0.1M at 25°C. The Membrane Electrode Assembly (MEA) used in fuel cell set-up was fabricated with catalyst-coated membrane (CCM) technique. The effect of Ni@Pt/C catalysts prepared with two methods as anode catalyst on the performance of direct borohydride-hydrogen peroxide fuel cell was studied. The maximum power density was obtained using Ni@Pt/C catalyst synthesized without SDS at 60°C, 1M NaBH 4 and 2M H 2 O 2 (133.38mWcm -2 ). Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Advanced catalyst supports for PEM fuel cell cathodes

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

Du, Lei; Shao, Yuyan; Sun, Junming

2016-11-01

Electrocatalyst support materials are key components for polymer exchange membrane (PEM) fuel cells, which play a critical role in determining electrocatalyst durability and activity, mass transfer and water management. The commonly-used supports, e.g. porous carbon black, cannot meet all the requirements under the harsh operation condition of PEM fuel cells. Great efforts have been made in the last few years in developing alternative support materials. In this paper, we selectively review recent progress on three types of important support materials: carbon, non-carbon and hybrid carbon-oxides nanocomposites. A perspective on future R&D of electrocatalyst support materials is also provided.

Highly exposed Fe-N4 active sites in porous poly-iron-phthalocyanine based oxygen reduction electrocatalyst with ultrahigh performance for air cathode.

PubMed

Anandhababu, Ganesan; Abbas, Syed Comail; Lv, Jiangquan; Ding, Kui; Liu, Qin; Babu, Dickson D; Huang, Yiyin; Xie, Jiafang; Wu, Maoxiang; Wang, Yaobing

2017-02-14

Progress in the development of efficient electrocatalysts for oxygen reduction reactions is imperative for various energy systems such as metal-air batteries and fuel cells. In this paper, an innovative porous two-dimensional (2D) poly-iron-phthalocyanine (PFe-Pc) based oxygen reduction electrocatalyst created with a simple solid-state chemical reaction without pyrolysis is reported. In this strategy, silicon dioxide nanoparticles play a pivotal role in preserving the Fe-N 4 structure during the polymerization process and thereby assist in the development of a porous structure. The new polymerized phthalocyanine electrocatalyst with tuned porous structure, improved specific surface area and more exposed catalytic active sites via the 2D structure shows an excellent performance towards an oxygen reduction reaction in alkaline media. The onset potential (E = 1.033 V) and limiting current density (I = 5.58 mA cm -2 ) are much better than those obtained with the commercial 20% platinum/carbon electrocatalyst (1.046 V and 4.89 mA cm -2 ) and also show better stability and tolerance to methanol crossover. For practical applications, a zinc-air (Zn-air) battery and methanol fuel cell equipped with the PFe-Pc electrocatalyst as an air cathode reveal a high open circuit voltage and maximum power output (1.0 V and 23.6 mW cm -2 for a methanol fuel cell, and 1.6 V and 192 mW cm -2 for the liquid Zn-air battery). In addition, using the PFe-Pc electrocatalyst as an air cathode in a flexible cable-type Zn-air battery exhibits excellent performance with an open-circuit voltage of 1.409 V. This novel porous 2D PFe-Pc has been designed logically using a new, simple strategy with ultrahigh electrochemical performances in Zn-air batteries and methanol fuel cell applications.

Shaping electrocatalysis through tailored nanomaterials

DOE PAGES

Kang, Yijin; Yang, Peidong; Markovic, Nenad M.; ...

2016-09-21

Electrocatalysis is a subclass of heterogeneous catalysis that is aimed towards increase of the electrochemical reaction rates that are taking place at the surface of electrodes. Real-world electrocatalysts are usually based on precious metals in the form of nanoparticles due to their high surface-to-volume ratio, which enables better utilization of employed materials. Ability to tailor nanostructure of an electrocatalyst is critical in order to tune their electrocatalytic properties. Over the last decade, that has mainly been achieved through implementation of fundamental studies performed on well-defined extended surfaces with distinct single crystalline and polycrystalline structures. Based on these studies, it hasmore » been demonstrated that performance of an electrocatalyst could be significantly changed through the control of size, composition, morphology and architecture of employed nanomaterials. Here, this review outlines the following steps in the process of rational development of an efficient electrocatalyst: 1) electrochemical properties of well-defined surfaces, 2) synthesis and characterization of different classes of electrocatalysts, and 3) correlation between physical properties (size, shape, composition and morphology) and electrochemical behavior (adsorption, electrocatalytic activity and durability) of electrocatalyst. In addition, this is a brief summary of the novel research platforms in the development of functional nano materials for energy conversion and storage applications such as fuel cells electrolyzers and batteries.« less

Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction

NASA Astrophysics Data System (ADS)

Liang, Hai-Wei; Zhuang, Xiaodong; Brüller, Sebastian; Feng, Xinliang; Müllen, Klaus

2014-09-01

Development of efficient, low-cost and stable electrocatalysts as the alternative to platinum for the oxygen reduction reaction is of significance for many important electrochemical devices, such as fuel cells, metal-air batteries and chlor-alkali electrolysers. Here we report a highly active nitrogen-doped, carbon-based, metal-free oxygen reduction reaction electrocatalyst, prepared by a hard-templating synthesis, for which nitrogen-enriched aromatic polymers and colloidal silica are used as precursor and template, respectively, followed by ammonia activation. Our protocol allows for the simultaneous optimization of both porous structures and surface functionalities of nitrogen-doped carbons. Accordingly, the prepared catalysts show the highest oxygen reduction reaction activity (half-wave potential of 0.85 V versus reversible hydrogen electrode with a low loading of 0.1 mg cm-2) in alkaline media among all reported metal-free catalysts. Significantly, when used for constructing the air electrode of zinc-air battery, our metal-free catalyst outperforms the state-of the-art platinum-based catalyst.

Evaluation of the Optimum Composition of Low-Temperature Fuel Cell Electrocatalysts for Methanol Oxidation by Combinatorial Screening.

PubMed

Antolini, Ermete

2017-02-13

Combinatorial chemistry and high-throughput screening represent an innovative and rapid tool to prepare and evaluate a large number of new materials, saving time and expense for research and development. Considering that the activity and selectivity of catalysts depend on complex kinetic phenomena, making their development largely empirical in practice, they are prime candidates for combinatorial discovery and optimization. This review presents an overview of recent results of combinatorial screening of low-temperature fuel cell electrocatalysts for methanol oxidation. Optimum catalyst compositions obtained by combinatorial screening were compared with those of bulk catalysts, and the effect of the library geometry on the screening of catalyst composition is highlighted.

A new electrocatalyst and its application method for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wei, Guanjie; Jing, Minghua; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei

2015-08-01

The edge plane in carbon structure has good electrocatalytic activity toward vanadium redox reaction. To apply it in vanadium redox flow battery (VRFB) practically, the graphite nanopowders (GNPs) containing amounts of edge planes are used as electrocatalyst and embedded in the electrospun carbon nanofibers (ECNFs) by different mass ratios to make composite electrodes. The morphology and electrochemical activity of the GNPs and the composite electrodes containing them are characterized. Compared with the pristine ECNFs, the composite electrodes show much higher electrochemical activity. With the increase of GNPs content in composite electrodes, the electrochemical reversibility of the vanadium redox couples also increases. It proves the addition of GNPs can surely improve the electrochemical activity of ECNFs. Among the composite electrodes, the ECNFs containing 30 nm GNP by mass ratio of 1:50 show the best electrochemical activity, largest active surface area and excellent stability. Due to the high performance of GNP/ECNFs composite electrode and its relatively low cost preparation process, the GNPs are expected to be used as electrocatalyst in VRFB on a large scale to improve the cell performance.

Ordered PdCu-Based Nanoparticles as Bifunctional Oxygen-Reduction and Ethanol-Oxidation Electrocatalysts

DOE PAGES

Jiang, Kezhu; Wang, Pengtang; Guo, Shaojun; ...

2016-06-02

Here, the development of superior non-platinum electrocatalysts for enhancing the electrocatalytic activity and stability for the oxygen-reduction reaction (ORR) and liquid fuel oxidation reaction is very important for the commercialization of fuel cells,but still agreat challenge.Herein, we demonstrate a new colloidal chemistry technique for making structurally ordered PdCu-based nanoparticles (NPs) with composition control from PdCu to PdCuNi and PtCuCo.Under the dual tuning on the composition and intermetallic phase,the ordered PdCuCo NPs exhibit better activity and much enhanced stability for ORR and ethanol-oxidation reaction (EOR)than those of disordered PdCuM NPs,the commercial Pt/Cand Pd/C catalysts.The density functional theory (DFT)calculations reveal that themore » improved ORR activity on the PdCuM NPs stems from the catalytically active hollow sites arising from the ligand effect and the compressive strain on thePd surface owing to the smaller atomic size of Cu, Co,and Ni.« less

Evaluation of oxygen reduction activity by the thin-film rotating disk electrode methodology: The effects of potentiodynamic parameters

DOE PAGES

Chen, Guangyu; Li, Meng; Kuttiyiel, Kurian A.; ...

2016-04-11

Here, an accurate and efficient assessment of activity is critical for the research and development of electrocatalysts for oxygen reduction reaction (ORR). Currently, the methodology combining the thin-film rotating disk electrode (TF-RDE) and potentiodynamic polarization is the most commonly used to pre-evaluate ORR activity, acquire kinetic data (i.e., kinetic current, Tafel slope, etc.), and gain understanding of the ORR mechanism. However, it is often neglected that appropriate potentiodynamic parameters have to be chosen to obtain reliable results. We first evaluate the potentiodynamic and potentiostatic polarization measurements with TF-RDE to examine the ORR activity of Pt nanoelectrocatalyst. Furthermore, our results demonstratemore » that besides depending on the nature of electrocatalyst, the apparent ORR kinetics also strongly depends on the associated potentiodynamic parameters, such as scan rate and scan region, which have a great effect on the coverage of adsorbed OH ad/O ad on Pt surface, thereby affecting the ORR activities of both nanosized and bulk Pt. However, the apparent Tafel slopes remained nearly the same, indicating that the ORR mechanism in all the measurements was not affected by different potentiodynamic parameters.« less

Nanostructured carbon-supported Pd electrocatalysts for ethanol oxidation: synthesis and characterization

NASA Astrophysics Data System (ADS)

Gacutan, E. M.; Climaco, M. I.; Telan, G. J.; Malijan, F.; Hsu, H. Y.; Garcia, J.; Fulo, H.; Tongol, B. J.

2012-12-01

The need to lower the construction cost of fuel cells calls for the development of non-Pt based electrocatalysts. Among others, Pd has emerged as a promising alternative to Pt for fuel cell catalysis. This research aims to investigate the synthesis and characterization of nanostructured Pd-based catalysts dispersed on carbon support as anode materials in direct ethanol fuel cells. For the preparation of the first Pd-based electrocatalyst, palladium nanoparticles (NPs) were synthesized via oleylamine (OAm)-mediated synthesis and precursor method with a mean particle size of 3.63 ± 0.59 nm as revealed by transmission electron microscopy (TEM). Carbon black was used as a supporting matrix for the OAm-capped Pd NPs. Thermal annealing and acetic acid washing were used to remove the OAm capping agent. To evaluate the electrocatalytic activity of the prepared electrocatalyst towards ethanol oxidation, cyclic voltammetry (CV) studies were performed using 1.0 M ethanol in basic medium. The CV data revealed the highest peak current density of 11.05 mA cm-2 for the acetic acid-washed Pd/C electrocatalyst. Meanwhile, the fabrication of the second Pd-based electrocatalyst was done by functionalization of the carbon black support using 3:1 (v/v) H2SO4:HNO3. The metal oxide, NiO, was deposited using precipitation method while polyol method was used for the deposition of Pd NPs. X-ray diffraction (XRD) analysis revealed that the estimated particle size of the synthesized catalysts was at around 9.0-15.0 nm. CV results demonstrated a 36.7% increase in the catalytic activity of Pd-NiO/C (functionalized) catalyst towards ethanol oxidation compared to the non-functionalized catalyst.

In situ electrodeposition of CoP nanoparticles on carbon nanomaterial doped polyphenylene sulfide flexible electrode for electrochemical hydrogen evolution

NASA Astrophysics Data System (ADS)

Wang, Tingxia; Jiang, Yimin; Zhou, Yaxin; Du, Yongling; Wang, Chunming

2018-06-01

Active and durable electrocatalyst for hydrogen evolution reaction (HER) is pivotal to generate molecular hydrogen more energy-efficient, but directly grafting electrocatalyst on electrode material by a single-step method without compromising the catalytic activity and stability remains a challenge. Herein, an intriguing electrode, reduced graphene oxide modified carbon nanotube/reduced graphene oxide/polyphenylene sulfide (RGO-CNT/RGO/PPS) film, is used to replace conventional electrodes. In situ electrodeposition is proposed to fabricate CoP on the RGO-CNT/RGO/PPS (CoP-RGO-CNT/RGO/PPS) electrode and achieves a favorably electrical contact between CoP nanoparticles and RGO-CNT/RGO/PPS electrode due to without any polymer binder. Additionally, the coupling of different electrodeposition stages with scanning electron microscope (SEM) can investigate the nanostructure evolution of CoP nanoparticles, which gives valuable insights into the optimized electrodeposition cycles. The rational integration of RGO onto CNT/RGO/PPS film is an effective approach for enhancing its intrinsic electrical conductivity and favoring the formation of a high density of dispersive CoP nanoparticles. The CoP-RGO-CNT/RGO/PPS film has shown outstanding HER electrocatalytic behaviors performed a current density of 10 mA cm-2 at a relatively low overpotential of 160 mV with a Tafel slope of 60 mV dec-1 in acidic medium, which can be mainly attributed to the synergistic effect between optimized morphology and accelerated kinetics. Additionally, this film electrocatalyst exhibits a good HER activity and stability under both neutral and basic conditions.

Pt-Richcore/Sn-Richsubsurface/Ptskin Nanocubes As Highly Active and Stable Electrocatalysts for the Ethanol Oxidation Reaction.

PubMed

Rizo, Rubén; Arán-Ais, Rosa M; Padgett, Elliot; Muller, David A; Lázaro, Ma Jesús; Solla-Gullón, José; Feliu, Juan M; Pastor, Elena; Abruña, Héctor D

2018-03-14

Direct ethanol fuel cells are one of the most promising electrochemical energy conversion devices for portable, mobile and stationary power applications. However, more efficient and stable and less expensive electrocatalysts are still required. Interestingly, the electrochemical performance of the electrocatalysts toward the ethanol oxidation reaction can be remarkably enhanced by exploiting the benefits of structural and compositional sensitivity and control. Here, we describe the synthesis, characterization, and electrochemical behavior of cubic Pt-Sn nanoparticles. The electrochemical activity of the cubic Pt-Sn nanoparticles was found to be about three times higher than that obtained with unshaped Pt-Sn nanoparticles and six times higher than that of Pt nanocubes. In addition, stability tests indicated the electrocatalyst preserves its morphology and remains well-dispersed on the carbon support after 5000 potential cycles, while a cubic (pure) Pt catalyst exhibited severe agglomeration of the nanoparticles after a similar stability testing protocol. A detailed analysis of the elemental distribution in the nanoparticles by STEM-EELS indicated that Sn dissolves from the outer part of the shell after potential cycling, forming a ∼0.5 nm Pt skin. This particular atomic composition profile having a Pt-rich core, a Sn-rich subsurface layer, and a Pt-skin surface structure is responsible for the high activity and stability.

Catalytic Activity of Platinum Monolayer on Iridium and Rhenium Alloy Nanoparticles for the Oxygen Reduction Reaction

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

Karan, Hiroko I.; Sasaki, Kotaro; Kuttiyiel, Kurian

2012-05-04

A new type of electrocatalyst with a core–shell structure that consists of a platinum monolayer shell placed on an iridium–rhenium nanoparticle core or platinum and palladium bilayer shell deposited on that core has been prepared and tested for electrocatalytic activity for the oxygen reduction reaction. Carbon-supported iridium–rhenium alloy nanoparticles with several different molar ratios of Ir to Re were prepared by reducing metal chlorides dispersed on Vulcan carbon with hydrogen gas at 400 °C for 1 h. These catalysts showed specific electrocatalytic activity for oxygen reduction reaction comparable to that of platinum. The activities of Pt ML/Pd ML/Ir 2Re 1,more » Pt ML/Pd 2layers/Ir 2Re 1, and Pt ML/Pd 2layers/Ir 7Re 3 catalysts were, in fact, better than that of conventional platinum electrocatalysts, and their mass activities exceeded the 2015 DOE target. Our density functional theory calculations revealed that the molar ratio of Ir to Re affects the binding strength of adsorbed OH and, thereby, the O 2 reduction activity of the catalysts. The maximum specific activity was found for an intermediate OH binding energy with the corresponding catalyst on the top of the volcano plot. The monolayer concept facilitates the use of much less platinum than in other approaches. Finally, the results with the Pt ML/Pd ML/Ir 2Re electrocatalyst indicate that it is a promising alternative to conventional Pt electrocatalysts in low-temperature fuel cells.« less

Bimetallic Platinum-Rhodium Alloy Nanodendrites as Highly Active Electrocatalyst for the Ethanol Oxidation Reaction.

PubMed

Bai, Juan; Xiao, Xue; Xue, Yuan-Yuan; Jiang, Jia-Xing; Zeng, Jing-Hui; Li, Xi-Fei; Chen, Yu

2018-06-13

Rationally designing and manipulating composition and morphology of precious metal-based bimetallic nanostructures can markedly enhance their electrocatalytic performance, including selectivity, activity, and durability. We herein report the synthesis of bimetallic PtRh alloy nanodendrites (ANDs) with tunable composition by a facile complex-reduction synthetic method under hydrothermal conditions. The structural/morphologic features, formation mechanism, and electrocatalytic performance of PtRh ANDs are investigated thoroughly by various physical characterization and electrochemical methods. The preformed Rh crystal nuclei effectively catalyze the reduction of Pt 2+ precursor, resulting in PtRh alloy generation due to the catalytic growth and atoms interdiffusion process. The Pt atoms deposition distinctly interferes in Rh atoms deposition on Rh crystal nuclei, resulting in dendritic morphology of PtRh ANDs. For the ethanol oxidation reaction (EOR), PtRh ANDs display the chemical composition and solution pH co-dependent electrocatalytic activity. Because of the alloy effect and particular morphologic feature, Pt 1 Rh 1 ANDs with optimized composition exhibit better reactivity and stability for the EOR than commercial Pt nanocrystals electrocatalyst.

General Strategy for the Synthesis of Transition-Metal Phosphide/N-Doped Carbon Frameworks for Hydrogen and Oxygen Evolution.

PubMed

Pu, Zonghua; Zhang, Chengtian; Amiinu, Ibrahim Saana; Li, Wenqiang; Wu, Lin; Mu, Shichun

2017-05-17

Transition metal phosphides (TMPs) have been identified as promising nonprecious metal electrocatalyst for hydrogen evolution reaction (HER) and other energy conversion reactions. Herein, we reported a general strategy for synthesis of a series of TMPs (Fe 2 P, FeP, Co 2 P, CoP, Ni 2 P, and Ni 12 P 5 ) nanoparticles (NPs) with different metal phases embedded in a N-doped carbon (NC) matrix using metal salt, ammonium dihydrogen phosphate, and melamine as precursor with varying molar ratios and thermolysis temperatures. The resultant TMPs can serve as highly active and durable bifunctional electrocatalyst toward HER and oxygen evolution reaction (OER). In particular, the Ni 2 P@NC phase only requires an overpotential of ∼138 mV to derive HER in 0.5 M H 2 SO 4, and ∼320 mV for OER in 1.0 M KOH at the current density of 10 mA cm -2 . Because of the encapsulation of NC that can effectively prevent corrosion of embedded TMP NPs, Ni 2 P@NC exhibits almost unfading catalytic performance even after 10 h under both acidic and alkaline solutions. This synthesis strategy provides a new avenue to exploring TMPs as highly active and stable electrocatalyst for the HER, OER, and other electrochemical applications.

First report of vertically aligned (Sn,Ir)O2:F solid solution nanotubes: Highly efficient and robust oxygen evolution electrocatalysts for proton exchange membrane based water electrolysis

NASA Astrophysics Data System (ADS)

Ghadge, Shrinath Dattatray; Patel, Prasad P.; Datta, Moni K.; Velikokhatnyi, Oleg I.; Shanthi, Pavithra M.; Kumta, Prashant N.

2018-07-01

One dimensional (1D) vertically aligned nanotubes (VANTs) of (Sn0.8Ir0.2)O2:10F are synthesized for the first time by a sacrificial template assisted approach. The aim is to enhance the electrocatalytic activity of F doped (Sn,Ir)O2 solid solution electrocatalyst for oxygen evolution reaction (OER) in proton exchange membrane (PEM) based water electrolysis by generating (Sn0.8Ir0.2)O2:10F nanotubes (NTs). The 1D vertical channels and the high electrochemically active surface area (ECSA ∼38.46 m2g-1) provide for facile electron transport. This results in low surface charge transfer resistance (4.2 Ω cm2), low Tafel slope (58.8 mV dec-1) and excellent electrochemical OER performance with ∼2.3 and ∼2.6 fold higher electrocatalytic activity than 2D thin films of (Sn0.8Ir0.2)O2:10F and benchmark IrO2 electrocatalysts, respectively. Furthermore, (Sn0.8Ir0.2)O2:10F NTs exhibit excellent mass activity (21.67 A g-1), specific activity (0.0056 mAcm-2) and TOF (0.016 s-1), which is ∼2-2.6 fold higher than thin film electrocatalysts at an overpotential of 270 mV, with a total mass loading of 0.3 mg cm-2. In addition, (Sn0.8Ir0.2)O2:10F NTs demonstrate remarkable electrochemical durability - comparable to thin films of (Sn0.8Ir0.2)O2:10F and pure IrO2, operated under identical testing conditions in PEM water electrolysis. These results therefore indicate promise of (Sn0.8Ir0.2)O2:10F NTs as OER electrocatalysts for efficient and sustainable hydrogen production.

Engineering the Interfaces of Superadsorbing Graphene-Based Electrodes with Gas and Electrolyte to Boost Gas Evolution and Activation Reactions.

PubMed

Zhang, Jun-Jun; Lv, Li-Bing; Zhao, Tian-Jian; Lin, Yun-Xiao; Yu, Qiu-Ying; Su, Juan; Hirano, Shin-Ichi; Li, Xin-Hao; Chen, Jie-Sheng

2018-05-30

Electrochemical gas evolution and activation reactions are complicated processes, involving not only active electrocatalysts but also the interaction among solid electrodes, electrolyte, and gas-phase products and reactants. In this study, multiphase interfaces of superadsorbing graphene-based electrodes were controlled without changing the active centers to significantly facilitate mass diffusion kinetics for superior performance. The achieved in-depth understanding of how to regulate the interfacial properties to promote the electrochemical performance could provide valuable clues for electrode manufacture and for the design of more active electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of an efficient heteroatom-doped carbon electro-catalyst for oxygen reduction reaction by pyrolysis of protein-rich pulse flour cooked with SiO2 nanoparticles.

PubMed

Gokhale, Rohan; Unni, Sreekuttan M; Puthusseri, Dhanya; Kurungot, Sreekumar; Ogale, Satishchandra

2014-03-07

Development of a highly durable, fuel-tolerant, metal-free electro-catalyst for oxygen reduction reaction (ORR) is essential for robust and cost-effective Anion Exchange Membrane Fuel Cells (AEMFCs). Herein, we report the development of a nitrogen-doped (N-doped) hierarchically porous carbon-based efficient ORR electrocatalyst from protein-rich pulses. The process involves 3D silica nanoparticle templating of the pulse flour(s) followed by their double pyrolysis. The detailed experiments are performed on gram flour (derived from chickpeas) without any in situ/ex situ addition of dopants. The N-doped porous carbon thus generated shows remarkable electrocatalytic activity towards ORR in the alkaline medium. The oxygen reduction on this material follows the desired 4-electron transfer mechanism involving the direct reduction pathway. Additionally, the synthesized carbon catalyst also exhibits good electrochemical stability and fuel tolerance. The results are also obtained and compared with the case of soybean flour having higher nitrogen content to highlight the significance of different parameters in the ORR catalyst performance.

Evaluation of Pd Nanoparticle-Decorated CeO2-MWCNT Nanocomposite as an Electrocatalyst for Formic Acid Fuel Cells

NASA Astrophysics Data System (ADS)

Saleem, Junaid; Safdar Hossain, SK.; Al-Ahmed, Amir; Rahman, Ateequr; McKay, Gordon; Hossain, Mohammed M.

2018-04-01

In this work, CeO2-modified Pd/CeO2-carbon nanotube (CNT) electrocatalyst for the electro-oxidation of formic acid has been investigated. The support CNT was first modified with different amounts (5-30 wt.%) of CeO2 using a precipitation-deposition method. The electrocatalysts were developed by dispersing Pd on the CeO2-CNT supports using the borohydride reduction method. The synthesized electrocatalysts were analyzed for composition, morphology and electronic structure using x-ray diffraction (XRD), scanning electron microscopy with energy-dispersive x-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) techniques. The formation of Pd nanoparticles on the CeO2-CNT support was confirmed using TEM. The activity of Pd/CeO2-CNT and of Pd-CNT samples upon oxidation of formic acid was evaluated by using carbon monoxide stripping voltammetry, cyclic voltammetry, and chronoamperometry. The addition of moderate amounts of cerium oxide (up to 10 wt.%) significantly improved the activity of Pd/CeO2-CNT compared to the unmodified Pd-CNT. Pd/10 wt.% CeO2-CNT showed a current density of 2 A mg-1, which is ten times higher than that of the unmodified Pd-CNT (0.2 A mg-1). Similarly, the power density obtained for Pd/10 wt.% CeO2-CNT in an air-breathing formic acid fuel cell was 6.8 mW/cm2 which is two times higher than Pd-CNT (3.2 mW/cm2), thus exhibiting the promotional effects of CeO2 to Pd/CeO2-CNT. A plausible justification for the improved catalytic performance and stability is provided in the light of the physical characterization results.

Synthesis and Characterization of CO-and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

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

Shamsuddin Ilias

2005-12-22

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we synthesized four Pt-based electrocatalysts catalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) on Vulcan XG72 Carbon support by both conventional and ultra-sonication method. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. Sonication method appears to provide better dispersion of catalysts on carbon support.« less

Hydrothermal transformation of dried grass into graphitic carbon-based high performance electrocatalyst for oxygen reduction reaction.

PubMed

Zhang, Haimin; Wang, Yun; Wang, Dan; Li, Yibing; Liu, Xiaolu; Liu, Porun; Yang, Huagui; An, Taicheng; Tang, Zhiyong; Zhao, Huijun

2014-08-27

In this work, we present a low cost and environmentally benign hydrothermal method using dried grass as the sole starting material without any synthetic chemicals to directly produce high quality nitrogen-doped carbon nanodot/nanosheet aggregates (N-CNAs), achieving a high yield of 25.2%. The fabricated N-CNAs possess an N/C atomic ratio of 3.41%, consist of three typed of doped N at a ratio of 2.6 (pyridinic):1.7 (pyrrolic):1 (graphitic). The experimental results reveal that for oxygen reduction reaction (ORR), the performance of N-CNAs, in terms of electrocatalytic activity, stability and resistance to crossover effects, is better or comparable to the commercial Pt/C electrocatalyst. The theoretical studies further indicate that the doped pyridinic-N plays a key role for N-CNAs' excellent four-electron ORR electrocatalytic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced activity of Au-Fe/C anodic electrocatalyst for direct borohydride-hydrogen peroxide fuel cell

NASA Astrophysics Data System (ADS)

Yi, Lanhua; Wei, Wei; Zhao, Caixian; Tian, Li; Liu, Jing; Wang, Xianyou

2015-07-01

Carbon supported Au-Fe bimetallic nanocatalysts (Au-Fe/C) are facilely prepared via a modified NaBH4 reduction method in aqueous solution at room temperature, and used as the anode electrocatalyst of direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the Au-Fe/C electrocatalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV), rotating disc electrode (RDE) voltammetry, chronoamperometry (CA), chronopotentiometry (CP), and fuel cell test. The results show that Au-Fe/C catalysts display higher catalytic activity for the direct electrooxidation of BH4- than carbon supported pure Au nanocatalyst (Au/C), especially Au50Fe50/C catalyst presents the highest catalytic activity among all as-prepared catalysts. Besides, the single DBHFC with Au50Fe50/C anode and Au/C cathode obtains the maximum power density as high as 34.9 mW cm-2 at 25 °C.

Tuning Surface Electronic Configuration of NiFe LDHs Nanosheets by Introducing Cation Vacancies (Fe or Ni) as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction.

PubMed

Wang, Yanyong; Qiao, Man; Li, Yafei; Wang, Shuangyin

2018-04-01

Intrinsically inferior electrocatalytic activity of NiFe layered double hydroxides (LDHs) nanosheets is considered as a limiting factor to inhibit the electrocatalytic properties for oxygen evolution reaction (OER). Proper defect engineering to tune the surface electronic configuration of electrocatalysts may significantly improve the intrinsic activity. In this work, the selective formation of cation vacancies in NiFe LDHs nanosheets is successfully realized. The as-synthesized NiFe LDHs-V Fe and NiFe LDHs-V Ni electrocatalysts show excellent activity for OER, mainly attributed to the introduction of rich iron or nickel vacancies in NiFe LDHs nanosheets, which efficiently tune the surface electronic structure increasing the adsorbing capacity of OER intermediates. Density functional theory (DFT) computational results also further indicate that the OER catalytic performance of NiFe LDHs can be pronouncedly improved by introducing Fe or Ni vacancies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures

PubMed Central

Zhang, Xing; Wu, Zishan; Zhang, Xiao; Li, Liewu; Li, Yanyan; Xu, Haomin; Li, Xiaoxiao; Yu, Xiaolu; Zhang, Zisheng; Liang, Yongye; Wang, Hailiang

2017-01-01

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm−2 and a turnover frequency of 4.1 s−1 at the overpotential of 0.52 V in a near-neutral aqueous solution. PMID:28272403

Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal-Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems.

PubMed

Tylus, Urszula; Jia, Qingying; Strickland, Kara; Ramaswamy, Nagappan; Serov, Alexey; Atanassov, Plamen; Mukerjee, Sanjeev

2014-05-01

Detailed understanding of the nature of the active centers in non-precious-metal-based electrocatalyst, and their role in oxygen reduction reaction (ORR) mechanistic pathways will have a profound effect on successful commercialization of emission-free energy devices such as fuel cells. Recently, using pyrolyzed model structures of iron porphyrins, we have demonstrated that a covalent integration of the Fe-N x sites into π-conjugated carbon basal plane modifies electron donating/withdrawing capability of the carbonaceous ligand, consequently improving ORR activity. Here, we employ a combination of in situ X-ray spectroscopy and electrochemical methods to identify the various structural and functional forms of the active centers in non-heme Fe/N/C catalysts. Both methods corroboratively confirm the single site 2e - × 2e - mechanism in alkaline media on the primary Fe 2+ -N 4 centers and the dual-site 2e - × 2e - mechanism in acid media with the significant role of the surface bound coexisting Fe/Fe x O y nanoparticles (NPs) as the secondary active sites.

Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal–Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems

PubMed Central

2015-01-01

Detailed understanding of the nature of the active centers in non-precious-metal-based electrocatalyst, and their role in oxygen reduction reaction (ORR) mechanistic pathways will have a profound effect on successful commercialization of emission-free energy devices such as fuel cells. Recently, using pyrolyzed model structures of iron porphyrins, we have demonstrated that a covalent integration of the Fe–Nx sites into π-conjugated carbon basal plane modifies electron donating/withdrawing capability of the carbonaceous ligand, consequently improving ORR activity. Here, we employ a combination of in situ X-ray spectroscopy and electrochemical methods to identify the various structural and functional forms of the active centers in non-heme Fe/N/C catalysts. Both methods corroboratively confirm the single site 2e– × 2e– mechanism in alkaline media on the primary Fe2+–N4 centers and the dual-site 2e– × 2e– mechanism in acid media with the significant role of the surface bound coexisting Fe/FexOy nanoparticles (NPs) as the secondary active sites. PMID:24817921

Rationally Designed Hierarchically Structured Tungsten Nitride and Nitrogen-Rich Graphene-Like Carbon Nanocomposite as Efficient Hydrogen Evolution Electrocatalyst.

PubMed

Zhu, Yanping; Chen, Gao; Zhong, Yijun; Zhou, Wei; Shao, Zongping

2018-02-01

Practical application of hydrogen production from water splitting relies strongly on the development of low-cost and high-performance electrocatalysts for hydrogen evolution reaction (HER). The previous researches mainly focused on transition metal nitrides as HER catalysts due to their electrical conductivity and corrosion stability under acidic electrolyte, while tungsten nitrides have reported poorer activity for HER. Here the activity of tungsten nitride is optimized through rational design of a tungsten nitride-carbon composite. More specifically, tungsten nitride (WN x ) coupled with nitrogen-rich porous graphene-like carbon is prepared through a low-cost ion-exchange/molten-salt strategy. Benefiting from the nanostructured WN x , the highly porous structure and rich nitrogen dopant (9.5 at%) of the carbon phase with high percentage of pyridinic-N (54.3%), and more importantly, their synergistic effect, the composite catalyst displays remarkably high catalytic activity while maintaining good stability. This work highlights a powerful way to design more efficient metal-carbon composites catalysts for HER.

Electrochemical oxidation of sulfites by DWCNTs, MWCNTs, higher fullerenes and manganese

NASA Astrophysics Data System (ADS)

Uzun, Dzhamal; Pchelarov, George; Dimitrov, Ognian; Vassilev, Sasho; Obretenov, Willi; Petrov, Konstantin

2018-03-01

Different electrocatalysts were tested for oxidation of sulfites to sulfates, namely, manganese thin films deposited on fullerenes and carbon nanotubes. The results presented clearly show that electrodes containing HFs (higher fullerenes), DWCNTs (double-wall carbon nanotubes) and manganese acetate are effective catalysts in S/O2 fuel cells. HFs and DWCNTs have high catalytic activity and can be employed as standalone catalysts. Manganese was deposited on DWCNTs, HFs and fullerenes C60/C70 by a thermal process. The electrocatalysts were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical testing was carried out by plotting the E/V polarization curve. The polarization curves of the electrodes composed of pristine DWCNTs showed the lowest overpotentials.

Synthesis and characterization of catalysts and electrocatalysts using combinatorial methods

NASA Astrophysics Data System (ADS)

Ramanathan, Ramnarayanan

This thesis documents attempts at solving three problems. Bead-based parallel synthetic and screening methods based on matrix algorithms were developed. The method was applied to search for new heterogeneous catalysts for dehydrogenation of methylcyclohexane. The most powerful use of the method to date was to optimize metal adsorption and evaluate catalysts as a function of incident energy, likely to be important in the future, should availability of energy be an optimization parameter. This work also highlighted the importance of order of addition of metal salts on catalytic activity and a portion of this work resulted in a patent with UOP LLC, Desplaines, Illinois. Combinatorial methods were also investigated as a tool to search for carbon-monoxide tolerant anode electrocatalysts and methanol tolerant cathode electrocatalysts, resulting in discovery of no new electrocatalysts. A physically intuitive scaling criterion was developed to analyze all experiments on electrocatalysts, providing insight for future experiments. We attempted to solve the CO poisoning problem in polymer electrolyte fuel cells using carbon molecular sieves as a separator. This approach was unsuccessful in solving the CO poisoning problem, possibly due to the tendency of the carbon molecular sieves to concentrate CO and CO 2 in pore walls.

Facile solvothermal synthesis of highly active and robust Pd1.87Cu0.11Sn electrocatalyst towards direct ethanol fuel cell applications

NASA Astrophysics Data System (ADS)

Jana, Rajkumar; Dhiman, Shikha; Peter, Sebastian C.

2016-08-01

Ordered intermetallic Pd1.87Cu0.11Sn ternary electrocatalyst has been synthesized by sodium borohydride reduction of precursor salts Pd(acac)2, CuCl2.2H2O and SnCl2 using one-pot solvothermal synthesis method at 220 °C with a reaction time of 24 h. To the best of our knowledge, here for the first time we report surfactant free synthesis of a novel ordered intermetallic ternary Pd1.87Cu0.11Sn nanoparticles. The ordered structure of the catalyst has been confirmed by powder x-ray diffraction, transmission electron microscopy (TEM). Composition and morphology of the nanoparticles have been confirmed through field emission scanning electron microscopy, energy-dispersive spectrometry and TEM. The electrocatalytic activity and stability of the ternary electrocatalyst towards ethanol oxidation in alkaline medium was investigated by cyclic voltammetry and chronoamperometry techniques. The catalyst is proved to be highly efficient and stable upto 500th cycle and even better than commercially available Pd/C (20 wt%) electrocatalysts. The specific and mass activity of the as synthesized ternary catalyst are found to be ∼4.76 and ∼2.9 times better than that of commercial Pd/C. The enhanced activity and stability of the ordered ternary Pd1.87Cu0.11Sn catalyst can make it as a promising candidate for the alkaline direct ethanol fuel cell application.

Cu@C nanoporous composites containing little copper oxides derived from dimethyl imidazole modified MOF199 as electrocatalysts for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Wei, Xuedong; Li, Na; Zhang, Xianming

2017-12-01

It remains a huge challenge to develop non precious electrocatalysts with high activity to substitute commercial Pt catalysts for hydrogen evolution reactions (HER). Here, the C-Cu-DI and C-Cu materials with the copper based nanoporous carbon structures were synthesized by carbonizing MOF199 and DI-MOF199. The composite structure and HER electrocatalytic properties of the C-Cu-DI and C-Cu materials are studied. The results show that C-Cu-DI and C-Cu samples exhibit good catalytic activity. And C-Cu-DI sample through the addition of Dimethyl imidazole(DI) in the DI-MOF199 precursor has higher electrocatalytic activity than the C-Cu sample. The superior catalytic activity is attributed to the special composite structure of nanoscale deposition particles on the framework with plenty of nano pores and nano copper and few copper oxidation particles distributed or wrapped into the amorphous porous carbon phase. The nano copper and few copper oxidation particles in the C-Cu and C-Cu-DI catalysts maybe provide the more effective catalytic activity sites. The C-Cu-DI composite with large size spherical hollow deposition particles has higher conductivity, better BET surface area and reasonable micro-meso-macro porous distribution, so the overpotentials at the current density of 1 mA cm-2 and 10 mA cm-2 are respectively 270 mV and 390 mV vs. RHE. Although the HER activity has a big gap with commercial platinum catalyst, this study can provide an important experimental exploration for the design of copper based non noble metal/nano porous carbon composite HER electrocatalyst.

High activity of cubic PtRh alloys supported on graphene towards ethanol electrooxidation.

PubMed

Rao, Lu; Jiang, Yan-Xia; Zhang, Bin-Wei; Cai, Yuan-Rong; Sun, Shi-Gang

2014-07-21

Cubic PtRh alloys supported on graphene (PtxRhy/GN) with different atomic ratio of Pt and Rh were directly synthesized for the first time using the modified polyol method with Br(-) for the shape-directing agents. The process didn't use surface-capping agents such as PVP that easily occupy the active sites of electrocatalysts and are difficult to remove. Graphene is the key factor for cubic shape besides Br(-) and keeping catalysts high-dispersed. The X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to characterize the structure and morphology of these electrocatalysts. The results showed that they were composed of homogeneous cubic PtRh alloys. Traditional electrochemical methods, such as cyclic voltammetry and chronoamperometry, were used to investigate the electrocatalytic properties of PtxRhy/GN towards ethanol electrooxidation. It can be seen that PtxRhy/GN with all atomic ratios exhibited high catalytic activity, and the most active one has a composition with Pt : Rh = 9 : 1 atomic ratio. Electrochemical in situ FTIR spectroscopy was used to evaluate the cleavage of C-C bond in ethanol at room temperature in acidic solutions, the results illustrated that Rh in an alloy can promote the split of C-C bond in ethanol, and the alloy catalyst with atomic ratio Pt : Rh = 1 : 1 showed obviously better performance for the C-C bond breaking in ethanol and higher selectivity for the enhanced activity of ethanol complete oxidation to CO2 than alloys with other ratios of Pt and Rh. The investigation indicates that high activity of PtxRhy/GN electrocatalyst towards ethanol oxidation is due to the specific shape of alloys and the synergistic effect of two metal elements as well as graphene support.

Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Su, Jianwei; Yang, Yang; Xia, Guoliang; Chen, Jitang; Jiang, Peng; Chen, Qianwang

2017-04-01

The scalable production of hydrogen could conveniently be realized by alkaline water electrolysis. Currently, the major challenge confronting hydrogen evolution reaction (HER) is lacking inexpensive alternatives to platinum-based electrocatalysts. Here we report a high-efficient and stable electrocatalyst composed of ruthenium and cobalt bimetallic nanoalloy encapsulated in nitrogen-doped graphene layers. The catalysts display remarkable performance with low overpotentials of only 28 and 218 mV at 10 and 100 mA cm-2, respectively, and excellent stability of 10,000 cycles. Ruthenium is the cheapest platinum-group metal and its amount in the catalyst is only 3.58 wt.%, showing the catalyst high activity at a very competitive price. Density functional theory calculations reveal that the introduction of ruthenium atoms into cobalt core can improve the efficiency of electron transfer from alloy core to graphene shell, beneficial for enhancing carbon-hydrogen bond, thereby lowing ΔGH* of HER.

Facile and one-pot synthesis of uniform PtRu nanoparticles on polydopamine-modified multiwalled carbon nanotubes for direct methanol fuel cell application.

PubMed

Chen, Fengxia; Ren, Junkai; He, Qian; Liu, Jun; Song, Rui

2017-07-01

A facile, environment-friendly and one-pot synthesis method for the preparation of high performance PtRu electrocatalysts on the multiwalled carbon nanotubes (MWCNTs) is reported. Herein, bimetallic PtRu electrocatalysts are deposited onto polydopamine (Pdop) - functionalized MWCNTs by mildly stirring at room temperature. Without the use of expensive chemicals or corrosive acids, this noncovalent functionalization of MWCNTs by Pdop is simple, facile and eco-friendly, and thus preserving the integrity and electronic structure of MWCNTs. Due to the well improved dispersion and the decreased size of alloy nanoparticles, the PtRu electrocatalysts on Pdop-functionalized MWCNTs show much better dispersion, higher electrochemically active surface area, and higher electrocatalytic activity for the electrooxidation of methanol in direct methanol fuel cells, compared with the conventional acid-treated MWCNTs. Copyright © 2017 Elsevier Inc. All rights reserved.

In Situ Fabrication and Reactivation of Highly Selective and Stable Ag Catalysts for Electrochemical CO2 Conversion.

PubMed

Ma, Ming; Liu, Kai; Shen, Jie; Kas, Recep; Smith, Wilson A

2018-06-08

In this work, the highly selective and stable electrocatalytic reduction of CO 2 to CO on nanostructured Ag electrocatalysts is presented. The Ag electrocatalysts are synthesized by the electroreduction of Ag 2 CO 3 formed by in situ anodic-etching of Ag foil in a KHCO 3 electrolyte. After 3 min of this etching treatment, the Ag 2 CO 3 -derived nanostructured Ag electrocatalysts are capable of producing CO with up to 92% Faradaic efficiency at an overpotential as low as 290 mV, which surpasses all of the reported Ag catalysts at identical conditions to date. In addition, the anodic-etched Ag retained ∼90% catalytic selectivity in the electroreduction of CO 2 to CO for more than 100 h. The Ag 2 CO 3 -derived Ag is able to facilitate the activation of CO 2 via reduction of the activation energy barrier of the initial electron transfer and provide an increased number of active sites, resulting in the dramatically improved catalytic activity for the reduction of CO 2 to CO.

Homogeneously Dispersed Co9S8 Anchored on Nitrogen and Sulfur Co-Doped Carbon Derived from Soybean as Bifunctional Oxygen Electrocatalysts and Supercapacitors.

PubMed

Xiao, Zhen; Xiao, Guozheng; Shi, Minhao; Zhu, Ying

2018-05-16

Developing low-cost and highly active multifunctional electrocatalysts to replace noble metal catalysts is crucial for the commercialization of future clean energy technology. Herein, homogeneous Co 9 S 8 nanoparticles anchored on nitrogen and sulfur co-doped porous carbon nanomaterials (CoS@NSCs) are fabricated by pyrolysis of natural soybean treated with cobalt nitrate. The unique porous structures of the soybean are utilized to provide space for the oxidation and complexation reactions for cobalt compounds, thus leading to in situ generation of homogenously dispersed cobalt sulfide nanoparticles that anchored on the N,S co-doped carbon framework. Because of the coupling effect of cobalt sulfide and doping heteroatoms, CoS@NSC-800 not only displays excellent electrocatalytic performances with low overpotential and high current density toward both oxygen reduction reaction and oxygen evolution reaction comparable to the commercial Pt/C catalyst and IrO 2 catalyst, but also might be a promising candidate for high-performance supercapacitors. The method for the preparation of the multifunctional hybrids is simple but effective for the formation of uniformly distributed metal sulfide nanoparticles anchored on carbon materials, therefore providing a new perspective for the design and synthesis of multifunctional electrocatalysts for electrochemical energy conversion and storage at a large scale.

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

NASA Astrophysics Data System (ADS)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting.

PubMed

Feng, Liang-Liang; Yu, Guangtao; Wu, Yuanyuan; Li, Guo-Dong; Li, Hui; Sun, Yuanhui; Asefa, Tewodros; Chen, Wei; Zou, Xiaoxin

2015-11-11

Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {2̅10} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.

Nitrogen-doped micropore-dominant carbon derived from waste pine cone as a promising metal-free electrocatalyst for aqueous zinc/air batteries

NASA Astrophysics Data System (ADS)

Lei, Xiaoke; Wang, Mengran; Lai, Yanqing; Hu, Langtao; Wang, Hao; Fang, Zhao; Li, Jie; Fang, Jing

2017-10-01

The exploitation for highly effective and low-cost metal-free catalysts with facile and environmental friendly method for oxygen reduction reaction is still a great challenge. To find an effective method for catalyst synthesis, in this manuscript, waste biomass pine cone is employed as raw material and nitrogen-doped micropore-dominant carbon material with excellent ORR catalytic activity is successfully synthesized. The as-prepared N-doped micropore-dominant carbon possesses a high surface area of 1556 m2 g-1. In addition, this carbon electrocatalyst loaded electrode exhibits a high discharge voltage 1.07 V at the current density of 50 mA cm-2, which can be ascribed to the rich micropores and high content of pyridinic N of the prepared carbon, indicative of great potential in the application of zinc/air batteries.

Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

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

Regmi, Yagya N.; Roy, Asa; King, Laurie A.

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less

Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

DOE PAGES

Regmi, Yagya N.; Roy, Asa; King, Laurie A.; ...

2017-10-19

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less

Carbon-supported iron complexes as electrocatalysts for the cogeneration of hydroxylamine and electricity in a NO-H2 fuel cell: A combined electrochemical and density functional theory study

NASA Astrophysics Data System (ADS)

Sheng, Xia; Alvarez-Gallego, Yolanda; Dominguez-Benetton, Xochitl; Baert, Kitty; Hubin, Annick; Zhao, Hailiang; Mihaylov, Tzvetan T.; Pierloot, Kristine; Vankelecom, Ivo F. J.; Pescarmona, Paolo P.

2018-06-01

Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types of iron complexes with tetradentate ligands, namely bis(salicylidene)ethylenediimine (Salen) and phthalocyanine (Pc), supported on activated carbon or graphite were prepared and evaluated as electrocatalysts, either without further treatment or after pyrolysis at 700 °C. The performance in the reduction of NO of gas diffusion cathodes based on these electrocatalysts was investigated in an electrochemical half cell (3-electrode configuration) using linear sweep voltammetry (LSV). The most promising electrocatalysts were studied further by chronoamperometric experiments in a H2-NO fuel cell, which allowed comparison in terms of power output and hydroxylamine production. Depending on the concentration of the NO feed (6 or 18%), the best electrocatalytic performance was delivered either by FePc or FeSalen. The gas diffusion electrode based on FeSalen supported on activated carbon with 0.3 wt% Fe-loading provided the highest current density (86 A/m2) and the best current efficiency (43%) towards the desired NH2OH when operating at the higher NO concentration (18%). Moreover, FeSalen offers the advantage of being cheaper than FePc. The experimental work was complemented by density functional theory (DFT) calculations, which allowed to shed more light on the reaction mechanism for the reduction of nitric oxide at the atomistic level.

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

DOE PAGES

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan; ...

2017-03-20

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Fluorine substituted (Mn,Ir)O 2:F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

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

Ghadge, Shrinath Dattatray; Patel, Prasad Prakash; Datta, Moni Kanchan

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2, RuO 2). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoreticalmore » calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2, denoted as (Mn 1-xIr x)O 2:F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2. In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-xIr x)O 2:F system as an OER electro-catalyst for PEM water electrolysis.« less

Facile preparation of efficient electrocatalysts for oxygen reduction reaction: One-dimensional meso/macroporous cobalt and nitrogen Co-doped carbon nanofibers

NASA Astrophysics Data System (ADS)

Yoon, Ki Ro; Choi, Jinho; Cho, Su-Ho; Jung, Ji-Won; Kim, Chanhoon; Cheong, Jun Young; Kim, Il-Doo

2018-03-01

Efficient electrocatalyst for oxygen reduction reaction (ORR) is an essential component for stable operation of various sustainable energy conversion and storage systems such as fuel cells and metal-air batteries. Herein, we report a facile preparation of meso/macroporous Co and N co-doped carbon nanofibers (Co-Nx@CNFs) as a high performance and cost-effective electrocatalyst toward ORR. Co-Nx@CNFs are simply obtained from electrospinning of Co precursor and bicomponent polymers (PVP/PAN) followed by temperature controlled carbonization and further activation step. The prepared Co-Nx@CNF catalyst carbonized at 700 °C (Co-Nx@CNF700) shows outstanding ORR performance, i.e., a low onset potential (0.941 V) and half wave potential (0.814 V) with almost four-electron transfer pathways (n= 3.9). In addition, Co-Nx@CNF700 exhibits a superior methanol tolerance and higher stability (>70 h) in Zn-air battery in comparison with Pt/C catalyst (∼30 h). The outstanding performance of Co-Nx@CNF700 catalysts is attributed to i) enlarged surface area with bimodal porosity achieved by leaching of inactive species, ii) increase of exposed ORR active Co-Nx moieties and graphitic edge sites, and iii) enhanced electrical conductivity and corrosion resistance due to the existence of numerous graphitic flakes in carbon matrix.

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.

SISGR-Fundamental Experimental and Theoretical Studies on a Novel Family of Oxide Catalyst Supports for Water Electrolysis

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

Kumta, Prashant

2014-10-03

Identification and development of non-noble metal based electro-catalysts or electro-catalysts with significant reduction of expensive noble metal contents (E.g. IrO2, Pt) with comparable electrochemical performance as the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would constitute a major breakthrough in the generation of hydrogen by water electrolysis. Accomplishing such a system would not only result reduction of the overall capital costs of PEM based water electrolyzers, but also help attain the targeted hydrogen production cost [< $ 3.0 / gallon gasoline equivalent (gge)] comparable to conventional liquid fuels. In line with these goals, it wasmore » demonstrated that fluorine doped IrO2 thin films and nanostructured high surface area powders display remarkably higher electrochemical activity, and comparable durability as pure IrO2 electro-catalyst for the oxygen evolution reaction (OER) in PEM based water electrolysis. Furthermore, corrosion resistant SnO2 and NbO2 support has been doped with F and coupled with IrO2 or RuO2 for use as an OER electro-catalyst. A solid solution of SnO2:F or NbO2:F with only 20 - 30 mol.% IrO2 or RuO2 yielding a rutile structure in the form of thin films and bulk nanoparticles displays similar electrochemical activity and stability as pure IrO2/RuO2. This would lead to more than 70 mol.% reduction in the noble metal oxide content. Novel nanostructured ternary (Ir,Sn,Nb)O2 thin films of different compositions FUNDAMENTAL STUDY OF NANOSTRUCTURED ELECTRO-CATALYSTS WITH REDUCED NOBLE METAL CONTENT FOR PEM BASED WATER ELECTROLYSIS 4 have also been studied. It has been shown that (Ir0.40Sn0.30Nb0.30)O2 shows similar electrochemical activity and enhanced chemical robustness as compared to pure IrO2. F doping of the ternary (Ir,Sn,Nb)O2 catalyst helps in further decreasing the noble metal oxide content of the catalyst. As a result, these reduced noble metal oxide catalyst systems would potentially be preferred as OER electro-catalysts for PEM electrolysis. The excellent performance of the catalysts coupled with its robustness would make them great candidates for contributing to significant reduction in the overall capital costs of PEM based water electrolyzers. This s.thesis provides a detailed fundamental study of the synthesis, materials, characterization, theoretical studies and detailed electrochemical response and potential mechanisms of these novel electro-catalysts for OER processes.« less

Electrocatalyst for alcohol oxidation at fuel cell anodes

DOEpatents

Adzic, Radoslav [East Setauket, NY; Kowal, Andrzej [Cracow, PL

2011-11-02

In some embodiments a ternary electrocatalyst is provided. The electrocatalyst can be used in an anode for oxidizing alcohol in a fuel cell. In some embodiments, the ternary electrocatalyst may include a noble metal particle having a surface decorated with clusters of SnO.sub.2 and Rh. The noble metal particles may include platinum, palladium, ruthenium, iridium, gold, and combinations thereof. In some embodiments, the ternary electrocatalyst includes SnO.sub.2 particles having a surface decorated with clusters of a noble metal and Rh. Some ternary electrocatalysts include noble metal particles with clusters of SnO.sub.2 and Rh at their surfaces. In some embodiments the electrocatalyst particle cores are nanoparticles. Some embodiments of the invention provide a fuel cell including an anode incorporating the ternary electrocatalyst. In some aspects a method of using ternary electrocatalysts of Pt, Rh, and SnO.sub.2 to oxidize an alcohol in a fuel cell is described.

Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: I. Impact of Impurities, Measurement Protocols and Applied Corrections

DOE PAGES

Shinozaki, Kazuma; Zack, Jason W.; Richards, Ryan M.; ...

2015-07-22

The rotating disk electrode (RDE) technique is being extensively used as a screening tool to estimate the activity of novel PEMFC electrocatalysts synthesized in lab-scale (mg) quantities. Discrepancies in measured activity attributable to glassware and electrolyte impurity levels, as well as conditioning, protocols and corrections are prevalent in the literature. Moreover, the electrochemical response to a broad spectrum of commercially sourced perchloric acid and the effect of acid molarity on impurity levels and solution resistance were also assessed. Our findings reveal that an area specific activity (SA) exceeding 2.0 mA/cm 2 (20 mV/s, 25°C, 100 kPa, 0.1 M HClO 4)more » for polished poly-Pt is an indicator of impurity levels that do not impede the accurate measurement of the ORR activity of Pt based catalysts. After exploring various conditioning protocols to approach maximum utilization of the electrochemical area (ECA) and peak ORR activity without introducing catalyst degradation, an investigation of measurement protocols for ECA and ORR activity was conducted. Down-selected protocols were based on the criteria of reproducibility, duration of experiments, impurity effects and magnitude of pseudo-capacitive background correction. In sum, statistical reproducibility of ORR activity for poly-Pt and Pt supported on high surface area carbon was demonstrated.« less

A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Miao, Yue-E.; Yan, Jiajie; Ouyang, Yue; Lu, Hengyi; Lai, Feili; Wu, Yue; Liu, Tianxi

2018-06-01

The bio-inspired hierarchical "grape cluster" superstructure provides an effective integration of one-dimensional carbon nanofibers (CNF) with isolated carbonaceous nanoparticles into three-dimensional (3D) conductive frameworks for efficient electron and mass transfer. Herein, a 3D N-doped porous carbon electrocatalyst consisting of carbon nanofibers with grape-like N-doped hollow carbon particles (CNF@NC) has been prepared through a simple electrospinning strategy combined with in-situ growth and carbonization processes. Such a bio-inspired hierarchically organized conductive network largely facilitates both the mass diffusion and electron transfer during the oxygen reduction reactions (ORR). Therefore, the metal-free CNF@NC catalyst demonstrates superior catalytic activity with an absolute four-electron transfer mechanism, strong methanol tolerance and good long-term stability towards ORR in alkaline media.

Palladium-cobalt nanotube arrays supported on carbon fiber cloth as high-performance flexible electrocatalysts for ethanol oxidation.

PubMed

Wang, An-Liang; He, Xu-Jun; Lu, Xue-Feng; Xu, Han; Tong, Ye-Xiang; Li, Gao-Ren

2015-03-16

PdCo nanotube arrays (NTAs) supported on carbon fiber cloth (CFC) (PdCo NTAs/CFC) are presented as high-performance flexible electrocatalysts for ethanol oxidation. The fabricated flexible PdCo NTAs/CFC exhibits significantly improved electrocatalytic activity and durability compared with Pd NTAs/CFC and commercial Pd/C catalysts. Most importantly, the PdCo NTAs/CFC shows excellent flexibility and the high electrocatalytic performance remains almost constant under the different distorted states, such as normal, bending, and twisting states. This work shows the first example of Pd-based alloy NTAs supported on CFC as high-performance flexible electrocatalysts for ethanol oxidation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of Alkylamine Modified Pt Nanoparticles as Oxygen Reduction Reaction Electrocatalyst for Fuel Cells via Electrochemical Impedance Spectroscopy.

PubMed

Joshi, Prerna; Okada, Toshihiko; Miyabayashi, Keiko; Miyake, Mikio

2018-05-15

Organically (octyl amine, OA) surface modified electrocatalyst (OA-Pt/CB) was studied for its oxygen reduction reaction (ORR) activity via dc methods and its charge and mass transfer properties were studied via electrochemical impedance spectroscopy (EIS). Comparison with a commercial catalyst (TEC10V30E) with similar Pt content was also carried out. In EIS, both the catalysts showed a single time-constant with an emerging high-frequency semicircle of very small diameter which was fitted using suitable equivalent circuits. The organically modified catalyst showed lower charge-transfer resistance and hence, low polarization resistance in high potential region as compared to the commercial catalyst. The dominance of kinetic processes was observed at 0.925-1.000 V, whereas domination of diffusion based processes was observed at lower potential region for the organic catalyst. No effect due to the presence of carbon was observed in the EIS spectra. Using the hydrodynamic method, higher current penetration depth was obtained for the organically modified catalyst at 1600 rpm. Exchange current density and Tafel slopes for both the electrocatalysts were calculated from the polarization resistance obtained from EIS which was in correlation with the results obtained from dc methods.

Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

PubMed

Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

2014-01-22

Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

Porous Carbon-Hosted Atomically Dispersed Iron-Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

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

Fu, Shaofang; Zhu, Chengzhou; Su, Dong

As one of the alternatives to replace precious metal catalysts, transition-metal–nitrogen–carbon (M–N–C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M–N–C catalysts can achieve good electrochemical perfor-mances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. In this work, metal–organic frameworks derived porous single-atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further posttreatment. Combining the X-ray absorption near-edge spectroscopy and electrochemical measure-ments, the SAEs have been identified with superior oxygen reduction reaction (ORR) activity and stability compared with Pt/C catalysts in alkaline condition.more » More impressively, the SAEs also show excellent ORR electrocatalytic perfor-mance in both acid and neutral media. This study of nonprecious catalysts provides new insights on nanoengineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH.« less

Nanostructured F doped IrO2 electro-catalyst powders for PEM based water electrolysis

NASA Astrophysics Data System (ADS)

Kadakia, Karan Sandeep; Jampani, Prashanth H.; Velikokhatnyi, Oleg I.; Datta, Moni Kanchan; Park, Sung Kyoo; Hong, Dae Ho; Chung, Sung Jae; Kumta, Prashant N.

2014-12-01

Fluorine doped iridium oxide (IrO2:F) powders with varying F content ranging from 0 to 20 wt.% has been synthesized by using a modification of the Adams fusion method. The precursors (IrCl4 and NH4F) are mixed with NaNO3 and heated to elevated temperatures to form high surface area nanomaterials as electro-catalysts for PEM based water electrolysis. The catalysts were then coated on a porous Ti substrate and have been studied for the oxygen evolution reaction in PEM based water electrolysis. The IrO2:F with an optimum composition of IrO2:10 wt.% F shows remarkably superior electrochemical activity and chemical stability compared to pure IrO2. The results have also been supported via kinetic studies by conducting rotating disk electrode (RDE) experiments. The RDE studies confirm that the electro-catalysts follow the two electron transfer reaction for electrolysis with calculated activation energy of ∼25 kJ mol-1. Single full cell tests conducted also validate the superior electrochemical activity of the 10 wt.% F doped IrO2.

Porous Carbon-Hosted Atomically Dispersed Iron–Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

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

Fu, Shaofang; Zhu, Chengzhou; Su, Dong

2018-02-01

As one of the alternatives to replace precious metal catalysts, transition-metal–nitrogen–carbon (M–N–C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M–N–C catalysts can achieve good electrochemical perfor-mances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. In this work, metal–organic frameworks derived porous single-atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further posttreatment. Combining the X-ray absorption near-edge spectroscopy and electrochemical measure-ments, the SAEs have been identified with superior oxygen reduction reaction (ORR) activity and stability compared with Pt/C catalysts in alkaline condition.more » More impressively, the SAEs also show excellent ORR electrocatalytic perfor-mance in both acid and neutral media. This study of nonprecious catalysts provides new insights on nanoengineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH.« less

Synthesis of nickel germanide (Ge12Ni19) nanoparticles for durable hydrogen evolution reaction in acid solutions.

PubMed

Chen, Jee-Yee; Jheng, Shao-Lou; Tuan, Hsing-Yu

2018-06-14

Desigining advanced materials as electrochemical catalysts for the hydrogen evolution reaction (HER) has caught great attention owing to the growing demand for clean and renewable energy. Nickel (Ni)-based compounds and alloys are promising non-noble-metal electrocatalysts due to their low cost and high activity. However, in most cases, Ni-based compounds and alloys have low durability in acid electrolyte, which limits their application in the electrolytic processes. In this study, monoclinic Ge12Ni19 nanoparticles were synthesized and exhibited high electrocatalytic activity and stability for the HER in acidic solution. Ge12Ni19 nanoparticles achieve an overpotential of 190 mV at cathodic current density of 10 mA cm-2 and a Tafel slope of 88.5 mV per decade in 0.50 M H2SO4 electrolyte. Moreover, the performance is maintained after a 10 000-cycle CV sweep (-0.3 to +0.1 V vs. RHE) or under a static overpotential of -0.7 V vs. RHE for 24 hours. The reported electrocatalytic performance of the Ge12Ni19 nanoparticles sufficiently proves the excellent endurance at lower required active overpotentials in acidic solution, enabling the broad applications of the Ni-based electrocatalysts. Finally, a large-area (5 cm2) electrocatalyst for HER was demonstrated for the first time. The great efficiency of the energy conversion performance sufficiently represented the potential of Ge12Ni19 nanoparticles as electrocatalysts in commercial fuel cells.

Gram-Scale Synthesized Pd2Co-Supported PtMonolayers Electrocatalysts for Oxygen Reduction Reaction

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

Zhou, W.P.; Sasaki, K.; Su, D.

2010-04-21

Gram-scale synthesis of Pt{sub ML} electrocatalysts with a well-defined core-shell structure has been carried out using method involving galvanic displacement of an underpotential deposition Cu layer. The Pt shell thickness can be controlled by stepwise deposition. The Pt{at}Pd{sub 2}Co/C nanoparticles were characterized by X-ray powder diffraction, aberration-corrected scanning transmission electron microscopy, high-resolution energy-loss spectrometry, and in situ X-ray absorption spectroscopy. A complete Pt shell of 0.6 nm on a Pd{sub 2}Co core has been confirmed. The Pt{at}Pd{sub 2}Co/C core-shell electrocatalysts showed a very high activity for the oxygen reduction reaction; the Pt mass and specific activity were 0.72 A mg{supmore » -1}{sub Pt} and 0.5 mA cm{sup -2}, respectively (3.5 and 2.5 times higher than the corresponding values for commercial Pt catalysts), at 0.9 V in 0.1 M HClO{sub 4} at room temperature. In an accelerated potential cycling test, a loss in active surface area and a decrease in catalytic activity for gram-scale-synthesized Pt{sub ML} catalysts were also determined.« less

Synthesis and Characterization of CO- and H2S-Tolerant Electrocatalysts for PEM Fuel Cell

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

Shamsuddin Ilias

2006-05-18

The present state-of-art Proton Exchange Membrane Fuel Cell (PEMFC) technology is based on platinum (Pt) as a catalyst for both the fuel (anode) and air (cathode) electrodes. This catalyst is highly active but susceptible to poisoning by CO, which may be present in the H{sub 2}-fuel used or may be introduced during the fuel processing. Presence of trace amount of CO and H{sub 2}S in the H{sub 2}-fuel poisons the anode irreversibly and decreases the performance of the PEMFCs. In an effort to reduce the Pt-loading and improve the PEMFC performance, we propose to synthesize a number of Pt-based binary,more » ternary, and quaternary electrocatalysts using Ru, Mo, Ir, Ni, and Co as a substitute for Pt. By fine-tuning the metal loadings and compositions of candidate electrocatalysts, we plan to minimize the cost and optimize the catalyst activity and performance in PEMFC. The feasibility of the novel electrocatalysts will be demonstrated in the proposed effort with gas phase CO and H{sub 2}S concentrations typical of those found in reformed fuel gas with coal/natural gas/methanol feedstocks. During this reporting period we used four Pt-based electrocatalysts (Pt/Ru/Mo/Se, Pt/Ru/Mo/Ir, Pt/Ru/Mo/W, Ptr/Ru/Mo/Co) in MEAs and these were evaluated for CO-tolerance with 20 and 100 ppm CO concentration in H{sub 2}-fuel. From current-voltage performance study, the catalytic activity was found in the increasing order of Pt/Ru/Mo/Ir > Pt/Ru/Mo/W > Pt/Ru/Mo/Co > Pt/Ru/MO/Se. From preliminary cost analysis it appears that could of the catalyst metal loading can reduced by 40% to 60% depending on the selection of metal combinations without compromising the fuel cell performance.« less

Formic acid electrooxidation on thallium-decorated shape-controlled platinum nanoparticles: an improvement in electrocatalytic activity.

PubMed

Busó-Rogero, Carlos; Perales-Rondón, Juan V; Farias, Manuel J S; Vidal-Iglesias, Francisco J; Solla-Gullon, Jose; Herrero, Enrique; Feliu, Juan M

2014-07-21

Thallium modified shape-controlled Pt nanoparticles were prepared and their electrocatalytic activity towards formic acid electrooxidation was evaluated in 0.5 M sulfuric acid. The electrochemical and in situ FTIR spectroscopic results show a remarkable improvement in the electrocatalytic activity, especially in the low potential region (around 0.1-0.2 V vs. RHE). Cubic Pt nanoparticles modified with Tl were found to be more active than the octahedral Pt ones in the entire range of Tl coverages and potential windows. In situ FTIR spectra indicate that the promotional effect produced by Tl results in the inhibition of the poisoning step leading to COads, thus improving the onset potential for the complete formic acid oxidation to CO2. Chronoamperometric experiments were also performed at 0.2 V to evaluate the stability of the electrocatalysts at constant potential. Finally, experiments with different concentrations of formic acid (0.05-1 M) were also carried out. In all cases, Tl-modified cubic Pt nanoparticles result to be the most active. All these facts reinforce the importance of controlling the surface structure of the electrocatalysts to optimize their electrocatalytic properties.

High-Performance Overall Water Splitting Electrocatalysts Derived from Cobalt-Based Metal–Organic Frameworks

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

You, Bo; Jiang, Nan; Sheng, Meili

2015-11-05

The design of active, robust, and nonprecious electrocatalysts with both H 2 and O 2 evolution reaction (HER and OER) activities for overall water splitting is highly desirable but remains a grand challenge. Here in this article, we report a facile two-step method to synthesize porous Co-P/NC nanopolyhedrons composed of CoP x (a mixture of CoP and Co 2P) nanoparticles embedded in N-doped carbon matrices as electrocatalysts for overall water splitting. The Co-P/NC catalysts were prepared by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Benefiting from the large specific surface area, controllable pore texture, and highmore » nitrogen content of ZIF (a subclass of metal–organic frameworks), the optimal Co-P/NC showed high specific surface area of 183 m 2 g -1 and large mesopores, and exhibited remarkable catalytic performance for both HER and OER in 1.0 M KOH, affording a current density of 10 mA cm -2 at low overpotentials of -154 mV for HER and 319 mV for OER, respectively. Furthermore, a Co-P/NC-based alkaline electrolyzer approached 165 mA cm -2 at 2.0 V, superior to that of Pt/IrO 2 couple, along with strong stability. Various characterization techniques including X-ray absorption spectroscopy (XAS) revealed that the superior activity and strong stability of Co-P/NC originated from its 3D interconnected mesoporosity with high specific surface area, high conductivity, and synergistic effect of CoP x encapsulated within N-doped carbon matrices.« less

Carbon supported MnO2-CoFe2O4 with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Ying; Liu, Qing; Hu, Tianjun; Zhang, Limin; Deng, Youquan

2017-05-01

The catalyst MnO2-CoFe2O4/C was firstly synthesized via a two-step process and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The composite exhibits better bifunctional activity than CoFe2O4/C and MnO2/C. Moreover, superior durability and high methanol tolerance in alkaline media outperforms the commercial Pt/C electrocatalyst, which signifying its excellent potential for applications in metal-air batteries and alkaline fuel cells.

Soft Chemical Fabrication of Iron-Based Thin Film Electrocatalyst for Water Oxidation under Neutral pH and Structure-Activity Tuning by Cerium Incorporation.

PubMed

Saha, Jony; Radhakrishnan, T P

2017-08-29

Design of electrocatalysts for the fundamentally important oxygen evolution reaction can be greatly aided by systematic structure-activity tuning via composition variation. We have explored the iron-cerium system as they are the most abundant transition and rare earth metals, and also due to the mutualistic impact of their size and electronic attributes that can induce critical changes in the structure and electrochemical activity. Submicrometer thick films of a series of Fe(III)-Ce(III) phosphate(oxyhydroxide) (FeCePH) are fabricated using a soft chemical strategy involving surfactant-aided assembly, spin-coating, and mild thermal annealing. FT-IR, Raman, and X-ray photoelectron spectroscopies, chemical analysis, X-ray diffraction, and electron microscopy reveal the systematic structural, electronic, and morphological variation, on tuning the iron-cerium composition. Nitrogen adsorption-desorption studies show the surface area increasing and pore size distribution shrinking with the cerium content, indicating its structure-directing role. The electrocatalysis of water oxidation by FeCePH films on FTO-coated glass is studied in neutral pH conditions. The overpotential and Tafel slope decrease with increasing cerium content, reaching minima at the optimal Fe:Ce ratio of 1:0.5; the turnover frequency shows a corresponding increase and maximum. The trends are explained on the basis of the structural changes in the films, and the coupling of Ce 3+ /Ce 4+ with Fe 3+ /Fe 4+ that leads to active state regeneration. This study presents a rational strategy to tune the efficiency of easily fabricated transition metal-based electrocatalyst thin films through rare earth metal incorporation; it should prove useful in the design of cost-effective catalysts for water oxidation.

A Molecular Ni-complex Containing Tetrahedral Nickel Selenide Core as Highly Efficient Electrocatalyst for Water Oxidation.

PubMed

Masud, Jahangir; Ioannou, Polydoros-Chrysovalantis; Levesanos, Nikolaos; Kyritsis, Panayotis; Nath, Manashi

2016-11-23

We report the highly efficient catalytic activity of a transition metal selenide-based coordination complex, [Ni{(SeP i Pr 2 ) 2 N} 2 ], (1) for oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solution. Very low overpotentials of 200 mV and 310 mV were required to achieve 10 mA cm -2 for OER and HER, respectively. The overpotential for OER is one of the lowest that has been reported up to now, making this one of the best OER electrocatalysts. In addition, this molecular complex exhibits an exceptionally high mass activity (111.02 A g -1 ) and a much higher TOF value (0.26 s -1 ) at a overpotential of 300 mV. This bifunctional electrocatalyst enables water electrolysis in alkaline solutions at a cell voltage of 1.54 V. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials.

PubMed

Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

2017-09-08

It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

Co@Co3O4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode.

PubMed

Aijaz, Arshad; Masa, Justus; Rösler, Christoph; Xia, Wei; Weide, Philipp; Botz, Alexander J R; Fischer, Roland A; Schuhmann, Wolfgang; Muhler, Martin

2016-03-14

Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal-air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core-shell Co@Co3O4 nanoparticles embedded in CNT-grafted N-doped carbon-polyhedra obtained by the pyrolysis of cobalt metal-organic framework (ZIF-67) in a reductive H2 atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO2 , and RuO2 and thus ranking them among one of the best non-precious-metal electrocatalysts for reversible oxygen electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

2018-03-01

Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

Porous yolk-shell microspheres as N-doped carbon matrix for motivating the oxygen reduction activity of oxygen evolution oriented materials

NASA Astrophysics Data System (ADS)

Zhou, Jinqiu; Wang, Mengfan; Qian, Tao; Liu, Sisi; Cao, Xuecheng; Yang, Tingzhou; Yang, Ruizhi; Yan, Chenglin

2017-09-01

It is highly challenging to explore high-performance bi-functional oxygen electrode catalysts for their practical application in next-generation energy storage and conversion devices. In this work, we synthesize hierarchical N-doped carbon microspheres with porous yolk-shell structure (NCYS) as a metal-free electrocatalyst toward efficient oxygen reduction through a template-free route. The enhanced oxygen reduction performances in both alkaline and acid media profit well from the porous yolk-shell structure as well as abundant nitrogen functional groups. Furthermore, such yolk-shell microspheres can be used as precursor materials to motivate the oxygen reduction activity of oxygen evolution oriented materials to obtain a desirable bi-functional electrocatalyst. To verify its practical utility, Zn-air battery tests are conducted and exhibit satisfactory performance, indicating that this constructed concept for preparation of bi-functional catalyst will afford a promising strategy for exploring novel metal-air battery electrocatalysts.

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution.

PubMed

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy-carbon core-shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10-30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2-6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

Fabrication of graphene-fullerene hybrid by self-assembly and its application as support material for methanol electrocatalytic oxidation reaction

NASA Astrophysics Data System (ADS)

Zhang, Xuan; Zhang, Jia-Wei; Xiang, Ping-Hua; Qiao, Jinli

2018-05-01

Graphene-fullerene hybrids were facilely fabricated by self-assembly of graphene oxide (GO) and multi-substituted fulleropyrrolidines (PyrC60). The hybrids (GO-PyrC60) were applied as support materials to deposit Pd nanoparticle catalyst by a simple hydrothermal co-reduction approach. The as-prepared electrocatalysts (Pd/RGO-PyrC60) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. The RGO-PyrC60 hybrid supported Pd catalyst with the optimal ratio of RGO to PyrC60, exhibited much enhanced electrocatalytic activity and stability toward methanol oxidation reaction (MOR) compared to the RGO alone supported Pd as well as commercial Pd/C. The introduction of fulleropyrrolidine as spacer between graphene layers could increase the electrocatalytic activity and improve the long-term stability. This strategy may contribute to developing graphene-fullerene hydrids as effective support materials for advanced electrocatalysts.

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

PubMed

Feng, Jin-Xian; Tong, Si-Yao; Tong, Ye-Xiang; Li, Gao-Ren

2018-04-18

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H + and hamper the ability of H + to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H + from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

2D PdAg Alloy Nanodendrites for Enhanced Ethanol Electroxidation.

PubMed

Huang, Wenjing; Kang, Xiaolin; Xu, Cheng; Zhou, Junhua; Deng, Jun; Li, Yanguang; Cheng, Si

2018-03-01

The development of highly active and stable electrocatalysts for ethanol electroxidation is of decisive importance to the successful commercialization of direct ethanol fuel cells. Despite great efforts invested over the past decade, their progress has been notably slower than expected. In this work, the facile solution synthesis of 2D PdAg alloy nanodendrites as a high-performance electrocatalyst is reported for ethanol electroxidation. The reaction is carried out via the coreduction of Pd and Ag precursors in aqueous solution with the presence of octadecyltrimethylammonium chloride as the structural directing agent. Final products feature small thickness (5-7 nm) and random in-plane branching with enlarged surface areas and abundant undercoordinated sites. They exhibit enhanced electrocatalytic activity (large specific current ≈2600 mA mgPd-1) and excellent operation stability (as revealed from both the cycling and chronoamperometric tests) for ethanol electroxidation. Control experiments show that the improvement comes from the combined electronic and structural effects. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

DOE PAGES

Saadi, Fadl H.; Carim, Azhar I.; Drisdell, Walter S.; ...

2017-08-28

Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η of -η < 100 mV at a current density of -10 mA cm -2 in 0.500 M H 2SO 4 (aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H 2SO 4 (aq).more » Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Lastly, operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.« less

Ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles for enhanced electrocatalytic hydrogen evolution

NASA Astrophysics Data System (ADS)

Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang

2018-06-01

Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy–carbon core–shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10–30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2–6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.

Electrocatalytic Reduction of Carbon Dioxide with a Well-Defined PN 3 -Ru Pincer Complex

DOE PAGES

Min, Shixiong; Rasul, Shahid; Li, Huaifeng; ...

2015-11-13

We established a well-defined PN 3-Ru pincer complex (5) bearing a redox-active bipyridine ligand with an aminophosphine arm as an effective and stable molecular electrocatalyst for CO 2 reduction to CO and HCOOH with negligible formation of H 2 in a H 2O/MeCN mixture.

Metal molybdate nanorods as non-precious electrocatalysts for the oxygen reduction

NASA Astrophysics Data System (ADS)

Wu, Tian; Zhang, Lieyu

2015-12-01

Development of non-precious electrocatalysts with applicable electrocatalytic activity towards the oxygen reduction reaction (ORR) is important to fulfill broad-based and large-scale applications of metal/air batteries and fuel cells. Herein, nickel and cobalt molybdates with uniform nanorod morphology are synthesized using a facile one-pot hydrothermal method. The ORR activity of the prepared metal molybdate nanorods in alkaline media are investigated by using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperomety in rotating disk electrode (RDE) techniques. The present study suggests that the prepared metal molybdate nanorods exhibit applicable electrocatalytic activities towards the ORR in alkaline media, promising the applications as non-precious cathode in fuel cells and metal-air batteries.

Electrocatalysts for carbon dioxide conversion

DOEpatents

Masel, Richard I; Salehi-Khojin, Amin

2015-04-21

Electrocatalysts for carbon dioxide conversion include at least one catalytically active element with a particle size above 0.6 nm. The electrocatalysts can also include a Helper Catalyst. The catalysts can be used to increase the rate, modify the selectivity or lower the overpotential of electrochemical conversion of CO.sub.2. Chemical processes and devices using the catalysts also include processes to produce CO, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

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.

Pt 3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction

DOE PAGES

Raciti, David; Kubal, Joseph; Ma, Cheng; ...

2015-12-25

Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt 3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well asmore » Density Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.« less

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.

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.

Electrochemical and Morphological Investigations of Ga Addition to Pt Electrocatalyst Supported on Carbon

PubMed Central

Paganoto, Giordano T.; Santos, Deise M.; Guimarães, Marco C. C.; Carneiro, Maria Tereza W. D.

2017-01-01

This paper is consisted in the synthesis of platinum-based electrocatalysts supported on carbon (Vulcan XC-72) and investigation of the addition of gallium in their physicochemical and electrochemical properties toward ethanol oxidation reaction (EOR). PtGa/C electrocatalysts were prepared through thermal decomposition of polymeric precursor method at a temperature of 350°C. Six different compositions were homemade: Pt50Ga50/C, Pt60Ga40/C, Pt70Ga30/C, Pt80Ga20/C, Pt90Ga10/C, and Pt100/C. These electrocatalysts were electrochemically characterized by cyclic voltammetry (CV), chronoamperometry (CA), chronopotentiometry (CP), and electrochemical impedance spectroscopy (EIS) in the presence and absence of ethanol 1.0 mol L−1. Thermogravimetric analysis (TGA), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and transmission electron microscopy (TEM) were also carried out for a physicochemical characterization of those materials. XRD results showed the main peaks of face-centered cubic Pt. The particle sizes obtained from XRD and TEM analysis range from 7.2 nm to 12.9 nm. The CV results indicate behavior typical of Pt-based electrocatalysts in acid medium. The CV, EIS, and CA data reveal that the addition of up to 31% of gallium to the Pt highly improves catalytic activity on EOR response when compared to Pt100/C. PMID:28466065

Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

DOE PAGES

Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

2014-10-30

The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

RuO2 nanoparticles decorated MnOOH/C as effective bifunctional electrocatalysts for lithium-air battery cathodes with long-cycling stability

NASA Astrophysics Data System (ADS)

Kim, Gil-Pyo; Lim, Dongwook; Park, Inyeong; Park, Hyelee; Shim, Sang Eun; Baeck, Sung-Hyeon

2016-08-01

Manganite (MnOOH) is one of the most effective electrocatalysts for oxygen reduction reaction (ORR), and RuO2 nanoparticles exhibit high activity for oxygen evolution reaction (OER). We herein report a facile means of producing well dispersed RuO2/MnOOH on Ketjen black (RuO2/MnOOH/C) as a bifunctional catalyst for lithium-air (Li-air) batteries. RuO2/MnOOH/C was simply synthesized using a hydrothermal/precipitation based method, and was used as a cathode for a Li-air battery using a Swagelok-type cell. The importance of dispersing active catalysts on a carbon support was clearly demonstrated by textural, charge-discharge voltammetric, and electrochemical impedance spectroscopic (EIS) analyses, comparing results with a catalyst produced by physically mixing RuO2/MnOOH with carbon (RuO2/MnOOH + C). RuO2/MnOOH/C showed low overpotential and stable cycleability up to 170th cycles with 1000 mAh g-1 of charge-discharge capacity, which was attributed to its enhanced active surface area and low charge-transfer resistance. The results obtained suggest that this strategy can be widely applied to bifunctional electrocatalysis, such as secondary batteries and regenerative fuel cell (RFC).

Electrochemical Characterization Laboratory | Energy Systems Integration

Science.gov Websites

proton exchange membrane fuel cells. Photo of an NREL researcher evaluating catalyst activity in the the following capabilities: Determination and benchmarking of novel electrocatalyst activity

KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

Porous Carbon-Hosted Atomically Dispersed Iron-Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

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

Fu, Shaofang; Zhu, Chengzhou; Su, Dong

As one of the alternatives to replace precious metal catalysts, transition metal-nitrogen-carbon (M-N-C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M-N-C catalysts can achieve good electrochemical performances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. Thus, M-N-C’s stability and selectivity have not been comparable to their noble metal counterparts. In this work, metal-organic frameworks (MOFs)-derived porous single-atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further post-treatment. Combining the X-ray absorption near-edge spectroscopy (XANES) and electrochemical measurements, the SAEs have been identifiedmore » with superior ORR activity and stability compared with Pt/C catalysts in alkaline condition. More impressively, the SAEs also show excellent ORR electrocatalytic performance in both acid and neutral media. Furthermore, this study of nonprecious catalysts provides new insights on nano-engineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH.« less

Porous Carbon-Hosted Atomically Dispersed Iron-Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

DOE PAGES

Fu, Shaofang; Zhu, Chengzhou; Su, Dong; ...

2018-02-12

As one of the alternatives to replace precious metal catalysts, transition metal-nitrogen-carbon (M-N-C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M-N-C catalysts can achieve good electrochemical performances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. Thus, M-N-C’s stability and selectivity have not been comparable to their noble metal counterparts. In this work, metal-organic frameworks (MOFs)-derived porous single-atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further post-treatment. Combining the X-ray absorption near-edge spectroscopy (XANES) and electrochemical measurements, the SAEs have been identifiedmore » with superior ORR activity and stability compared with Pt/C catalysts in alkaline condition. More impressively, the SAEs also show excellent ORR electrocatalytic performance in both acid and neutral media. Furthermore, this study of nonprecious catalysts provides new insights on nano-engineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH.« less

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering.

PubMed

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-21

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

PubMed Central

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-01-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

NASA Astrophysics Data System (ADS)

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Inhibitive effect of Pt on Pd-hydride formation of Pd@Pt core-shell electrocatalysts: An in situ EXAFS and XRD study

DOE PAGES

Wise, Anna M.; Richardson, Peter W.; Price, Stephen W. T.; ...

2017-12-27

In situ EXAFS and XRD have been used to study the electrochemical formation of hydride phases, H abs, in 0.5 M H 2SO 4 for a Pd/C catalyst and a series of Pd@Pt core-shell catalysts with varying Pt shell thickness, from 0.5 to 4 monolayers. Based on the XRD data a 3% lattice expansion is observed for the Pd/C core catalyst upon hydride formation at 0.0 V. In contrast, the expansion was ≤0.6% for all of the core-shell catalysts. The limited extent of the lattice expansion observed suggests that hydride formation, which may occur during periodic active surface area measurementsmore » conducting during accelerated aging tests or driven by H 2 crossover in PEM fuel cells, is unlikely to contribute significantly to the degradation of Pd@Pt core-shell electrocatalysts in contrast to the effects of oxide formation.« less

Inhibitive effect of Pt on Pd-hydride formation of Pd@Pt core-shell electrocatalysts: An in situ EXAFS and XRD study

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

Wise, Anna M.; Richardson, Peter W.; Price, Stephen W. T.

In situ EXAFS and XRD have been used to study the electrochemical formation of hydride phases, H abs, in 0.5 M H 2SO 4 for a Pd/C catalyst and a series of Pd@Pt core-shell catalysts with varying Pt shell thickness, from 0.5 to 4 monolayers. Based on the XRD data a 3% lattice expansion is observed for the Pd/C core catalyst upon hydride formation at 0.0 V. In contrast, the expansion was ≤0.6% for all of the core-shell catalysts. The limited extent of the lattice expansion observed suggests that hydride formation, which may occur during periodic active surface area measurementsmore » conducting during accelerated aging tests or driven by H 2 crossover in PEM fuel cells, is unlikely to contribute significantly to the degradation of Pd@Pt core-shell electrocatalysts in contrast to the effects of oxide formation.« less

Nitrogen and Phosphorus Codoped Mesoporous Carbon Derived from Polypyrrole as Superior Metal-Free Electrocatalyst toward the Oxygen Reduction Reaction.

PubMed

Zhang, Zhengping; Sun, Junting; Dou, Meiling; Ji, Jing; Wang, Feng

2017-05-17

To replace high-cost platinum group metal (PGM) electrocatalysts for oxygen reduction reaction (ORR) that is the crucial cathode reaction in fuel cell technology and metal-air battery, the development of low-cost and high-efficiency non-PGM catalysts for ORR has attracted much attention during the past decades. As one of the promising candidates, N-doped carbon is highly desirable for its strong designability and outstanding catalytic activity and stability. In this work, a facile and rational strategy is demonstrated for preparation of N,P-codoped mesoporous carbon (N,P-MC) for ORR by the direct pyrolysis treatment of polypyrrole with phytic acid as P-dopant and polystyrene sphere as template. The resultant N,P-MC exhibits a mesoporous structure with the optimized ORR active sites originating from the N,P-codoping. Owing to these features, N,P-MC exhibits excellent ORR activity, remarkable electrochemical stability, and superior methanol tolerance, comparable or even better than that of commercial Pt/C catalyst. The origin of enhanced ORR performance can be attributed to both the increased active sites and the mesoporous structure, which is expected to guide the future preparation of more capable carbon-based electrocatalysts for oxygen reduction and other electrocatalytic application.

Strategic design of a ruthenium catalyst for both CO2 reduction and H2O oxidation: the electronic influence of the co-ligands.

PubMed

Das, Biswanath; Ezzedinloo, Lida; Bhadbhade, Mohan; Bucknall, Martin P; Colbran, Stephen B

2017-09-05

A new ruthenium(ii) complex capable of catalysing both CO 2 reduction and water oxidation was designed and synthesised. The electro-catalytic efficiency and robustness of the complex together with the electronic effect of its co-ligands were investigated to develop next generation dual activity electrocatalysts.

Synthesis and characterization of an Fe(i) cage complex with high stability towards strong H-acids.

PubMed

Voloshin, Yan Z; Novikov, Valentin V; Nelyubina, Yulia V; Belov, Alexander S; Roitershtein, Dmitrii M; Savitsky, Anton; Mokhir, Andriy; Sutter, Jörg; Miehlich, Matthias E; Meyer, Karsten

2018-04-03

The first synthesized and X-ray structurally characterized "classical" iron(i) dioximate showed an unrivaled stability towards strong acids, thus calling for a reassessment of the origins of the electrocatalytic activity of similar low-valent cobalt and iron cage complexes with electron-withdrawing ribbed substituents, shown previously to be effective electrocatalysts of the HER.

Nitrogen-doped graphdiyne as a metal-free catalyst for high-performance oxygen reduction reactions

NASA Astrophysics Data System (ADS)

Liu, Rongji; Liu, Huibiao; Li, Yuliang; Yi, Yuanping; Shang, Xinke; Zhang, Shuangshuang; Yu, Xuelian; Zhang, Suojiang; Cao, Hongbin; Zhang, Guangjin

2014-09-01

Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts.Fuel cells and metal-air batteries will only become widely available in everyday life when the expensive platinum-based electrocatalysts used for the oxygen reduction reactions are replaced by other efficient, low-cost and stable catalysts. We report here the use of nitrogen-doped graphdiyne as a metal-free electrode with a comparable electrocatalytic activity to commercial Pt/C catalysts for the oxygen reduction reaction in alkaline fuel cells. Nitrogen-doped graphdiyne has a better stability and increased tolerance to the cross-over effect than conventional Pt/C catalysts. Electronic supplementary information (ESI) available: Detailed RDE and RRDE experiments, additional tables and figures. See DOI: 10.1039/c4nr03185g

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

PubMed

Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

2014-11-21

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Effect of pH in a Pd-based ethanol membraneless air breathing nanofluidic fuel cell with flow-through electrodes

NASA Astrophysics Data System (ADS)

López-Rico, C. A.; Galindo-de-la-Rosa, J.; Ledesma-García, J.; Arriaga, L. G.; Guerra-Balcázar, M.; Arjona, N.

2015-12-01

In this work, a nanofluidic fuel cell (NFC) in which streams flow through electrodes was used to investigate the role of pH in the cell performance using ethanol as fuel and two Pd nanoparticles as electrocatalysts: one commercially available (Pd/C from ETEK) and other synthesized using ionic liquids (Pd/C IL). The cell performances for both electrocatalysts in acid/acid (anodic/cathodic) streams were of 18.05 and 9.55 mW cm-2 for Pd/C ETEK and Pd/C IL. In alkaline/alkaline streams, decrease to 15.94 mW cm-2 for Pd/C ETEK and increase to 15.37 mW cm-2 for Pd/C IL. In alkaline/acidic streams both electrocatalysts showed similar cell voltages (up to 1 V); meanwhile power densities were of 87.6 and 99.4 mW cm-2 for Pd/C ETEK and Pd/C IL. The raise in cell performance can be related to a decrease in activation losses, the combined used of alkaline and acidic streams and these high values compared with flow-over fuel cells can be related to the enhancement of the cathodic mass transport by using three dimensional porous electrodes and two sources of oxygen: from air and from a saturated solution.

Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene.

PubMed

Ma, Wei; Ma, Renzhi; Wu, Jinghua; Sun, Pengzhan; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2016-05-21

Ni(2+)Mn(3+) layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni(2+)/Mn(2+) salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery.

Crack-tips enriched platinum-copper superlattice nanoflakes as highly efficient anode electrocatalysts for direct methanol fuel cells.

PubMed

Zheng, Lijun; Yang, Dachi; Chang, Rong; Wang, Chengwen; Zhang, Gaixia; Sun, Shuhui

2017-07-06

We have developed "crack-tips" and "superlattice" enriched Pt-Cu nanoflakes (NFs), benefiting from the synergetic effects of "crack-tips" and "superlattice crystals"; the Pt-Cu NFs exhibit 4 times higher mass activity, 6 times higher specific activity and 6 times higher stability than those of the commercial Pt/C catalyst, respectively. Meanwhile, the Pt-Cu NFs show more enhanced CO tolerance than the commercial Pt/C catalyst.

Preparation and evaluation of advanced electrocatalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hochmuth, J.; Pagliaro, P.

1981-01-01

A number of electrocatalyst combinations were prepared and characterized. These electrocatalysts were formulated to contain platinum combined with transition metal carbide forming elements (W, Mo, V) for cathodes and platinum combined with palladium for anodes. High resolution electron microscopy was used to determine the crystallite size and dispersion of platinum-palladium alloy electrocatalysts in order to provide analytical support for the electrochemical determinations of the particle dispersions. An equation was derived which correlates palladium crystallite size with electrochemical hydrogen adsorption. Based on comparisons of electrocatalyst performances in the presence of pure hydrogen and hydrogen containing carbon monoxide, it was shown that the apparent poisoning of the electrocatalyst by carbon monoxide is influenced by the electrode structure.

Surface-oxidized cobalt phosphide used as high efficient electrocatalyst in activated carbon air-cathode microbial fuel cell

NASA Astrophysics Data System (ADS)

Yang, Tingting; Wang, Zhong; Li, Kexun; Liu, Yi; Liu, Di; Wang, Junjie

2017-09-01

Herein, we report a simplistic method to fabricate the surface-oxidized cobalt phosphide (CoP) nanocrystals (NCs), which is used as electrocatalyst for oxygen reduction reaction (ORR) in microbial fuel cell (MFC) for the first time. The corallite-like CoP NCs are successfully prepared by a hydrothermal reaction following a phosphating treatment in N2 atmosphere. When used as an ORR catalyst, cobalt phosphide shows comparable onset potential, inferior resistance, as well as a small Tafel slope with long-term stability in neutral media. The maximum power density of MFC embellished with 10% CoP reached 1914.4 ± 59.7 mW m-2, which is 108.5% higher than the control. The four-electron pathway, observed by the RDE, plays a crucial role in electrochemical catalytic activity. In addition, material characterizations indicate that the surface oxide layer (CoOx) around the metallic CoP core is important and beneficial for ORR. Accordingly, it can be expected that the as-synthesized CoP will be a promising candidate of the non-precious metal ORR electrocatalysts for electrochemical energy applications.

Pt-Pd Bimetal Popcorn Nanocrystals: Enhancing the Catalytic Performance by Combination Effect of Stable Multipetals Nanostructure and Highly Accessible Active Sites.

PubMed

Ma, Yanxia; Yin, Lisi; Cao, Guojian; Huang, Qingli; He, Maoshuai; Wei, Wenxian; Zhao, Hong; Zhang, Dongen; Wang, Mingyan; Yang, Tao

2018-04-01

Exploration of highly efficient electrocatalysts is significantly urgent for the extensive adoption of the fuel cells. Because of their high activity and super stability, Pt-Pd bimetal nanocrystals have been widely recognized as one class of promising electrocatalysts for oxygen reduction. This article presents the synthesis of popcorn-shaped Pt-Pd bimetal nanoparticles with a wide composition range through a facile hydrothermal strategy. The hollow-centered nanoparticles are surrounded by several petals and concave surfaces. By exploring the oxygen reduction reaction on the carbon supported Pt-Pd popcorns in perchloric acid solution, it is found that compared with the commercial Pt/C catalyst the present catalysts display superior catalytic performances in aspects of catalytic activity and stability. More importantly, the Pt-Pd popcorns display minor performance degradations through prolonged potential cycling. The enhanced performances can be mainly attributed to the unique popcorn structure of the Pt-Pd components, which allows the appearance and long existence of the high active sites with more accessibility. The present work highlights the key roles of accessible high active sites in the oxygen reduction reaction, which will ultimately guide the design of highly durable Pt-Pd catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Advances in Developing Platinum Monolayer Electrocatalysts for the O2 Reduction Reaction

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

Vukmirovic,M.B.; Sasaki, K.; Zhou, W.-P.

2008-09-15

For Pt, the best single-element catalyst for many reactions, the question of content and loading is exceedingly important because of its price and availability. Using platinum as a fuel-cell catalyst in automotive applications will cause an unquantifiable increase in the demand for this metal. This big obstacle for using fuel cells in electric cars must be solved by decreasing the content of Pt, which is a great challenge of electrocatalysis Over the last several years we inaugurated a new class of electrocatalysts for the oxygen reduction reaction (ORR) based on a monolayer of Pt deposited on metal or alloy carbon-supportedmore » nanoparticles. The possibility of decreasing the Pt content in the ORR catalysts down to a monolayer level has a considerable importance because this reaction requires high loadings due to its slow kinetics. The Pt-monolayer approach has several unique features and some of them are: high Pt utilization, enhanced (or decreased) activity, enhanced stability, and direct activity correlations. The synthesis of Pt monolayer (ML) electrocatalysts was facilitated by our new synthesis method which allowed us to deposit a monolayer of Pt on various metals, or alloy nanoparticles [1, 2] for the cathode electrocatalyst. In this synthesis approach Pt is laid down by the galvanically displacing a Cu monolayer, which was deposited at underpotentials in a monolayer-limited reaction on appropriate metal substrate, with Pt after immersing the electrode in a K{sub 2}PtCl{sub 4} solution.« less

Development of efficient electrocatalysts via molecular hybridization of NiMn layered double hydroxide nanosheets and graphene

NASA Astrophysics Data System (ADS)

Ma, Wei; Ma, Renzhi; Wu, Jinghua; Sun, Pengzhan; Liu, Xiaohe; Zhou, Kechao; Sasaki, Takayoshi

2016-05-01

Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery.Ni2+Mn3+ layered double hydroxide (LDH) nanoplatelets have been hydrothermally synthesized in a homogeneous precipitation of mixed Ni2+/Mn2+ salts at a molar ratio of 2 : 1 via the hydrolysis of hexamethylenetetramine (HMT) and in situ oxidation with H2O2. After anion-exchange, NiMn LDH was exfoliated into unilamellar nanosheets. Subsequent flocculation of NiMn LDH nanosheets with (reduced) graphene oxide (GO/rGO) into superlattice composites was achieved and further tested as electrocatalysts for oxygen evolution reaction (OER). The face-to-face heteroassembly of NiMn LDH nanosheets with conductive rGO at an alternating sequence resulted in a small overpotential of 0.26 V and a Tafel slope of 46 mV per decade, which is much superior to as-exfoliated nanosheets. The analyses of electrochemical activity surface area (ECSA) and impedance spectra clearly indicated that the superlattice structure was ideal in facilitating the migration/transfer of the charge and reactants, revealing the electrochemical energetics and mechanism behind the synergistic effect arising from molecular hybridization. The proof of concept toward total water splitting using the newly developed hybrid electrocatalyst was demonstrated by an electrolysis cell powered by a single AA battery. Electronic supplementary information (ESI) available: Typical TG-DSC curves, XRD patterns, elemental mapping profiles, LSV curves, Tafel plots, current density difference curves, current density against ECSA curves and designed water-splitting cell. See DOI: 10.1039/c6nr00988c

An ultrafine platinum-cobalt alloy decorated cobalt nanowire array with superb activity toward alkaline hydrogen evolution.

PubMed

Wang, Ziqiang; Ren, Xiang; Luo, Yonglan; Wang, Liang; Cui, Guanwei; Xie, Fengyu; Wang, Hongjing; Xie, Ying; Sun, Xuping

2018-06-22

It is highly desired to design and develop highly efficient electrocatalysts for alkaline hydrogen evolution reactions. Herein, we report the development of ultrafine PtCo alloy nanoparticle decorated one-dimensional Co nanowires grown on Ti mesh (PtCo-Co/TiM). Owing to its favorable composition and structure, the PtCo-Co/TiM can deliver an ultrahigh current density of 46.5 mA cm-2 at an overpotential of 70 mV in 1.0 M KOH, superior to recently reported Pt-based electrocatalysts. This catalyst also provides excellent long-term electrochemical durability with its catalytic activity being maintained for at least 50 h.

Spinel CuCo2O4 nanoparticles supported on N-doped reduced graphene oxide: a highly active and stable hybrid electrocatalyst for the oxygen reduction reaction.

PubMed

Ning, Rui; Tian, Jingqi; Asiri, Abdullah M; Qusti, Abdullah H; Al-Youbi, Abdulrahman O; Sun, Xuping

2013-10-29

In this Letter, for the first time, we demonstrated the preparation of a highly efficient electrocatalyst, spinel CuCo2O4 nanoparticles supported on N-doped reduced graphene oxide (CuCo2O4/N-rGO), for an oxygen reduction reaction (ORR) under alkaline media. The hybrid exhibits higher ORR catalytic activity than CuCo2O4 or N-rGO alone, the physical mixture of CuCo2O4 nanoparticles and N-rGO, and Co3O4/N-rGO. Moreover, such a hybrid affords superior durability to the commercial Pt/C catalyst.

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

The Study on the Performance of Carbon Supported PtSnM (M = W, Pd, and Ni) Ternary Electro-Catalysts for Ethanol Electro-Oxidation Reaction.

PubMed

Noh, Chang Soo; Heo, Dong Hyun; Lee, Ki Rak; Jeon, Min Ku; Sohn, Jung Min

2016-05-01

PtSn/C and Pt5Sn4M/C (M = W, Pd, Ni) electrocatalysts were prepared by impregnation method using NaBH4 as a reducing agent. Chemical composition, crystalline size, and alloy formation were determined by EDX, XRD and TEM. The average particle sizes of the synthesized catalysts were approximately 3.64-4.95 nm. The electro-chemical properties were measured by CO stripping, cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. The maximum specific activity of the electro-catalysts for ethanol electro-oxidation was 406.08 mA m(-2) in Pt5Sn4Pd/C. The poisoning rate of the Pt5Sn4Pd/C (0.0017% s(-1)) was 4.5 times lower than that of the PtSn/C (0.0076% s(-1)).

A molecular approach to self-supported cobalt-substituted ZnO materials as remarkably stable electrocatalysts for water oxidation.

PubMed

Pfrommer, Johannes; Lublow, Michael; Azarpira, Anahita; Göbel, Caren; Lücke, Marcel; Steigert, Alexander; Pogrzeba, Martin; Menezes, Prashanth W; Fischer, Anna; Schedel-Niedrig, Thomas; Driess, Matthias

2014-05-12

In regard to earth-abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt-substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low-temperature solvolysis of molecular heterobimetallic Co(4-x)Zn(x) O4 (x = 1-3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self-supported water-oxidation electrocatalyst, which was observed by HR-TEM on FIB lamellas of the EPD layers. The Co-rich hydroxide-oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Noble Metal Aerogels—Synthesis, Characterization, and Application as Electrocatalysts

PubMed Central

2015-01-01

Conspectus Metallic and catalytically active materials with high surface area and large porosity are a long-desired goal in both industry and academia. In this Account, we summarize the strategies for making a variety of self-supported noble metal aerogels consisting of extended metal backbone nanonetworks. We discuss their outstanding physical and chemical properties, including their three-dimensional network structure, the simple control over their composition, their large specific surface area, and their hierarchical porosity. Additionally, we show some initial results on their excellent performance as electrocatalysts combining both high catalytic activity and high durability for fuel cell reactions such as ethanol oxidation and the oxygen reduction reaction (ORR). Finally, we give some hints on the future challenges in the research area of metal aerogels. We believe that metal aerogels are a new, promising class of electrocatalysts for polymer electrolyte fuel cells (PEFCs) and will also open great opportunities for other electrochemical energy systems, catalysis, and sensors. The commercialization of PEFCs encounters three critical obstacles, viz., high cost, insufficient activity, and inadequate long-term durability. Besides others, the sluggish kinetics of the ORR and alcohol oxidation and insufficient catalyst stability are important reasons for these obstacles. Various approaches have been taken to overcome these obstacles, e.g., by controlling the catalyst particle size in an optimized range, forming multimetallic catalysts, controlling the surface compositions, shaping the catalysts into nanocrystals, and designing supportless catalysts with extended surfaces such as nanostructured thin films, nanotubes, and porous nanostructures. These efforts have produced plenty of excellent electrocatalysts, but the development of multisynergetic functional catalysts exhibiting low cost, high activity, and high durability still faces great challenges. In this Account, we demonstrate that the sol–gel process represents a powerful “bottom-up” strategy for creating nanostructured materials that tackles the problems mentioned above. Aerogels are unique solid materials with ultralow densities, large open pores, and ultimately high inner surface areas. They magnify the specific properties of nanomaterials to the macroscale via self-assembly, which endow them with superior properties. Despite numerous investigations of metal oxide aerogels, the investigation of metal aerogels is in the early stage. Recently, aerogels including Fe, Co, Ni, Sn, and Cu have been obtained by nanosmelting of hybrid polymer–metal oxide aerogels. We report here exclusively on mono-, bi- and multimetallic noble metal aerogels consisting of Ag, Au, Pt, and Pd and their application as electrocatalysts. PMID:25611348

Nitro Lignin-Derived Nitrogen-Doped Carbon as an Efficient and Sustainable Electrocatalyst for Oxygen Reduction.

PubMed

Graglia, Micaela; Pampel, Jonas; Hantke, Tina; Fellinger, Tim-Patrick; Esposito, Davide

2016-04-26

The use of lignin as a precursor for the synthesis of materials is nowadays considered very interesting from a sustainability standpoint. Here we illustrate the synthesis of a micro-, meso-, and macroporous nitrogen-doped carbon (NDC) using lignin extracted from beech wood via alkaline hydrothermal treatment and successively functionalized via aromatic nitration. The so obtained material is thus carbonized in the eutectic salt melt KCl/ZnCl2. The final NDC shows an excellent activity as electrocatalyst for the oxygen reduction reaction.

Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks

DOE PAGES

Barkholtz, Heather M.; Liu, Di -Jia

2016-11-14

Over the past several years, metal-organic framework (MOF)-derived platinum group metal free (PGM-free) electrocatalysts have gained considerable attention due to their high efficiency and low cost as potential replacement for platinum in catalyzing oxygen reduction reaction (ORR). In this review, we summarize the recent advancements in design, synthesis and characterization of MOF-derived ORR catalysts and their performances in acidic and alkaline media. As a result, we also discuss the key challenges such as durability and activity enhancement critical in moving forward this emerging electrocatalyst science.

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.

Electrocatalyst advances for hydrogen oxidation in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.

1984-01-01

The important considerations that presently exist for achieving commercial acceptance of fuel cells are centered on cost (which translates to efficiency) and lifetime. This paper addresses the questions of electrocatalyst utilization within porous electrode structures and the preparation of low-cost noble metal electrocatalyst combinations with extreme dispersions of the metal. Now that electrocatalyst particles can be prepared with dimensions of 10 A, either singly or in alloy combinations, a very large percentage of the noble metal atoms in a crystallite are available for reaction. The cost savings for such electrocatalysts in the present commercially driven environment are considerable.

PdCo porous nanostructures decorated on polypyrrole @ MWCNTs conductive nanocomposite-Modified glassy carbon electrode as a powerful catalyst for ethanol electrooxidation

NASA Astrophysics Data System (ADS)

Fard, Leyla Abolghasemi; Ojani, Reza; Raoof, Jahan Bakhsh; Zare, Ehsan Nazarzadeh; Lakouraj, Moslem Mansour

2017-04-01

In the current study, well-defined PdCo porous nanostructure (PdCo PNS) is prepared by a simple one-pot wet-chemical method and polypyrrole@multi-walled carbon nanotubes (PPy@MWCNTs) nanocomposite is used as a catalyst support. The morphology and the structural properties of the prepared catalyst were studied by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The electrocatalytic performance of PdCo PNS/PPy@MWCNTs on glassy carbon electrode has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) techniques. The specific activity of PdCo PNS/PPy@MWCNTs for ethanol electrooxidation (1.65 mA cm-2) is higher than those of other compared electrocatalysts. Also, PdCo PNS/PPy@MWCNTs catalyst represented higher electrocatalytic activity, better long-term stability and high level of poisoning tolerance to the carbonaceous oxidative intermediates for ethanol electrooxidation reaction in alkaline media. Furthermore, the presence of PPY@MWCNTs on the surface of GCE produce a high activity to electrocatalyst, which might be due to the easier charge transfer at polymer/carbon nanotubes interfaces, higher electrochemically accessible surface areas and electronic conductivity. The superior catalytic activity of PdCo PNS/PPy@MWCNTs suggests it to be as a promising electrocatalyst for future direct ethanol fuel cells.

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst.

PubMed

Zheng, Yao; Jiao, Yan; Zhu, Yihan; Li, Lu Hua; Han, Yu; Chen, Ying; Jaroniec, Mietek; Qiao, Shi-Zhang

2016-12-14

Hydrogen evolution reaction (HER) is a critical process due to its fundamental role in electrocatalysis. Practically, the development of high-performance electrocatalysts for HER in alkaline media is of great importance for the conversion of renewable energy to hydrogen fuel via photoelectrochemical water splitting. However, both mechanistic exploration and materials development for HER under alkaline conditions are very limited. Precious Pt metal, which still serves as the state-of-the-art catalyst for HER, is unable to guarantee a sustainable hydrogen supply. Here we report an anomalously structured Ru catalyst that shows 2.5 times higher hydrogen generation rate than Pt and is among the most active HER electrocatalysts yet reported in alkaline solutions. The identification of new face-centered cubic crystallographic structure of Ru nanoparticles was investigated by high-resolution transmission electron microscopy imaging, and its formation mechanism was revealed by spectroscopic characterization and theoretical analysis. For the first time, it is found that the Ru nanocatalyst showed a pronounced effect of the crystal structure on the electrocatalytic activity tested under different conditions. The combination of electrochemical reaction rate measurements and density functional theory computation shows that the high activity of anomalous Ru catalyst in alkaline solution originates from its suitable adsorption energies to some key reaction intermediates and reaction kinetics in the HER process.

Nitrogen and sulfur dual-doped chitin-derived carbon/graphene composites as effective metal-free electrocatalysts for dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Di, Yi; Xiao, Zhanhai; Yan, Xiaoshuang; Ru, Geying; Chen, Bing; Feng, Jiwen

2018-05-01

The photovoltaic performance of dye-sensitized solar cell (DSSC) is strongly influenced by the electrocatalytic ability of its counter electrode (CE) materials. To obtain the affordable and high-performance electrocatalysts, the N/S dual-doped chitin-derived carbon materials SCCh were manufactured via in-situ S-doped method in the annealing process, where richer active sites are created compared to the pristine chitin-derived carbon matrix CCh, thus enhancing the intrinsic catalytic activity of carbon materials. When SCCh is incorporated with graphene, the yielded composites hold a further boosted catalytic activity due to facilitating the electronic fast transfer. The DSSC assembled with the optimizing rGO-SCCh-3 composite CE shows a favourable power conversion efficiency of 6.36%, which is comparable with that of the Pt-sputtering electrode (6.30%), indicate of the outstanding I3- reduction ability of the composite material. The electrochemical characterizations demonstrate that the low charge transfer resistance and excellent electrocatalytic activity all contribute to the superior photovoltaic performance. More importantly, the composite CE exhibits good electrochemical stability in the practical operation. In consideration of the low cost and the simple preparation procedure, the present metal-free carbonaceous composites could be used as a promising counter electrode material in future large scale production of DSSCs.

Rational geometrical engineering of palladium sulfide multi-arm nanostructures as a superior bi-functional electrocatalyst.

PubMed

Nandan, R; Nanda, K K

2017-08-31

Geometrical tunability offers sharp edges and an open-armed structure accompanied with a high electrochemical active surface area to ensure the efficient and effective utilization of materials by exposing the electrochemical active sites for facile accessibility of reactant species. Herein, we report a one-step, single-pot, surfactant-free, electroless, and economic route to synthesize palladium sulfide nanostructures with different geometries at mild temperatures and their catalytic properties towards the oxygen reduction reaction (ORR) and methanol electro-oxidation (MOR). For ORR, the positive on-set, half wave potentials, smaller Tafel slope, high electrochemical active surface area, large roughness factor, and better cyclic stability of the proposed nanostructures as compared to those of the commercial state-of-the-art Pt-C/PdS catalysts suggest their superiority in an alkaline medium. In addition, high mass activity (J f ∼ 715 mA mg -1 ), in comparison with that of the commercial state-of-the-art Pt-C/PdS catalysts (J f ∼ 138/41 mA mg -1 , respectively), and high J f /J b (1.52) along with the superior operational stability of the multi-arm palladium sulfide nanostructures towards MOR advocates the bi-functional behavior of the catalyst and its potential as a promising Pt-free anode/cathode electrocatalyst in fuel cells.

Synergistic interaction and controllable active sites of nitrogen and sulfur co-doping into mesoporous carbon sphere for high performance oxygen reduction electrocatalysts

NASA Astrophysics Data System (ADS)

Oh, Taeseob; Kim, Myeongjin; Park, Dabin; Kim, Jooheon

2018-05-01

Nitrogen and sulfur co-doped mesoporous carbon sphere (NSMCS) was prepared as a metal-free catalyst by an economical and facile pyrolysis process. The mesoporous carbon spheres were derived from sodium carboxymethyl cellulose as the carbon source and the nitrogen and sulfur dopants were derived from urea and p-benzenedithiol, respectively. The doping level and chemical states of nitrogen and sulfur in the prepared NSMCS can be easily adjusted by controlling the pyrolysis temperature. The NSMCS pyrolyzed at 900 °C (NSMCS-900) exhibited higher oxygen reduction reaction activity than the mesoporous carbon sphere doped solely with nitrogen or sulfur, due to the synergistic effect of co-doping. Among all the NSMCS samples, NSMCS-900 exhibited excellent ORR catalytic activity owing to the presence of a highly active site, consisting of pyridinic N, graphitic N, and thiophene S. Remarkably, the NSMCS-900 catalyst was comparable with commercial Pt/C, in terms of the onset and the half-wave potentials and showed better durability than Pt/C for ORR in an alkaline electrolyte. The approach demonstrated in this work could be used to prepare promising metal-free electrocatalysts for application in energy conversion and storage.

Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Pan, Fuping; Cao, Zhongyue; Zhao, Qiuping; Liang, Hongyu; Zhang, Junyan

2014-12-01

The successful commercialization of fuel cells requires the efficient electrocatalyst to make the oxygen reduction reaction (ORR) fast because of the sluggish nature of ORR and the high cost of the platinum catalysts. In this work, we report the excellent performance of metal-free nitrogen-doped porous carbon nanosheets (NPCN) with hierarchical porous structure and a high surface area of 1436.02 m2 g-1 for catalyzing ORR. The active NPCN is synthesized via facile high-temperature carbonization of natural ginkgo leaves followed by purification and ammonia post-treatment without using additional supporting templates and activation processes. In O2-saturated 0.1 M KOH solution, the resultant NPCN exhibits a high kinetic-limiting current density of 13.57 mA cm-2 at -0.25 V (vs. Ag/AgCl) approaching that of the commercial Pt/C catalyst (14 mA cm-2) and long-term electrochemical stability. Notably, the NPCN shows a slightly negative ORR half-wave potential in comparison with Pt/C (ΔE1/2 = 19 mV). The excellent electrocatalytic properties of NPCN originate from the combined effect of optimal nitrogen doping, high surface area, and porous architecture, which induce the high-density distribution of highly active and stable catalytic sites.

Refining cocoon to prepare (N, S, and Fe) ternary-doped porous carbon aerogel as efficient catalyst for the oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Li, Changqing; Sun, Fengzhan; Lin, Yuqing

2018-04-01

Various advanced sulfur doped Fe-N-C non-noble metal catalysts of oxygen reduction reaction (ORR) have been recently designed and reported with excellent catalytic activity. Herein, we refined cocoon with several steps to form silk fibroin solution, treated with iron salt to prepare an easy available, heteroatom (N, S, and Fe) ternary-doped, porous carbon aerogel (HDCA). Heteroatom existed in organic compounds in silk fibroin endow active site for ORR of the resultant carbon frameworks. Moreover, the amino acids presented in silk fibroin acted as ligands, functioning with Fe ions to form FeNx coordination compounds, which also served as active sites towards ORR. The synthesized HDCA electrocatalysts, especially HDCA-800 (obtained at 800 °C) displayed excellent catalytic activity with onsets, half-wave potential of 0.94 V, 0.79 V and higher limited current density of 3.80 mA cm-2 through a near four-electron reduction pathway with an average electron transferred number of 3.86, making them promising alternatives for state-of-the-art ORR electrocatalysts in fuel cell field. The porous structure with synergistic effect of N and S heteroatom doping has been proposed to play a key role in facilitating the desired ORR reaction.

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

Ultrathin layered double hydroxide nanosheets with Ni(III) active species obtained by exfoliation for highly efficient ethanol electrooxidation.

PubMed

Xu, Liang; Wang, Zhe; Chen, Xu; Qu, Zongkai; Li, Feng; Yang, Wensheng

2018-01-10

The development of non-precious metal electrocatalysts for renewable energy conversion and storage is compelling but greatly challenging due to low activity of the existing catalysts. Herein, the ultrathin NiAl-layered double hydroxide nanosheets (NiAl-LDH-NSs) are prepared by simple liquid-exfoliation of bulk NiAl-LDHs and first used as ethanol electrooxidation catalysts. The ultrathin two-dimensional (2D) structure ensures that the LDH nanosheets expose a greater number of active sites. More importantly, much Ni(III) active species (NiOOH) in the ultrathin nanosheets are formed by the exfoliation process, which play an authentic catalytic role in the ethanol oxidation reaction (EOR). The presence of NiOOH remarkably improves the reactivity and electrical conductivity of LDH nanosheets. These synergistic effects lead to strikingly more than 30 times enhanced EOR activity of NiAl-LDH-NSs compared to bulk NiAl-LDHs. The obtained electrocatalytic activity is also much better than those of most Ni- and LDH-based EOR catalysts reported to date. In addition, the ultrathin NiAl-LDH-NS electrocatalyst also exhibits good long-term stability (maintain 81.8% of the original value after 10000 s). This study not only provides a highly competitive EOR catalyst, but also opens new avenues toward the design of highly efficient electrode materials that have various potential applications in supercapacitor, Ni-MH battery and other electrocatalytic systems.

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.

Porous Co3O4 nanorods anchored on graphene nanosheets as an effective electrocatalysts for aprotic Li-O2 batteries

NASA Astrophysics Data System (ADS)

Yuan, Mengwei; Yang, Yan; Nan, Caiyun; Sun, Genban; Li, Huifeng; Ma, Shulan

2018-06-01

The large over-potential during the battery operation is a great obstacle for the application of Li-O2 batteries. The porous structure and electrical conductivity of the electrocatalysts are significant for the electrocatalytic performance of Li-O2 batteries. In this work, a porous Co3O4/GN nanocomposite (Co3O4 nanorods anchored on graphene nanosheets) is prepared via a facile hydrothermal method assisted with heat treatment. The unique structure of Co3O4/GN endows efficient electrocatalystic activity for Li-O2 batteries. In comparison to the Co3O4, the Co3O4/GN demonstrates a better cycle performance showing more than 40 cycles with a 1500 mAh g-1 capacity limit strategy at a current density of 300 mA g-1, and a reduced over-potential of 110 mV at high current density (1200 mA g-1). The Co3O4/GN also displays a high initial specific capacity (7600 mAh g-1) and a good reversibility in full cycle with a coulombic efficiency of 99.8% in the first cycle. The impressed cyclability, specific capacity, rate performance, and low over-potentials indicate that the as-prepared Co3O4/GN nanocomposite is a promising catalyst candidate for reversible Li-O2 batteries.

Carbon nanofiber growth optimization for their use as electrocatalyst support in proton exchange membrane (PEM) fuel cells.

PubMed

Lázaro, M J; Sebastián, D; Suelves, I; Moliner, R

2009-07-01

Carbon nanofiber (CNF) growth by catalytic decomposition of methane in a fixed-bed reactor was studied out to elucidate the influence of some important reaction conditions: temperature, space velocity and reactant partial pressure, in the morphological properties of the carbonaceous material obtained. The main objective is to synthesize a suitable carbonaceous nanomaterial to be used as support in platinum based electrocatalysts for Proton Exchange Membrane Fuel Cells (PEMFC) which improves current carbon blacks. High specific surface area is required in an electrocatalyst support since platinum dispersion is enhanced and so a cost-effective usage and high catalytic activity. Good electrical conductivity of carbon support is also required since the fuel cell power density is improved. With this proposal, characterization was carried out by nitrogen physisorption, XRD, SEM and TPO. The results were analysed by a factorial design and analysis of variance (ANOVA) in order to find an empirical correlation between operating conditions and CNF characteristics. It was found that the highest specific surface area and pore volume were found at 823 K and at a space velocity of 10 L gcat(-1) h(-1). The graphitic character of CNF, which is known to influence the electrical conductivity, presented a maximum value at temperatures between 923 K and 973 K. SEM images showed a narrow size distribution of CNF diameter between 40 and 90 nm and homogeneous appearance.

(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.

High performance robust F-doped tin oxide based oxygen evolution electro-catalysts for PEM based water electrolysis

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

Datta, Moni Kanchan; Kadakia, Karan; Velikokhatnyi, Oleg I

2013-01-01

Identification and development of non-noble metal based electro-catalysts or electro-catalysts comprising compositions with significantly reduced amounts of expensive noble metal contents (e.g. IrO{sub 2}, Pt) with comparable electrochemical performance to the standard noble metal/metal oxide for proton exchange membrane (PEM) based water electrolysis would signify a major breakthrough in hydrogen generation via water electrolysis. Development of such systems would lead to two primary outcomes: first, a reduction in the overall capital costs of PEM based water electrolyzers, and second, attainment of the targeted hydrogen production costs (<$3.00/gge delivered by 2015) comparable to conventional liquid fuels. In line with these goals,more » by exploiting a two-pronged theoretical first principles and experimental approach herein, we demonstrate for the very first time a solid solution of SnO{sub 2}:10 wt% F containing only 20 at.% IrO{sub 2} [e.g. (Sn{sub 0.80}Ir{sub 0.20})O{sub 2}:10F] displaying remarkably similar electrochemical activity and comparable or even much improved electrochemical durability compared to pure IrO{sub 2}, the accepted gold standard in oxygen evolution electro-catalysts for PEM based water electrolysis. We present the results of these studies.« less

Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

PubMed

Wang, Vincent C-C

2016-08-10

Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

Microbial synthesis of highly dispersed PdAu alloy for enhanced electrocatalysis

PubMed Central

Liu, Jiawei; Zheng, Yue; Hong, Zilan; Cai, Kai; Zhao, Feng; Han, Heyou

2016-01-01

Biosynthesis based on the reducing capacity of electrochemically active bacteria is frequently used in the reduction of metal ions into nanoparticles as an eco-friendly way to recycle metal resources. However, those bionanoparticles cannot be used directly as electrocatalysts because of the poor conductivity of cell substrates. This problem was solved by a hydrothermal reaction, which also contributes to the heteroatom doping and alloying between Pd and Au. With the protection of graphene, the aggregation of nanoparticles was successfully avoided, and the porous structure was maintained, resulting in better electrocatalytic activity and durability than commercial Pd/C under both alkaline (CH3CH2OH, 6.15-fold of mass activity) and acidic (HCOOH, 6.58-fold of mass activity) conditions. The strategy developed in this work opens up a horizon into designing electrocatalysts through fully utilizing the abundant resources in nature. PMID:27704047

Highly Active PdNi/RGO/Polyoxometalate Nanocomposite Electrocatalyst for Alcohol Oxidation.

PubMed

Hu, Jing; Wu, Xiaofeng; Zhang, Qingfan; Gao, Mingyan; Qiu, Haifang; Huang, Keke; Feng, Shouhua; Wang, Tingting; Yang, Ying; Liu, Zhelin; Zhao, Bo

2018-02-27

A PdNi/RGO/polyoxometalate nanocomposite has been successfully synthesized by a simple wet-chemical method. Characterizations such as transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy are employed to verify the morphology, structure, and elemental composition of the as-prepared nanocomposite. Inspired by the fast-developing fuel cells, the electrochemical catalytic performance of the nanocomposite toward methanol and ethanol oxidation in alkaline media is further tested. Notably, the nanocomposite exhibits excellent catalytic activity and long-term stability toward alcohol electrooxidation compared with the PdNi/RGO and commercial Pd/C catalyst. Furthermore, the electrochemical results reveal that the prepared nanocomposite is attractive as a promising electrocatalyst for direct alcohol fuel cells, in which the phosphotungstic acid plays a crucial role in enhancing the electrocatalytic activities of the catalyst.

Comparative assessment of synthetic strategies toward active platinum-rhodium-tin electrocatalysts for efficient ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Erini, Nina; Krause, Paul; Gliech, Manuel; Yang, Ruizhi; Huang, Yunhui; Strasser, Peter

2015-10-01

The present work explores the effect of autoclave-based autogenous-pressure vs. ambient pressure conditions on the synthesis and properties of carbon-supported Pt-Rh-Sn nanoparticle electrocatalysts. The Pt-Rh-Sn nanoparticles were characterized by X-ray spectroscopy, electron microscopy and mass spectroscopy and deployed as catalysts for the electrocatalytic ethanol oxidation reaction. Pt-Rh-Sn catalysts precipitated with carbon already present showed narrow particle size distribution around 7 nm, while catalysts supported on carbon after particle formation showed broader size distribution ranging from 8 to 16 nm, similar metal loadings between 40 and 48 wt.% and similar atomic ratios of Pt:Rh:Sn of 30:10:60. The highest ethanol oxidation activity at low overpotentials associated with exceptionally early ethanol oxidation onset potential was observed for ambient-pressure catalysts with the active ternary alloy phase formed in presence of the carbon supports. In contrast, catalysts prepared under ambient pressure in a two-step approach, involving alloy particle formation followed by particle separation and subsequent deposition on the carbon support, yielded the highest overall mass activities. Based on the observed synthesis-activity correlations, a comparative assessment is provided of the synthetic techniques at high vs. low pressures, and in presence and absence of carbon support. Plausible hypotheses in terms of particle dispersion and interparticle distance accounting for these observed differences are discussed.

Achieving high-powered Zn/air fuel cell through N and S co-doped hierarchically porous carbons with tunable active-sites as oxygen electrocatalysts

NASA Astrophysics Data System (ADS)

Tang, Qiaowei; Wang, Luming; Wu, Mingjie; Xu, Nengneng; Jiang, Lei; Qiao, Jinli

2017-10-01

Electrochemical reduction of oxygen is the heart of the next-generation energy technologies to fuel cells and metal-air batteries, of which the reference catalysts suffer from two critical bottlenecks lying in their insufficient electroactivities and unclear active site structures. Herein, we introduce the effectively hierarchically porous carbons (HPCs) as the active-sites enriched platform for oxygen electroreduction. Three quaternized copolymers (PUB, PAADDA and PICP) with different chemical structures are used to pursue Fe/N/S-tailored ORR electrocatalysts. The most efficient one prepared by PAADDA gives the onset potential of 0.94 V and a half-wave potential of 0.85 V in basic solution, as well as superb electroactivities of low H2O2% and high electron transfer number in both alkaline and acidic medium. Surprisingly, they all display high discharge power density as applied to Zn-air fuel cells, and the HPCs-PAADDA catalyst thrillingly reaches 516.3 mW cm-2 when catalyst loading is optimized to 5.0 mg cm-2. The results elucidate that the polymer with long aliphatic chain is propitious to trap metals to create active sites and enwrap silica template to construct uniform pore structure. Only two kinds of nitrogen configuration (pyridinic-N and graphitic-N) are found with distinct structure in these HPCs, which happens to be active sites.

Comparative studies of electrochemical properties of carbon nanotubes and nanostructured boron carbide

NASA Astrophysics Data System (ADS)

Singh, Paviter; Kaur, Gurpreet; Singh, Kulwinder; Singh, Bikramjeet; Kaur, Manjot; Kumar, Manjeet; Bala, Rajni; Kumar, Akshay

2018-05-01

Boron carbide (B4C) and carbon nanotubes (CNTs) have the potential to act as electrocatalyst as these material show bifunctional behavior. B4C and CNTs were synthesized using solvothermal method. B4C display great catalytic activity as compared to CNTs. Raman spectra confirmed the formation of nanostructured carbon nanotubes. The observed onset potential was smaller 1.58 V in case of B4C as compared to CNTs i.e. 1.96 V in cyclic voltammetry. B4C material can emerge as a promising bifunctional electrocatalyst for battery applications.

Metal-organic framework derived Fe/Fe3C@N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions.

PubMed

Song, Chunsen; Wu, Shikui; Shen, Xiaoping; Miao, Xuli; Ji, Zhenyuan; Yuan, Aihua; Xu, Keqiang; Liu, Miaomiao; Xie, Xulan; Kong, Lirong; Zhu, Guoxing; Ali Shah, Sayyar

2018-08-15

The development of simple and cost-effective synthesis methods for electrocatalysts of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is critical to renewable energy technologies. Herein, we report an interesting bifunctional HER and ORR electrocatalyst of Fe/Fe 3 C@N-doped-carbon porous hierarchical polyhedrons (Fe/Fe 3 C@N-C) by a simple metal-organic framework precursor route. The Fe/Fe 3 C@N-C polyhedrons consisting of Fe and Fe 3 C nanocrystals enveloped by N-doped carbon shells and accompanying with some carbon nanotubes on the surface were prepared by thermal annealing of Zn 3 [Fe(CN) 6 ] 2 ·xH 2 O polyhedral particles in nitrogen atmosphere. This material exhibits a large specific surface area of 182.5 m 2  g -1 and excellent ferromagnetic property. Electrochemical tests indicate that the Fe/Fe 3 C@N-C hybrid has apparent HER activity with a relatively low overpotential of 236 mV at the current density of 10 mA cm -2 and a small Tafel slope of 59.6 mV decade -1 . Meanwhile, this material exhibits excellent catalytic activity toward ORR with an onset potential (0.936 V vs. RHE) and half-wave potential (0.804 V vs. RHE) in 0.1 M KOH, which is comparable to commercial 20 wt% Pt/C (0.975 V and 0.820 V), and shows even better stability than the Pt/C. This work provides a new insight to developing multi-functional materials for renewable energy application. Copyright © 2018 Elsevier Inc. All rights reserved.

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

Recent Progress in Nanostructured Electrocatalysts for PEM Fuel Cells

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

Zhang, Sheng; Shao, Yuyan; Yin, Geping

2013-03-30

Polymer electrolyte membrane (PEM) fuel cells are attracting much attention as promising clean power sources and an alternative to conventional internal combustion engines, secondary batteries, and other power sources. Much effort from government laboratories, industry, and academia has been devoted to developing PEM fuel cells, and great advances have been achieved. Although prototype cars powered by fuel cells have been delivered, successful commercialization requires fuel cell electrocatalysts, which are crucial components at the heart of fuel cells, meet exacting performance targets. In this review, we present a brief overview of the recent progress in fuel cell electrocatalysts, which involves catalystmore » supports, Pt and Pt-based electrocatalysts, and non-Pt electrocatalysts.« less

Electro-oxidation of methanol and ethanol using PtRu/C, PtSn/C and PtSnRu/C electrocatalysts prepared by an alcohol-reduction process

NASA Astrophysics Data System (ADS)

Neto, Almir Oliveira; Dias, Ricardo R.; Tusi, Marcelo M.; Linardi, Marcelo; Spinacé, Estevam V.

PtRu/C, PtSn/C and PtSnRu/C electrocatalysts were prepared by the alcohol reduction process using ethylene glycol as the solvent and reduction agent and Vulcan Carbon XC72 as the support. The electrocatalysts were characterized by EDX, XRD and cyclic voltammetry. The electrochemical oxidation of methanol and ethanol were studied by chronoamperometry using a thin porous coating technique. The PtSn/C electrocatalyst prepared by this methodology showed superior performance compared to the PtRu/C and PtSnRu/C electrocatalysts for methanol and ethanol oxidation at room temperature.

Synthesis, characterization and optimization of platinum-alloy nanoparticle catalysts in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Srivastava, Ratndeep

Renewable hydrogen-fuelled proton exchange membrane (PEMFC) fuel cells have consistently demonstrated great promise as a future source of energy due to their high conversion efficiency, lower temperature of operation and lack of greenhouse emissions. One of the major impediments in the commercialization of polymer electrolyte membrane fuel cells is the insufficient catalytic reactivity and higher cost of Pt electrocatalysts which are utilized for the electroreduction of oxygen from air. This dissertation focuses primarily on a family of Pt alloy fuel cell electrocatalysts referred to as de-alloyed core-shell electrocatalysts. These materials are bimetallic or multimetallic nanoparticles, mostly supported on conductive supports which were first described in a dissertation by Dr. S. Koh earlier in 2009.1 De-alloyed Pt nanoparticle electrocatalysts are formed from base metal rich binary Pt-M and ternary Pt-M1-M 2 (M, M1, M2 = Cu, Co, Ni, Fe and Cr) alloy nanoparticle precursors. The precursors are transformed and activated by electrochemical selective dissolution of the less noble metal component of the precursors (de-alloying). They have shown exceptional activity for oxygen reduction reaction (ORR) in idealized electrochemical half cell measurements, in particular rotating disk electrode experiments. However, these materials were never tested or implemented in realistic Membrane Electrode Assemblies (MEA) and single PEM fuel cells. The objective of this work was to implement de-alloyed Pt particle catalysts in realistic fuel cell electrode layers as well as a detailed characterization of their behavior and stability. The major challenges of MEA implementation consists of the behavior of the new nanostructured electrocatalysts inside the complex three-phase interface of polymer membrane ionomer, liquid water, metal catalyst, support, and reactant gas. Activity measurements were followed by medium and long-term durability analysis by potential cycling of the membrane electrode assemblies to high potentials. These de-alloyed catalysts show improved resistance to electro-chemical surface area degradation as compared to state of the art available commercial Pt/C catalysts. TEM imaging with combination of electrochemical characterization helps in determining the mechanisms for particle growth and failures. Anomalous small angle x-ray scattering (ASAXS) and x-ray diffraction (XRD) techniques were also used in the characterization of these materials.

Photocatalytic methods for preparation of electrocatalyst materials

DOEpatents

Li, Wen; Kawamura, Tetsuo; Nagami, Tetsuo; Takahashi, Hiroaki; Muldoon, John; Shelnutt, John A; Song, Yujiang; Miller, James E; Hickner, Michael A; Medforth, Craig

2013-09-24

The invention relates to methods of preparing metal particles on a support material, including platinum-containing nanoparticles on a carbon support. Such materials can be used as electrocatalysts, for example as improved electrocatalysts in polymer electrolyte membrane fuel cells (PEM-FCs).

Photocatalytic methods for preparation of electrocatalyst materials

DOEpatents

Nwoga, Tochi Tudor; Kawahara, Kazuo; Li, Wen; Song, Yujiang; Shelnutt, John A; Miller, James E; Medforth, Craig John; Ueno, Yukiyoshi; Kawamura, Tetsuo

2013-12-17

The invention relates to methods of preparing metal particles on a support material, including platinum-containing nanoparticles on a carbon support. Such materials can be used as electrocatalysts, for example as improved electrocatalysts in proton exchange membrane fuel cells (PEM-FCs).

Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts

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

Ho, Ming-Hsun; Rousseau, Roger; Roberts, John A. S.

2015-09-04

Design of fast, efficient electrocatalysts for energy production and energy utilization requires a systematic approach to predict and tune the energetics of reaction intermediates and the kinetic barriers between them as well as to tune reaction conditions (e.g., concentration of reactants, acidity of the reaction medium, and applied electric potential). Thermodynamics schemes based on the knowledge of pKa values, hydride donor ability, redox potentials, and other relevant thermodynamic properties have been demonstrated to be very effective for exploring possible reaction pathways. We seek to identify high-energy intermediates, which may represent a catalytic bottleneck, and low-energy intermediates, which may represent amore » thermodynamic sink. In this study, working on a well-established Ni-based bioinspired electrocatalyst for H2 production, we performed a detailed kinetic analysis of the catalytic pathways to assess the limitations of our current (standard state) thermodynamic analysis with respect to prediction of optimal catalyst performance. To this end, we developed a microkinetic model based on extensive ab initio simulations. The model was validated against available experimental data, and it reproduces remarkably well the observed turnover rate as a function of the acid concentration and catalytic conditions, providing valuable information on the main factors limiting catalysis. Using this kinetic analysis as a reference, we show that indeed a purely thermodynamic analysis of the possible reaction pathways provides us with valuable information, such as a qualitative picture of the species involved during catalysis, identification of the possible branching points, and the origin of the observed overpotential, which are critical insights for electrocatalyst design. However, a significant limitation of this approach is understanding how these insights relate to rate, which is an equally critical piece of information. Taking our analysis a step further, we show that the kinetic model can easily be extended to different catalytic conditions by using linear free energy relationships for activation barriers based on simple thermodynamics quantities, such as pKa values. We also outline a possible procedure to extend it to other catalytic platforms, making it a general and effective way to design catalysts with improved performance.« less

Carbon-Coated Core-Shell Fe-Cu Nanoparticles as Highly Active and Durable Electrocatalysts for a Zn-Air Battery.

PubMed

Nam, Gyutae; Park, Joohyuk; Choi, Min; Oh, Pilgun; Park, Suhyeon; Kim, Min Gyu; Park, Noejung; Cho, Jaephil; Lee, Jang-Soo

2015-06-23

Understanding the interaction between a catalyst and oxygen has been a key step in designing better electrocatalysts for the oxygen reduction reaction (ORR) as well as applying them in metal-air batteries and fuel cells. Alloying has been studied to finely tune the catalysts' electronic structures to afford proper binding affinities for oxygen. Herein, we synthesized a noble-metal-free and nanosized transition metal CuFe alloy encapsulated with a graphitic carbon shell as a highly efficient and durable electrocatalyst for the ORR in alkaline solution. Theoretical models and experimental results demonstrated that the CuFe alloy has a more moderate binding strength for oxygen molecules as well as the final product, OH(-), thus facilitating the oxygen reduction process. Furthermore, the nitrogen-doped graphitic carbon-coated layer, formed catalytically under the influence of iron, affords enhanced charge transfer during the oxygen reduction process and superior durability. These benefits were successfully confirmed by realizing the catalyst application in a mechanically rechargeable Zn-air battery.

Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

PubMed

Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

2017-08-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology inherence from hollow MOFs to hollow carbon polyhedrons in preparing carbon-based electrocatalysts

DOE PAGES

Pei, Yuchen; Qi, Zhiyuan; Li, Xinle; ...

2017-02-21

Hollow carbon nanostructures are emerging as advanced electrocatalysts for the oxygen reduction reaction (ORR) due to the effective usage of active sites and the reduced dependence on expensive noble metals. Conventional preparation of these hollow structures is achieved through templates (e.g. SiO 2, CdS, and Ni 3C), which serve to retain the void interiors during carbonization, leading to an essential template-removal procedure using hazardous chemical etchants. Herein, we demonstrate the direct carbonization of unique hollow zeolitic imidazolate frameworks (ZIFs) for the synthesis of hollow carbon polyhedrons (HCPs) with well-defined morphologies. The hollow ZIF particles behave bi-functionally as a carbon sourcemore » and a morphology directing agent. This method evidences the strong morphology inherence from the hollow ZIFs during the carbonization, advancing the significant simplicity and environmental friendliness of this synthesis strategy. The as-prepared HCPs show a uniform polyhedral morphology and large void interiors, which enable their superior ORR activity. Iron can be doped into the HCPs (Fe/HCPs), providing the Fe/HCPs with enhanced ORR properties ( E 1/2 = 0.850 V) in comparison with those of HCPs. As a result, we highlight the efficient structural engineering to transform ZIFs into advanced carbon nanostructures accomplishing morphological control and high electrocatalytic activity.« less

Morphology inherence from hollow MOFs to hollow carbon polyhedrons in preparing carbon-based electrocatalysts

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

Pei, Yuchen; Qi, Zhiyuan; Li, Xinle

Hollow carbon nanostructures are emerging as advanced electrocatalysts for the oxygen reduction reaction (ORR) due to the effective usage of active sites and the reduced dependence on expensive noble metals. Conventional preparation of these hollow structures is achieved through templates (e.g. SiO 2, CdS, and Ni 3C), which serve to retain the void interiors during carbonization, leading to an essential template-removal procedure using hazardous chemical etchants. Herein, we demonstrate the direct carbonization of unique hollow zeolitic imidazolate frameworks (ZIFs) for the synthesis of hollow carbon polyhedrons (HCPs) with well-defined morphologies. The hollow ZIF particles behave bi-functionally as a carbon sourcemore » and a morphology directing agent. This method evidences the strong morphology inherence from the hollow ZIFs during the carbonization, advancing the significant simplicity and environmental friendliness of this synthesis strategy. The as-prepared HCPs show a uniform polyhedral morphology and large void interiors, which enable their superior ORR activity. Iron can be doped into the HCPs (Fe/HCPs), providing the Fe/HCPs with enhanced ORR properties ( E 1/2 = 0.850 V) in comparison with those of HCPs. As a result, we highlight the efficient structural engineering to transform ZIFs into advanced carbon nanostructures accomplishing morphological control and high electrocatalytic activity.« less

MIL-100-Fe derived N-doped Fe/Fe3C@C electrocatalysts for efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Guo, Dakai; Han, Sancan; Wang, Jiacheng; Zhu, Yufang

2018-03-01

N-doped porous Fe/Fe3C@C electrocatalysts were prepared by the pyrolysis of the hexamethylenetetramine (HMT)-incorporated MIL-100-Fe at different temperatures (700-1000 °C) under N2 atmosphere. Rotary evaporation of MIL-100-Fe and HMT solution could make more N-enriched HMT molecules enter into the pores of MIL-100-Fe, thus improving nitrogen contents of the final pyrolyzed samples. All pyrolyzed samples show porous textures with middle specific surface areas. The X-ray photoelectron spectroscopy (XPS) results demonstrate the successful introduction of N atoms into carbon framework. Sample Fe-N2-800 prepared by annealing the precursors with the HMT/MIL-100-Fe weight ratio of 2 at 800 °C exhibits the best electrocatalytic activity towards the oxygen reduction reaction (ORR) in terms of onset potential and current density because of high graphitic N and pyridinic N content. The enwrapped Fe/Fe3C nanoparticles and Fe-Nx active sites in these samples could also boost the ORR activity synergistically. Moreover, sample Fe-N2-800 demonstrates a dominant four electron reduction process, as well as excellent long-term operation stability and methanol crossover resistance. Thus, the N-doped Fe/Fe3C@C composites derived from the HMT-incorporated MIL-100-Fe are promising electrocatalysts to replace Pt/C for ORR in practical applications.

Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation.

PubMed

Rakowski DuBois, M; DuBois, Daniel L

2009-12-21

The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light-harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This Account focuses on work from our laboratories on developing molecular electrocatalysts for CO(2) reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO(2) from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox-active CO(2) carriers for concentrating CO(2). We have developed catalysts for CO(2) reduction to form CO based on a [Pd(triphosphine)(solvent)](2+) platform. Catalytic activity requires the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)](2+) units suggest that participation of a second metal in CO(2) binding may also be required for achieving very active catalysts. We also describe molecular electrocatalysts for H(2) production and oxidation based on [Ni(diphosphine)(2)](2+) complexes. Similar to palladium CO(2) reduction catalysts, these species require the optimization of both first and second coordination spheres. In this case, we use structural features of the first coordination sphere to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H(2). We use the second coordination sphere to incorporate pendant bases that assist in a number of important functions including H(2) binding, H(2) cleavage, and the transfer of protons between nickel and solution. These pendant bases, or proton relays, are likely to be important in the design of catalysts for a wide range of fuel production and fuel utilization reactions involving multiple electron and proton transfer steps. The generation of fuels from abundant substrates such as CO(2) and water remains a daunting research challenge, requiring significant advances in new inexpensive materials for light harvesting and the development of fast, stable, and efficient electrocatalysts. Although we describe progress in the development of redox-active carriers capable of concentrating CO(2) and molecular electrocatalysts for CO(2) reduction, hydrogen production, and hydrogen oxidation, much more remains to be done.

3D-hierarchical MoSe2 nanoarchitecture as a highly efficient electrocatalyst for hydrogen evolution

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Chen, Yuanfu; Qi, Fei; Wang, Xinqiang; Zhang, Wanli; Li, Yanrong; Li, Xuesong

2017-06-01

Clean hydrogen split from water by hydrogen evolution reaction (HER) is significant for sustainability, environmental emissions, and energy security. So far, it is still a big challenge to develop highly efficient noble metal-free electrocatalysts with comparable HER efficiency to platinum-based catalysts, which are mainly hindered by the intrinsic electrocatalytic property and particularly the reasonable nanostructure design of the electrocatalyst. Here we report a newly-designed three-dimensional hierarchical MoSe2 nanoarchitecture (3D-MoSe2) with outstanding HER performance. The 3D-MoSe2 is grown by chemical vapor deposition method with using perylene-3, 4, 9, 10-tetracarboxylic acid tetrapotassium salt as a seeding promoter. The as-grown 3D-MoSe2 nanoarchitecture is highly crystalline and constructed with curly few-layered vertical nanosheets onto the horizontal layer, which has much larger (~12 times) electrochemically active area and much smaller (only 2%) charge transfer resistance compared to conventional horizontal MoSe2 layer. With these advantages, the Tafel slope of 3D-MoSe2 can be as small as 47.3 mV/dev, which is the smallest record ever reported for pure MoSe2, even for pure two-dimensional transition metal dichalcogenides (2D-TMDs) catalysts. Furthermore, when 3D-MoSe2 is grown on the multiwall carbon nanotube film, its Tafel slope can be further reduced down to 32.5 mV/dec, which is close to the theoretical limit (29 mV/dec) of HER, and comparable to platinum-based electrocatalysts, making it promising as a highly efficient electrocatalyst for hydrogen evolution.

Electrocatalyst for alcohol oxidation in fuel cells

DOEpatents

Adzic, Radoslav R.; Marinkovic, Nebojsa S.

2001-01-01

Binary and ternary electrocatalysts are provided for oxidizing alcohol in a fuel cell. The binary electrocatalyst includes 1) a substrate selected from the group consisting of NiWO.sub.4 or CoWO.sub.4 or a combination thereof, and 2) Group VIII noble metal catalyst supported on the substrate. The ternary electrocatalyst includes 1) a substrate as described above, and 2) a catalyst comprising Group VIII noble metal, and ruthenium oxide or molybdenum oxide or a combination thereof, said catalyst being supported on said substrate.

Ultrasensitive thrombin detection based on direct electrochemistry of highly loaded hemoglobin spheres-encapsulated platinum nanoparticles as labels and electrocatalysts.

PubMed

Wu, Yongmei; Xu, Wenju; Bai, Lijuan; Yuan, Yali; Yi, Huayu; Chai, Yaqin; Yuan, Ruo

2013-12-15

For the first time, a sandwich-type electrochemical method was proposed for ultrasensitive thrombin (TB) detection based on direct electrochemistry of highly loaded hemoglobin spheres-encapsulated platinum nanoparticles (PtNPs@Hb) as labels and electrocatalysts. The prepared PtNPs@Hb not only exhibited good biocompatibility, excellent electrocatalytic activity, but also presented redox activity of Hb. Thus, it was employed for the fabrication of aptasensor without any extraneous redox mediators, leading to a simple preparation process for the aptasensor. The high loading of Hb spheres as redox mediators could enhance the electrochemical signal. Importantly, the synergetic electrocatalytic behavior of Hb and PtNPs toward H2O2 reduction greatly amplified the electrochemical signal, resulting in the high sensitivity of aptasensor. Consequently, under optimal conditions, the designed aptasensor exhibited a lower detection limit of 0.05 pM and wide dynamic linear range from 0.15 pM to 40 nM for TB detection. Additionally, the proposed mediator-free and signal-amplified electrochemical aptasensor showed great potential in portable and cost-effective TB sensing devices. Copyright © 2013 Elsevier B.V. All rights reserved.

Co- and defect-rich carbon nanofiber films as a highly efficient electrocatalyst for oxygen reduction

NASA Astrophysics Data System (ADS)

Kim, Il To; Song, Myeong Jun; Shin, Seoyoon; Shin, Moo Whan

2018-03-01

Many efforts are continuously devoted to developing high-efficiency, low-cost, and highly scalable oxygen reduction reaction (ORR) electrocatalysts to replace precious metal catalysts. Herein, we successfully synthesize Co- and defect-rich carbon nanofibers (CNFs) using an efficient heat treatment approach involving the pyrolysis of electrospun fibers at 370 °C under air. The heat treatment process produces Co-decorated CNFs with a high Co mass ratio, enriched pyridinic N, Co-pyridinic Nx clusters, and defect-rich carbon structures. The synergistic effects from composition and structural changes in the designed material increase the number of catalytically active sites for the ORR in an alkaline solution. The prepared Co- and defect-rich CNFs exhibit excellent ORR activities with a high ORR onset potential (0.954 V vs. RHE), a large reduction current density (4.426 mA cm-2 at 0.40 V), and a nearly four-electron pathway. The catalyst also exhibits a better long-term durability than commercial Pt/C catalysts. This study provides a novel hybrid material as an efficient ORR catalyst and important insight into the design strategy for CNF-based hybrid materials as electrochemical electrodes.

Co3O4 based non-enzymatic glucose sensor with high sensitivity and reliable stability derived from hollow hierarchical architecture.

PubMed

Tian, Liangliang; He, Gege; Cai, Yanhua; Wu, Shenping; Su, Yongyao; Yan, Hengqing; Yang, Cong; Chen, Yanling; Li, Lu

2018-02-16

Inspired by kinetics, the design of hollow hierarchical electrocatalysts through large-scale integration of building blocks is recognized as an effective approach to the achievement of superior electrocatalytic performance. In this work, a hollow, hierarchical Co 3 O 4 architecture (Co 3 O 4 HHA) was constructed using a coordinated etching and precipitation (CEP) method followed by calcination. The resulting Co 3 O 4 HHA electrode exhibited excellent electrocatalytic activity in terms of high sensitivity (839.3 μA mM -1 cm -2 ) and reliable stability in glucose detection. The high sensitivity could be attributed to the large specific surface area (SSA), ample unimpeded penetration diffusion paths and high electron transfer rate originating from the unique two-dimensional (2D) sheet-like character and hollow porous architecture. The hollow hierarchical structure also affords sufficient interspace for accommodation of volume change and structural strain, resulting in enhanced stability. The results indicate that Co 3 O 4 HHA could have potential for application in the design of non-enzymatic glucose sensors, and that the construction of hollow hierarchical architecture provides an efficient way to design highly active, stable electrocatalysts.

Co3O4 based non-enzymatic glucose sensor with high sensitivity and reliable stability derived from hollow hierarchical architecture

NASA Astrophysics Data System (ADS)

Tian, Liangliang; He, Gege; Cai, Yanhua; Wu, Shenping; Su, Yongyao; Yan, Hengqing; Yang, Cong; Chen, Yanling; Li, Lu

2018-02-01

Inspired by kinetics, the design of hollow hierarchical electrocatalysts through large-scale integration of building blocks is recognized as an effective approach to the achievement of superior electrocatalytic performance. In this work, a hollow, hierarchical Co3O4 architecture (Co3O4 HHA) was constructed using a coordinated etching and precipitation (CEP) method followed by calcination. The resulting Co3O4 HHA electrode exhibited excellent electrocatalytic activity in terms of high sensitivity (839.3 μA mM-1 cm-2) and reliable stability in glucose detection. The high sensitivity could be attributed to the large specific surface area (SSA), ample unimpeded penetration diffusion paths and high electron transfer rate originating from the unique two-dimensional (2D) sheet-like character and hollow porous architecture. The hollow hierarchical structure also affords sufficient interspace for accommodation of volume change and structural strain, resulting in enhanced stability. The results indicate that Co3O4 HHA could have potential for application in the design of non-enzymatic glucose sensors, and that the construction of hollow hierarchical architecture provides an efficient way to design highly active, stable electrocatalysts.

Develop high activity, low cost non-PGM fuel cell electrocatalyst and stable supports

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

Colon-Mercado, H. R.; Elvington, M. C.; Garcia-Diaz, B. L.

2016-09-28

A unique approach has been developed to probe the non-PGM catalyst active site for the Oxygen Reduction Reaction (ORR) for PEMFC. Iron based functionalities have been engineered into Metallic Organic Framework (MOF) catalysts to evaluate their impact on activity for the ORR. A series of FePhen@MOF catalysts have been synthesized with varying [Fe] to investigate the effect on electrochemical and electrocatalytic properties. The magnitude of the Fe II/III redox couple and the electrochemical surface area are analyzed to determine if there is a correlation between [Fe] and the ORR onset potential and/or the relative number of active sites.

Homogeneous deposition-assisted synthesis of iron-nitrogen composites on graphene as highly efficient non-precious metal electrocatalysts for microbial fuel cell power generation

NASA Astrophysics Data System (ADS)

Liu, Yuan; Jin, Xiao-Jun; Dionysiou, Dionysios D.; Liu, Hong; Huang, Yu-Ming

2015-03-01

This work proposed a novel strategy for synthesizing highly efficient non-precious metal oxygen reduction reaction (ORR) electrocatalysts. Fe complexes were homogeneously deposited (HD) on graphene oxide through in situ hydrolysis of urea, followed by two-step pyrolysis under Ar and NH3 atmospheres, resulting in formation of Fe- and N-functionalized graphene (HD-FeN/G). The morphology, crystalline structure and elemental composition of HD-FeN/G were characterized. ORR activity was evaluated by using a rotary disk electrode (RDE) electrochemical system. HD improved the loading and distribution of the Fe-Nx composites on graphene. The ORR activity of the as-prepared HD-FeN/G in neutral medium was comparable to that of the state-of-the-art commercial Pt/C and significantly superior to a FeN/G counterpart produced via traditional approach. The ORR electron transfer number of HD-FeN/G was as high as 3.83 ± 0.08, which suggested that ORR catalysis proceeds through a four-electron pathway. HD-FeN/G was used as a cathodic electrocatalyst in microbial fuel cells (MFCs), and the resultant HD-FeN/G-MFC showed comparable voltage output and maximum power density to those of Pt/C-MFC. The HD-FeN/G-MFC achieved a maximum power density of 885 mW m-2, which was much higher than that of FeN/G-MFC (708 mW m-2). These findings demonstrate that HD-FeN/G produced through the novel synthesis strategy proposed in this work would be a good candidate as cathodic electrocatalyst in MFCs.

Fabrication of hierarchically branched SnO2 nanowires by two-step deposition method and their applications to electrocatalyst support and Li ion electrode

NASA Astrophysics Data System (ADS)

Lee, Sang Ho; Jo, Yong-Ryun; Noh, Yuseong; Kim, Bong-Joong; Kim, Won Bae

2017-11-01

This paper reports hierarchically branched structures of tin dioxide nanowires for use in electrochemical energy conversion and storage electrode systems. The shallow tin dioxide branches are epitaxially grown on the tin dioxide nanowire backbones that are directly formed on current collectors. The branched tin dioxide nanowires are applied as anode electrodes for lithium-ion batteries, while palladium-incorporated branched nanowires are utilized as electrocatalysts for ethanol electrooxidation reactions. The structural benefits of these hierarchical platforms, such as enlarged electrochemical active surface area, void space formed between the branched structures, and conformal contact of the electroactive materials with current collectors, play important roles in improving the electrochemical Li-ion storage as well as electrocatalytic activity.

Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance.

PubMed

Song, Fang; Bai, Lichen; Moysiadou, Aliki; Lee, Seunghwa; Hu, Chao; Liardet, Laurent; Hu, Xile

2018-06-27

Water splitting is the essential chemical reaction to enable the storage of intermittent energies such as solar and wind in the form of hydrogen fuel. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting. Though metal oxides had been reported as OER electrocatalysts more than half a century ago, the recent interest in renewable energy storage has spurred a renaissance of the studies of transition metal oxides as Earth-abundant and nonprecious OER catalysts. This Perspective presents major progress in several key areas of the field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials. A personal overview of the past achievements and future challenges is also provided.

Rhodium Nanoparticle-mesoporous Silicon Nanowire Nanohybrids for Hydrogen Peroxide Detection with High Selectivity

PubMed Central

Song, Zhiqian; Chang, Hucheng; Zhu, Weiqin; Xu, Chenlong; Feng, Xinjian

2015-01-01

Developing nanostructured electrocatalysts, with low overpotential, high selectivity and activity has fundamental and technical importance in many fields. We report here rhodium nanoparticle and mesoporous silicon nanowire (RhNP@mSiNW) hybrids for hydrogen peroxide (H2O2) detection with high electrocatalytic activity and selectivity. By employing electrodes that loaded with RhNP@mSiNW nanohybrids, interference caused from both many electroactive substances and dissolved oxygen were eliminated by electrochemical assaying at an optimal potential of +75 mV. Furthermore, the electrodes exhibited a high detection sensitivity of 0.53 μA/mM and fast response (< 5 s). This high-performance nanohybrid electrocatalyst has great potential for future practical application in various oxidase-base biosensors. PMID:25588953

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.

Fabrication of Highly Stable and Efficient PtCu Alloy Nanoparticles on Highly Porous Carbon for Direct Methanol Fuel Cells.

PubMed

Khan, Inayat Ali; Qian, Yuhong; Badshah, Amin; Zhao, Dan; Nadeem, Muhammad Arif

2016-08-17

Boosting the durability of Pt nanoparticles by controlling the composition and morphology is extremely important for fuel cells commercialization. We deposit the Pt-Cu alloy nanoparticles over high surface area carbon in different metallic molar ratios and optimize the conditions to achieve desired material. The novel bimetallic electro-catalyst {Pt-Cu/PC-950 (15:15%)} offers exceptional electrocatalytic activity when tested for both oxygen reduction reaction and methanol oxidation reactions. A high mass activity of 0.043 mA/μgPt (based on Pt mass) is recorded for ORR. An outstanding longevity of this electro-catalyst is noticed when compared to 20 wt % Pt loaded either on PC-950 or commercial carbon. The high surface area carbon support offers enhanced activity and prevents the nanoparticles from agglomeration, migration, and dissolution as evident by TEM analysis.

The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells.

PubMed

Liu, Qingtao; Liu, Xiaofang; Zheng, Lirong; Shui, Jianglan

2018-01-26

The environmentally friendly synthesis of highly active Fe-N-C electrocatalysts for proton-exchange membrane fuel cells (PEMFCs) is desirable but remains challenging. A simple and scalable method is presented to fabricate Fe II -doped ZIF-8, which can be further pyrolyzed into Fe-N-C with 3 wt % of Fe exclusively in Fe-N 4 active moieties. Significantly, this Fe-N-C derived acidic PEMFC exhibits an unprecedented current density of 1.65 A cm -2 at 0.6 V and the highest power density of 1.14 W cm -2 compared with previously reported NPMCs. The excellent PEMFC performance can be attributed to the densely and atomically dispersed Fe-N 4 active moieties on the small and uniform catalyst nanoparticles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-doped carbon@Ni-Al2O3 nanosheet array@graphene oxide composite as an electrocatalyst for hydrogen evolution reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Wang, Juan; Qiu, Tian; Chen, Xu; Lu, Yanluo; Yang, Wensheng

2015-10-01

An NiAl-layered double-hydroxide (NiAl-LDH) nanosheet array is grown on a graphene oxide (GO) substrate (NiAl-LDH@GO) by the hydrothermal method. The NiAl-LDH@GO is used as the precursor to synthetize an N-doped carbon@Ni-Al2O3 nanosheet array@GO composite (N-C@Ni-Al2O3@GO) by coating with dopamine followed by calcination. The N-C@Ni-Al2O3@GO is used as a non-noble metal electrocatalyst for hydrogen evolution reaction in alkaline medium, and exhibits high electrocatalytic activity with low onset overpotential (-75 mV). The improved electrocatalytic performance of N-C@Ni-Al2O3@GO arises from its intrinsic features. First, it has a high specific surface area with the Ni nanoparticles in the composite dispersed well and the sizes of Ni nanoparticles are small, which lead to the exposure of more active sites for electrocatalysis. Second, there is a synergistic effect between the Ni nanoparticles and the N-C coating layer, which is beneficial to reduce the activation energy of the Volmer step and improve the electrocatalytic activity. Third, the N-C coating layer and the XC-72 additive can form an electrically conductive network, which serves as a bridge for the transfer of electrons from the electrode to the Ni nanoparticles.

Ultrathin layered double hydroxide nanosheets with Ni(III) active species obtained by exfoliation for highly efficient ethanol electrooxidation

PubMed Central

Xu, Liang; Wang, Zhe; Chen, Xu; Qu, Zongkai; Li, Feng; Yang, Wensheng

2018-01-01

The development of non-precious metal electrocatalysts for renewable energy conversion and storage is compelling but greatly challenging due to low activity of the existing catalysts. Herein, the ultrathin NiAl-layered double hydroxide nanosheets (NiAl-LDH-NSs) are prepared by simple liquid-exfoliation of bulk NiAl-LDHs and first used as ethanol electrooxidation catalysts. The ultrathin two-dimensional (2D) structure ensures that the LDH nanosheets expose a greater number of active sites. More importantly, much Ni(III) active species (NiOOH) in the ultrathin nanosheets are formed by the exfoliation process, which play an authentic catalytic role in the ethanol oxidation reaction (EOR). The presence of NiOOH remarkably improves the reactivity and electrical conductivity of LDH nanosheets. These synergistic effects lead to strikingly more than 30 times enhanced EOR activity of NiAl-LDH-NSs compared to bulk NiAl-LDHs. The obtained electrocatalytic activity is also much better than those of most Ni- and LDH-based EOR catalysts reported to date. In addition, the ultrathin NiAl-LDH-NS electrocatalyst also exhibits good long-term stability (maintain 81.8% of the original value after 10000 s). This study not only provides a highly competitive EOR catalyst, but also opens new avenues toward the design of highly efficient electrode materials that have various potential applications in supercapacitor, Ni-MH battery and other electrocatalytic systems. PMID:29622818

An electrochemical impedance spectroscopy study of polymer electrolyte membrane fuel cells electrocatalyst single wall carbon nanohorns-supported.

PubMed

Brandão, Lúcia; Boaventura, Marta; Passeira, Carolina; Gattia, Daniele Mirabile; Marazzi, Renzo; Antisari, Marco Vittori; Mendes, Adélio

2011-10-01

Electrochemical impedance spectroscopy (EIS) was used to study the polymer electrolyte membrane fuel cells (PEMFC) performance when using single wall carbon nanohorns (SWNH) to support Pt nanoparticles. Additionally, as-prepared and oxidized SWNH Pt-supports were compared with conventional carbon black. Two different oxidizing treatments were considered: oxygen flow at 500 degrees C and reflux in an acid solution at 85 degrees C. Both oxidizing treatments increased SWNH surface area; oxygen treatment increased surface area 4 times while acid treatment increased 2.6 times. The increase in surface area should be related to the opening access to the inner tube of SWNH. Acid treatment of SWNH increased chemical fragility and decreased electrocatalyst load in comparison with as-prepared SWNH. On the other hand, the oxygen treated SWNH sample allowed to obtain the highest electrocatalyst load. The use of as-prepared and oxygen treated SWNH showed in both cases catalytic activities 60% higher than using conventional carbon black as electrocatalyst support in PEMFC. Moreover, EIS analysis indicated that the major improvement in performance is related to the cathode kinetics in the as-prepared SWNH sample, while concerning the oxidized SWNH sample, the improvements are related to the electrokinetics in both anode and cathode electrodes. These improvements should be related with differences in the hydrophobic character between SWNH and carbon black.

Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

PubMed

Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, Nebojsa S; More, Karren; Adzic, Radoslav R

2013-01-09

Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

Ultrafine Co Nanoparticles Encapsulated in Carbon-Nanotubes-Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction.

PubMed

Chen, Ziliang; Wu, Renbing; Liu, Yang; Ha, Yuan; Guo, Yanhui; Sun, Dalin; Liu, Miao; Fang, Fang

2018-06-10

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm -2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H 2 SO 4 , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evident Enhancement of Photoelectrochemical Hydrogen Production by Electroless Deposition of M-B (M = Ni, Co) Catalysts on Silicon Nanowire Arrays.

PubMed

Yang, Yong; Wang, Mei; Zhang, Peili; Wang, Weihan; Han, Hongxian; Sun, Licheng

2016-11-09

Modification of p-type Si surface by active and stable earth-abundant electrocatalysts is an effective strategy to improve the sluggish kinetics for the hydrogen evolution reaction (HER) at p-Si/electrolyte interface and to develop highly efficient and low-cost photocathodes for hydrogen production from water. To this end, Si nanowire (Si-NW) array has been loaded with highly efficient electrocatalysts, M-B (M = Ni, Co), by facile and quick electroless plating to build M-B catalyst-modified Si nanowire-array-textured photocathodes for water reduction to H 2 . Compared with the bare Si-NW array, composite Si-NWs/M-B arrays display evidently enhanced photoelectrochemical (PEC) performance. The onset potential (V phon ) of cathodic photocurrent is positively shifted by 530-540 mV to 0.44-0.45 V vs RHE, and the short-circuit current density (J sc ) is up to 19.5 mA cm -2 in neutral buffer solution under simulated 1 sun illumination. Impressively, the half-cell photopower conversion efficiencies (η hc ) of the optimized Si-NWs/Co-B (2.53%) and Si-NWs/Ni-B (2.45%) are comparable to that of Si-NWs/Pt (2.46%). In terms of the large J sc , V phon , and η hc values, as well as the high Faradaic efficiency, Si-NWs/M-B electrodes are among the top performing Si photocathodes which are modified with HER electrocatalysts but have no buried solid/solid junction.

Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications

NASA Astrophysics Data System (ADS)

Mellinger, Zachary J.

One of the major challenges in the commercialization of proton exchange membrane fuel cells (PEMFC) is the cost, and low CO tolerance of the anode electrocatalyst material. The anode typically requires a high loading of precious metal electrocatalyst (Pt or Pt--Ru) to obtain a useful amount of electrical energy from the electrooxidation of methanol (CH3OH) or ethanol (C2H5OH). The complete electro--oxidation of methanol or ethanol on these catalysts produces strongly adsorbed CO on the surface, which reduces the activity of the Pt or Pt--Ru catalysts. Another major disadvantage of these electrocatalyst components is the scarcity and consequently high price of both Pt and Ru. Tungsten monocarbide (WC) has shown similar catalytic properties to Pt, leading to the utilization of WC and metal modified WC as replacements to Pt and Pt--Ru. In this thesis we investigated WC and Pt--modified WC as a potentially more CO--tolerant electrocatalysts as compared to pure Pt. These catalysts would reduce or remove the high loading of Pt used industrially. The binding energy of CO, estimated using temperature programmed desorption, is weaker on WC and Pt/WC than on Pt, suggesting that it should be easier to oxidize CO on WC and Pt/WC. This hypothesis was verified using cyclic voltammetry to compare the electro--oxidation of CO on WC, Pt/WC, and Pt supported on carbon substrates, which showed a lower voltage for the onset of oxidation of CO on WC and Pt/WC than on Pt. After observing these improved properties on the Pt/WC catalysts, we decided to expand our studies to investigate Pd--modified WC as Pd is less expensive than Pt and has shown more ideal properties for alcohol electrocatalysis in alkaline media. Pd/WC showed a lower binding energy of CO than both its parent metal Pd as well as Pt. Then, density functional theory (DFT) calculations were performed to determine how the presence of Pd affected the bonding of methanol and ethanol on the WC surface. The DFT studies showed that the binding energies for methanol and methoxy as well as ethanol and ethoxy on one monolayer (ML) Pd/WC are more similar to Pd than to WC. This predicts that the ML Pd/WC surface should have catalytic properties more similar to Pd than to WC. Ultra--high vacuum (UHV) experiments were then performed to determine the reaction products and pathways for methanol and ethanol on Pd(111), WC, and Pd/WC surfaces. These studies showed that the WC surface was very active toward the O--H bond cleavage to produce a methoxy intermediate, although WC was also undesirable because it was active for C--O bond scission and less active for the C--H bond scission. Adding Pd on WC enhanced the scission of the C--H bonds of methoxy while removing the C--O bond scission reaction pathway, suggesting a synergistic effect of using Pd/WC as electrocatalysts for methanol and ethanol decomposition. Dissociation of water, which is important for CO tolerance, was also investigated using UHV techniques with the conclusion that both the WC and Pd/WC surfaces dissociated water. The predictions from UHV studies was verified in electrochemical experiments using cyclic voltammetry (CV) and chronoamperometry (CA) measurements of electro--oxidation of methanol and ethanol in an alkaline environment. These experiments showed that Pd/WC was electrochemically active towards methanol and ethanol decomposition and has greater electrochemical stability over time than pure Pd, potentially due to higher CO tolerance for Pd/WC.

Multiscale Principles To Boost Reactivity in Gas-Involving Energy Electrocatalysis.

PubMed

Tang, Cheng; Wang, Hao-Fan; Zhang, Qiang

2018-04-17

Various gas-involving energy electrocatalysis, including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER), has witnessed increasing concerns recently for the sake of clean, renewable, and efficient energy technologies. However, these heterogeneous reactions exhibit sluggish kinetics due to multistep electron transfer and only occur at triple-phase boundary regions. Up to now, tremendous attention has been attracted to develop cost-effective and high-performance electrocatalysts to boost the electrocatalytic activities as promising alternatives to noble metal counterparts. In addition to the prolific achievements in materials science, the advances in interface chemistry are also very critical in consideration of the complex phenomena proceeded at triple-phase boundary regions, such as mass diffusion, electron transfer, and surface reaction. Therefore, insightful principles and effective strategies for a comprehensive optimization, ranging from active sites to electrochemical interface, are necessary to fully enhance the electrocatalytic performance aiming at practical device applications. In this Account, we give an overview of our recent attempts toward efficient gas-involving electrocatalysis with multiscale principles from the respect of electronic structure, hierarchical morphology, and electrode interface step by step. It is widely accepted that the intrinsic activity of individual active sites is directly influenced by their electronic structure. Heteroatom doping and topological defects are demonstrated to be the most effective strategies for metal-free nanocarbon materials, while the cationic (e.g., Ni, Fe, Co, Sn) and anionic (e.g., O, S, OH) regulation is revealed to be a promising method for transition metal compounds, to alter the electronic structure and generate high activity. Additionally, the apparent activity of the whole electrocatalyst is significantly impacted by its hierarchical morphology. The active sites of nanocarbon materials are expected to be enriched on the surface for a full exposure and utilization; the hybridization of other active components with nanocarbon materials should achieve a uniform dispersion in nanoscale and a strongly coupled interface, thereby ensuring the electron transfer and boosting the activity. Furthermore, steady and favorable electrochemical interfaces are strongly anticipated in working electrodes for optimal reaction conditions. The powdery electrocatalysts are suggested to be constructed into self-supported electrodes for more efficient and stable catalysis integrally, while the local microenvironment can be versatilely modified by ionic liquids with more beneficial gas solubility and hydrophobicity. Collectively, with the all-round regulation of the electronic structure, hierarchical morphology, and electrode interface, the electrocatalytic performances are demonstrated to be comprehensively facilitated. Such multiscale principles stemmed from the in-depth insights on the structure-activity relationship and heterogeneous reaction characteristics will no doubt pave the way for the future development of gas-involving energy electrocatalysis, and also afford constructive inspirations in a broad range of research including CO 2 reduction reaction, hydrogen peroxide production, nitrogen reduction reaction, and other important electrocatalytic activation of small molecules.

Nanofibrous electrocatalysts

DOEpatents

Liu, Di Jia; Shui, Jianglan; Chen, Chen

2016-05-24

A nanofibrous catalyst and method of manufacture. A precursor solution of a transition metal based material is formed into a plurality of interconnected nanofibers by electro-spinning the precursor solution with the nanofibers converted to a catalytically active material by a heat treatment. Selected subsequent treatments can enhance catalytic activity.

Biomimetics with a self-assembled monolayer of catalytically active tethered isoalloxazine on Au.

PubMed

Calvo, Ernesto J; Rothacher, M Silvina; Bonazzola, Cecilia; Wheeldon, Ian R; Salvarezza, Roberto C; Vela, Maria Elena; Benitez, Guillermo

2005-08-16

A new biomimetic nanostructured electrocatalyst comprised of a self-assembled monolayer (SAM) of flavin covalently attached to Au by reaction of methylformylisoalloxazine with chemisorbed cysteamine is introduced. Examinations by Fourier transform infrared spectroscopy and scanning tunneling microscopy (STM) show that the flavin molecules are oriented perpendicular to the surface with a 2 nm separation between flavin molecules. As a result of the contrast observed in the STM profiles between areas only covered by unreacted cysteamine and those covered by flavin-cysteamine moieties, it can be seen that the flavin molecules rise 0.7 nm above the chemisorbed cysteamines. The SAM flavin electrocatalyst undergoes fast electron transfer with the underlying Au and shows activity toward the oxidation of enzymatically active beta-NADH at pH 7 and very low potential (-0.2 V vs Ag/AgCl), a requirement for use in an enzymatic biofuel cell, and a 100-fold increase in activity with respect to the collisional reaction in solution.

Control of Architecture in Rhombic Dodecahedral Pt–Ni Nanoframe Electrocatalysts

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

Becknell, Nigel; Son, Yoonkook; Kim, Dohyung

Platinum-based alloys are known to demonstrate advanced properties in electrochemical reactions that are relevant for proton exchange membrane fuel cells and electrolyzers. Further development of Pt alloy electrocatalysts relies on the design of architectures with highly active surfaces and optimized utilization of the expensive elpment, Pt. Here, we show that the three-dimensional Pt anisotropy of Pt-Ni rhombic dodecahedra can be tuned by controlling the ratio between Pt and Ni precursors such that either a completely hollow nanoframe or a new architecture, the excavated nanoframe, can be obtained. The excavated nanoframe showed similar to 10 times higher specific and similar tomore » 6 times higher mass activity for the oxygen reduction reaction than Pt/C, and twice the mass activity of the hollow nanoframe. The high activity is attributed to enhanced Ni content in the near-surface region and the extended two-dimensional sheet structure within the nanoframe that minimizes the number of buried Pt sites.« less

Graphene-cobaltite-Pd hybrid materials for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells.

PubMed

Sharma, Chandra Shekhar; Awasthi, Rahul; Singh, Ravindra Nath; Sinha, Akhoury Sudhir Kumar

2013-12-14

Hybrid materials comprising of Pd, MCo2O4 (where M = Mn, Co or Ni) and graphene have been prepared for use as efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells. Structural and electrochemical characterizations were carried out using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, chronoamperometry and cyclic, CO stripping, and linear sweep voltammetries. The study revealed that all the three hybrid materials are active for both methanol oxidation (MOR) and oxygen reduction (ORR) reactions in 1 M KOH. However, the Pd-MnCo2O4/GNS hybrid electrode exhibited the greatest MOR and ORR activities. This active hybrid electrode has also outstanding stability under both MOR and ORR conditions, while Pt- and other Pd-based catalysts undergo degradation under similar experimental conditions. The Pd-MnCo2O4/GNS hybrid catalyst exhibited superior ORR activity and stability compared to even Pt in alkaline solutions.

Non-noble electrocatalysts for alkaline fuel cells

NASA Technical Reports Server (NTRS)

Sarangapani, S.; Lessner, P.; Manoukian, M.; Giner, J.

1989-01-01

The doping of solid phase precursors followed by pyrolysis or the copyrolysis of gas phase precursors has allowed us to produce catalysts with good activity toward oxygen reduction. Efforts are currently underway to better understand the reasons for the catalytic activity of the bulk doped catalysts with a view toward further improving their activity.

Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

PubMed Central

Tran, Phong D.; Tran, Thu V.; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

2017-01-01

Molybdenum sulfides are very attractive noble-metal free electrocatalysts for the hydrogen evolution reaction (HER) from water. Atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx) which displays significantly higher HER activity compared to its crystalline counterpart. Here we show that HER–active a-MoSx, prepared either as nanoparticles or as films, is a molecular–based coordination polymer consisting of discrete [Mo3S13]2– building blocks. Of the three terminal disulfide (S22–) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimisation of this HER electrocatalyst as an alternative to platinum. PMID:26974410

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

Shi, Qiurong; Zhu, Chengzhou; Bi, Cuixia

Intermetallic nanocrystals are currently receiving extensive attention due to their well-defined crystal structures, highly ordered atomic distribution and superior structural stability that endow them with optimized catalytic activities, stabilities and high selectivity for use as electrocatalysts for fuel cells.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution.

PubMed

Hua, Wei; Liu, Huanyan; Wang, Jian-Gan; Wei, Bingqing

2017-12-06

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O) x ·MoO x nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O) x and amorphous MoO x , as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm -2 , a low Tafel slope of 54 mV dec -1 , and excellent cycling stability.

Self-Supported Ni(P, O)x·MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution

PubMed Central

Hua, Wei; Liu, Huanyan

2017-01-01

Earth-abundant and low-cost catalysts with excellent electrocatalytic hydrogen evolution reaction (HER) activity in alkaline solution play an important role in the sustainable production of hydrogen energy. In this work, a catalyst of Ni(P, O)x·MoOx nanowire array on nickel foam has been prepared via a facile route for efficient alkaline HER. Benefiting from the collaborative advantages of Ni(P, O)x and amorphous MoOx, as well as three-dimensional porous conductive nickel scaffold, the hybrid electrocatalyst shows high catalytic activity in 1 M KOH aqueous solution, including a small overpotential of 59 mV at 10 mA cm−2, a low Tafel slope of 54 mV dec-1, and excellent cycling stability. PMID:29210991

Co(II)-Doped Cd-MOF as an Efficient Water Oxidation Catalyst: Doubly Interpenetrated Boron Nitride Network with the Encapsulation of Free Ligand Containing Pyridine Moieties.

PubMed

Maity, Kartik; Bhunia, Kousik; Pradhan, Debabrata; Biradha, Kumar

2017-11-01

Development of an efficient and inexpensive water oxidation electrocatalyst using the earth-abundant elements is still far to go. Herein, a novel strategy has been demonstrated for developing the OER electrocatalyst by doping Co(II) in to a three-dimensional Cd-based MOF that contains a naked pyridine moieties in the form of uncoordinated ligand. Electrochemically active CoCd-MOF was resulted through the doping of Co(II) into the inactive Cd-MOF. CoCd-MOF exhibited very high catalytic activity in water oxidation reaction. An overpotential of 353 mV is required to produce an anodic current density of 1 mA/cm 2 under alkaline conditions. Further, the CoCd-MOF exhibits remarkable recyclability over 1000 cycles.

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

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

Homogeneous coating of ionomer on electrocatalyst assisted by polybenzimidazole as an adhesive layer and its effect on fuel cell performance

NASA Astrophysics Data System (ADS)

Yang, Zehui; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-12-01

The fabrication of homogeneous ionomer distribution in fuel cell catalyst layers is necessary and important to improve the platinum utilization as well as the power density. Here, we focus on the effect of poly[2,2‧-(2,6-pyridine)-5,5‧-bibenzimidazole] (PyPBI) wrapped on multi-walled carbon nanotubes (MWNTs) for anchoring Nafion ionomer to the electrocatalyst, in which PyPBI functions as the binding sites for platinum nanoparticles (Pt-NPs) used as a catalyst. Based on the result using a control composite without having PyPBI, a strong interaction of the Nafion onto the PyPBI layer is recognized. Importantly, we find that the membrane-electrode assembly (MEA) shows a much higher maximum power density than that of the MEA without PyPBI. A homogeneous coating of Nafion on the electrocatalyst using the PyPBI forms a long-range network of the ionomer, leading to an improved Pt-NP utilization efficiency as well as an enhanced power density of the MEA.

Cobalt Phosphide Hollow Polyhedron as Efficient Bifunctional Electrocatalysts for the Evolution Reaction of Hydrogen and Oxygen.

PubMed

Liu, Mengjia; Li, Jinghong

2016-01-27

The development of efficient and low-cost hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) electrocatalysts for renewable-energy conversion techniques is highly desired. A kind of hollow polyhedral cobalt phosphide (CoP hollow polyhedron) is developed as efficient bifunctional electrocatalysts for HER and OER templated by Co-centered metal-organic frameworks. The as-prepared CoP hollow polyhedron, which have large specific surface area and high porosity providing rich catalytic active sites, show excellent electrocatalytic performances for both HER and OER in acidic and alkaline media, respectively, with onset overpotentials of 35 and 300 mV, Tafel slopes of 59 and 57 mV dec(-1), and a current density of 10 mA cm(-2) at overpotentials of 159 and 400 mV for HER and OER, respectively, which are remarkably superior to those of particulate CoP (CoP particles) and comparable to those of commercial noble-metal catalysts. In addition, the CoP hollow polyhedron also show good durability after long-term operations.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions.

PubMed

Jiao, Yan; Zheng, Yao; Jaroniec, Mietek; Qiao, Shi Zhang

2015-04-21

A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

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.

A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Ma, Juanjuan; Liu, Lin; Chen, Qian; Yang, Min; Wang, Danping; Tong, Zhiwei; Chen, Zhong

2017-03-01

Elaborate design and synthesis of efficient and stable non-Pt electrocatalysts for some renewable energy related conversion/storage processes are one of the major goals of sustainable chemistry. Herein, we report a facile method to fabricate Co porphyrin functionalized electrochemically reduced graphene oxide (CoTMPyP/ERGO) thin film by direct assembly of oppositely charged tetrakis(N-methylpyridyl) porphyrinato cobalt (CoTMPyP) and GO nanosheets under mild conditions followed by an electrochemical reduction procedure. STEM analysis confirms that CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. The electrochemical properties of CoTMPyP/ERGO were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. The results demonstrate that CoTMPyP/ERGO nanohybrid film can serve as excellent electrocatalyst for hydrogen evolution in alkaline solution with high activity and stability. The intimate contact and efficient electron transfer between CoTMPyP and ERGO, as well as the crumpled structure, contribute to the improvement of the electrocatalytic performance.

Ce-Doped NiFe-Layered Double Hydroxide Ultrathin Nanosheets/Nanocarbon Hierarchical Nanocomposite as an Efficient Oxygen Evolution Catalyst.

PubMed

Xu, Huajie; Wang, Bingkai; Shan, Changfu; Xi, Pinxian; Liu, Weisheng; Tang, Yu

2018-02-21

Developing convenient doping to build highly active oxygen evolution reaction (OER) electrocatalysts is a practical process for solving the energy crisis. Herein, a facile and low-cost in situ self-assembly strategy for preparing a Ce-doped NiFe-LDH nanosheets/nanocarbon (denoted as NiFeCe-LDH/CNT, LDH = layered double hydroxide and CNT = carbon nanotube) hierarchical nanocomposite is established for enhanced OER, in which the novel material provides its overall advantageous structural features, including high intrinsic catalytic activity, rich redox properties, high, flexible coordination number of Ce 3+ , and strongly coupled interface. Further experimental results indicate that doped Ce into NiFe-LDH/CNT nanoarrays brings about the reinforced specific surface area, electrochemical surface area, lattice defects, and the electron transport between the LDH nanolayered structure and the framework of CNTs. The effective synergy prompts the NiFeCe-LDH/CNT nanocomposite to possess superior OER electrocatalytic activity with a low onset potential (227 mV) and Tafel slope (33 mV dec -1 ), better than the most non-noble metal-based OER electrocatalysts reported. Therefore, the combination of the remarkable catalytic ability and the facile normal temperature synthesis conditions endows the Ce-doped LDH nanocomposite as a promising catalyst to expand the field of lanthanide-doped layered materials for efficient water-splitting electrocatalysis with scale-up potential.

Cobalt nanoparticles/nitrogen-doped graphene with high nitrogen doping efficiency as noble metal-free electrocatalysts for oxygen reduction reaction.

PubMed

Liang, Jingwen; Hassan, Mehboob; Zhu, Dongsheng; Guo, Liping; Bo, Xiangjie

2017-03-15

Nitrogen-doped graphene (N/GR) has been considered as active metal-free electrocatalysts for oxygen reduction reaction (ORR). However, the nitrogen (N) doping efficiency is very low and only few N atoms are doped into the framework of GR. To boost the N doping efficiency, in this work, a confined pyrolysis method with high N doping efficiency is used for the preparation of cobalt nanoparticles/nitrogen-doped GR (Co/N/GR). Under the protection of SiO 2 , the inorganic ligand NH 3 in cobalt amine complex ([Co(NH 3 ) 6 ] 3+ ) is trapped in the confined space and then can be effectively doped into the framework of GR without the introduction of any carbon residues. Meanwhile, due to the redox reaction between the cobalt ions and carbon atoms of GR, Co nanoparticles are supported into the framework of N/GR. Due to prevention of GR layer aggregation with SiO 2 , the Co/N/GR with high dispersion provides sufficient surface area and maximum opportunity for the exposure of Co nanoparticles and active sites of N dopant. By combination of enhanced N doping efficiency, Co nanoparticles and high dispersion of GR sheets, the Co/N/GR is remarkably active, cheap and selective noble-metal free catalysts for ORR. Copyright © 2016 Elsevier Inc. All rights reserved.

Porous Ni0.1Mn0.9O1.45 microellipsoids as high-performance anode electrocatalyst for microbial fuel cells.

PubMed

Zeng, Lizhen; Zhang, Wenguang; Xia, Pan; Tu, Wenqiang; Ye, Changchun; He, Miao

2018-04-15

A novel bi-component composite of porous self-assembled micro-/nanostructured Ni 0.1 Mn 0.9 O 1.45 microellipsoids as high-performance anode electrocatalyst for microbial fuel cells (MFCs) is successfully synthesized via a simple coprecipitation reaction in microemulsion and calcination method in air atmosphere. The morphology and structural characterization indicate that the as-fabricated Ni 0.1 Mn 0.9 O 1.45 product is consist of Mn 2 O 3 and NiMn 2 O 4 (n(Mn 2 O 3) : n(NiMn 2 O 4 ) = 0.35: 0.1) and has a porous microellipsoidal morphology. The microellipsoids are compose of numerous layered micro-/nanostructured blocks and the special porous microellipsoids structure of Ni 0.1 Mn 0.9 O 1.45 offers a large specific surface area for bacteria adhesion. The porous Ni 0.1 Mn 0.9 O 1.45 microellipsoids as anode electrocatalyst for MFCs exhibits excellent electrocatalytic activity to promote the extracellular electron transfer (EET) between the anode and bacteria, hence improves the performance of MFC. The MFC equipped with Ni 0.1 Mn 0.9 O 1.45 /CF anode achieves a maximum power density of 1.39 ± 0.02Wm -2 , is significantly higher than that of commercial carbon felt anode. This work proposes a new method for the synthesis of high-performance and environmentally friendly anode electrocatalyst for MFCs. Copyright © 2017 Elsevier B.V. All rights reserved.

A Metal-Organic Framework Derived Porous Cobalt Manganese Oxide Bifunctional Electrocatalyst for Hybrid Na-Air/Seawater Batteries.

PubMed

Abirami, Mari; Hwang, Soo Min; Yang, Juchan; Senthilkumar, Sirugaloor Thangavel; Kim, Junsoo; Go, Woo-Seok; Senthilkumar, Baskar; Song, Hyun-Kon; Kim, Youngsik

2016-12-07

Spinel-structured transition metal oxides are promising non-precious-metal electrocatalysts for oxygen electrocatalysis in rechargeable metal-air batteries. We applied porous cobalt manganese oxide (CMO) nanocubes as the cathode electrocatalyst in rechargeable seawater batteries, which are a hybrid-type Na-air battery with an open-structured cathode and a seawater catholyte. The porous CMO nanocubes were synthesized by the pyrolysis of a Prussian blue analogue, Mn 3 [Co(CN) 6 ] 2 ·nH 2 O, during air-annealing, which generated numerous pores between the final spinel-type CMO nanoparticles. The porous CMO electrocatalyst improved the redox reactions, such as the oxygen evolution/reduction reactions, at the cathode in the seawater batteries. The battery that used CMO displayed a voltage gap of ∼0.53 V, relatively small compared to that of the batteries employing commercial Pt/C (∼0.64 V) and Ir/C (∼0.73 V) nanoparticles and without any catalyst (∼1.05 V) at the initial cycle. This improved performance was due to the large surface area (catalytically active sites) and the high oxidation states of the randomly distributed Co and Mn cations in the CMO. Using a hard carbon anode, the Na-metal-free seawater battery exhibited a good cycle performance with an average discharge voltage of ∼2.7 V and a discharge capacity of ∼190 mAh g -1 hard carbon during 100 cycles (energy efficiencies of 74-79%).

Fuel cell electrocatalyst using polybenzimidazole-modified carbon nanotubes as support materials.

PubMed

Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2013-03-25

Toward the next generation fuel cell systems, the development of a novel electrocatalyst for the polymer electrolyte fuel cell (PEFC) is crucial to overcome the drawbacks of the present electrocatalyst. As a conductive supporting material for the catalyst, carbon nanotubes (CNTs) have emerged as a promising candidate, and many attempts have been carried out to introduce CNT, in place of carbon black. On the other hand, as a polymer electrolyte, polybenzimidazoles (PBIs) have been recognized as a powerful candidate due to the high proton conductivity above 100 °C under non-humid conditions. In 2008, we found that these two materials have a strong physical interaction and form a stable hybrid material, in which the PBIs uniformly wrap the surfaces of the CNTs. Furthermore, PBIs serve as effective binding sites for the formation of platinum (Pt) nanoparticles to fabricate a ternary composite (CNT/PBIs/Pt). In this review article, we summarize the fundamental properties of the CNT/PBIs/Pt and discuss their potential as a new electrocatalyst for the PEFC in comparison with the conventional ones. Furthermore, potential applications of CNT/PBIs including use of the materials for oxygen reduction catalysts and reinforcement of PBI films are summarized. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increase of electrodeposited catalyst stability via plasma grown vertically oriented graphene nanoparticle movement restriction.

PubMed

Vanrenterghem, Bart; Hodnik, Nejc; Bele, Marjan; Šala, Martin; Amelinckx, Giovanni; Neukermans, Sander; Zaplotnik, Rok; Primc, Gregor; Mozetič, Miran; Breugelmans, Tom

2017-08-17

Beside activity, electrocatalyst stability is gaining in importance. The most common degradation mechanism is the loss of the active surface area due to nanoparticle growth via coalescence/agglomeration. We propose a particle confinement strategy via vertically oriented graphene deposition to overcome degradation of the nanoparticles.

Intercalation of Cobalt into the Interlayer of Birnessite Improves Oxygen Evolution Catalysis

DOE PAGES

Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H.; ...

2016-10-10

Here we show that the activity of cobalt for the oxygen evolution reaction (OER) can be enhanced by confining it in the interlayer region of birnessite (layered manganese oxide). The cobalt intercalation was verified by employing state-of-the-art characterization techniques such as XRD, Raman and electron microscopy. It is demonstrated that the Co 2+/birnessite electrocatalyst can reach 10 mA cm -2 at an overpotential of 360 mV with near unity Faradaic efficiency. This overpotential is lower than that which can be achieved by using a pure cobalt hydroxide electrocatalyst for the OER. Furthermore, the Co 2+/birnessite catalyst shows no degradation aftermore » 1000 electrochemical cycles.« less

Core-Shell Co/CoO Integrated on 3D Nitrogen Doped Reduced Graphene Oxide Aerogel as an Enhanced Electrocatalyst for the Oxygen Reduction Reaction

PubMed Central

Wang, Meng; Hou, Yuyang; Slade, Robert C. T.; Wang, Jiazhao; Shi, Dongqi; Wexler, David; Liu, Huakun; Chen, Jun

2016-01-01

Here, we demonstrate that Cobalt/cobalt oxide core-shell nanoparticles integrated on nitrogen-doped (N-doped) three-dimensional reduced graphene oxide aerogel-based architecture (Co/CoO-NGA) were synthesized through a facile hydrothermal method followed by annealing treatment. The unique endurable porous structure could provide sufficient mass transfer channels and ample active sites on Co/CoO-NGA to facilitate the catalytic reaction. The synthesized Co/CoO-NGA was explored as an electrocatalyst for the oxygen reduction reaction, showing comparable oxygen reduction performance with excellent methanol resistance and better durability compared with Pt/C. PMID:27597939

Non-platinum metal-organic framework based electro-catalyst for promoting oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Das, Dipanwita; Raut, Vrushali; Kireeti, Kota V. M. K.; Jha, Neetu

2018-04-01

We developed two non-precious Metal Organic Framework (MOF) based electrocatalysts, MOF-5 and MOF-i using solvothermal and refluxing methods. The MOFs prepared has been characterized by powder X-ray diffractometer (XRD), Fourier Transform Infra-Red Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) for structural and morphological insights. SEM images reveal cubic shape for solvothermally synthesized MOF-5, whereas refluxing method leads to platelet morphology of MOF-i. The synthesized MOFs has been investigated for Oxygen Reduction Reaction (ORR) studies using Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), with MOF modified Glassy Carbon (GC) as working electrode. The electrochemical data suggests higher activity of MOF-5 towards ORR compared to MOF-i.

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte.

PubMed

Wang, Nan; Li, Ligui; Zhao, Dengke; Kang, Xiongwu; Tang, Zhenghua; Chen, Shaowei

2017-09-01

Nitrogen and sulfur-codoped graphene composites with Co 9 S 8 (NS/rGO-Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO 2 catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only -0.193 V to reach 10 mA cm -2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half-wave potential in ORR and the potential to reach 10 mA cm -2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm -2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S-codoped rGO, and Co 9 S 8 nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiFe layered double hydroxide/reduced graphene oxide nanohybrid as an efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions

NASA Astrophysics Data System (ADS)

Zhan, Tianrong; Zhang, Yumei; Liu, Xiaolin; Lu, SiSi; Hou, Wanguo

2016-11-01

Highly active and low-cost bifunctional electrocatalysts for oxygen evolution and reduction reactions (OER and ORR) hold a heart position for the renewable energy technologies such as metal-air batteries and fuel cells. Here, we reported the synthesis of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanohybrid via the facile solvothermal method followed by chemical reduction. The template role of surfactant and the hybridization of rGO supplied the NiFe-LDH/rGO catalyst with a porous nanostructure and an enhanced conductivity, favoring both mass transport and charge communication of electrocatalytic reactions. The NiFe-LDH/rGO composite not only displayed highly efficient OER activity in alkaline solution with a low onset overpotential of 240 mV, but also only needed an overpotential of 250 mV to reach the 10 mA cm-2 current density. The NiFe-LDH/rGO nanohybrid also offered excellent ORR catalytic activity with onset potential at 0.796 V in alkaline media. The rotating-disk and rotating-ring-disk electrodes both revealed that the ORR on NiFe-LDH/rGO mainly involved a direct four-electron reaction pathways accompanying part of the two-electron process. The excellent bifunctional activity of the NiFe-LDH/rGO nanohybrid could be attributed to the synergistic effects of rGO and NiFe-LDH components due to the strongly coupled interactions.

Manganese oxide/poly(3,4-ethylenedioxythiophene) hybrid electrocatalysts for the oxygen reduction reaction in alkaline fuel cells

DOE PAGES

Lambert, Timothy N.; Vigil, Julian A.

2016-08-22

Manganese oxide/poly(3,4-ethylene-dioxythiophene) (MnO x/ PEDOT) nanostructured hybrid thin films were prepared using a simple anodic electrodeposition process from aqueous solution, and then tested for oxygen reduction reaction (ORR) activity in alkaline electrolyte using rotating disk electrode and rotating ring disk electrode methods. MnO x/PEDOT provided improvements over MnO x-only and PEDOT-only control films, with > 0.2 V decrease in onset and half-wave overpotentials, and > 1.5 times increase in terminal current density. The MnO x/PEDOT film exhibited only a slightly lower n value (n = 3.86-3.92) than the 20% Pt/C benchmark electrocatalyst (n = 3.98) across all potentials. MnO x/PEDOTmore » also displayed a more positive half-wave potential and superior electrocatalytic selectivity for the ORR upon methanol exposure than 20% Pt/C. Here, the high activity and synergism of MnO x/PEDOT towards the ORR is attributed to effective intermixing/dispersion of the two materials, intimate substrate contact with improved charge transfer processes attained by co-electrodepositing MnO x with PEDOT and due to the increase in Mn 3+ content at the surface of the oxide.« less

Manganese oxide/poly(3,4-ethylenedioxythiophene) hybrid electrocatalysts for the oxygen reduction reaction in alkaline fuel cells

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

Lambert, Timothy N.; Vigil, Julian A.

Manganese oxide/poly(3,4-ethylene-dioxythiophene) (MnO x/ PEDOT) nanostructured hybrid thin films were prepared using a simple anodic electrodeposition process from aqueous solution, and then tested for oxygen reduction reaction (ORR) activity in alkaline electrolyte using rotating disk electrode and rotating ring disk electrode methods. MnO x/PEDOT provided improvements over MnO x-only and PEDOT-only control films, with > 0.2 V decrease in onset and half-wave overpotentials, and > 1.5 times increase in terminal current density. The MnO x/PEDOT film exhibited only a slightly lower n value (n = 3.86-3.92) than the 20% Pt/C benchmark electrocatalyst (n = 3.98) across all potentials. MnO x/PEDOTmore » also displayed a more positive half-wave potential and superior electrocatalytic selectivity for the ORR upon methanol exposure than 20% Pt/C. Here, the high activity and synergism of MnO x/PEDOT towards the ORR is attributed to effective intermixing/dispersion of the two materials, intimate substrate contact with improved charge transfer processes attained by co-electrodepositing MnO x with PEDOT and due to the increase in Mn 3+ content at the surface of the oxide.« less

Hollow-spherical Co/N-C nanoparticle as an efficient electrocatalyst used in air cathode microbial fuel cell.

PubMed

Yang, Tingting; Li, Kexun; Pu, Liangtao; Liu, Ziqi; Ge, Baochao; Pan, Yajun; Liu, Ying

2016-12-15

The hollow-spherical Co/N-C nanoparticle, which is synthesized via a simple hydrothermal reaction followed by heat treatment, is firstly used as electrocatalyst for oxygen reduction reaction (ORR) in air-cathode microbial fuel cell (MFC). The maximum power density of MFC with 10% Co/N-C air-cathode is as high as 2514±59mWm(-2), which is almost 174% higher than the control. The exchange current density (i0) of cathode equipped with 10% Co/N-C is 238% higher than that of untreated AC. While the total resistance of treated samples decreases from 13.017 to 10.255Ω. The intensity ratio of Raman D to G band (ID/IG) decreases from 0.93 (N-C) to 0.73 (Co/N-C), indicating the catalyst forms graphite structure. Both XRD and XPS testify that Co is bonded to N within graphitic sheets and serves as the active sites in ORR. The four-electron pathway of the Co/N-C also plays a crucial role in electrochemical catalytic activity. As a result, it can be expected that the as-synthesized Co/N-C, with extraordinary electro-catalytic performance towards ORR, will be a promising alternative to the state-of-the-art non-precious metal ORR electro-catalysts for electrochemical energy applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Molybdenum Carbide Nanoparticles Coated into the Graphene Wrapping N-Doped Porous Carbon Microspheres for Highly Efficient Electrocatalytic Hydrogen Evolution Both in Acidic and Alkaline Media.

PubMed

Wei, Huifang; Xi, Qiaoya; Chen, Xi'an; Guo, Daying; Ding, Feng; Yang, Zhi; Wang, Shun; Li, Juan; Huang, Shaoming

2018-03-01

Molybdenum carbide (Mo 2 C) is recognized as an alternative electrocatalyst to noble metal for the hydrogen evolution reaction (HER). Herein, a facile, low cost, and scalable method is provided for the fabrication of Mo 2 C-based eletrocatalyst (Mo 2 C/G-NCS) by a spray-drying, and followed by annealing. As-prepared Mo 2 C/G-NCS electrocatalyst displays that ultrafine Mo 2 C nanopartilces are uniformly embedded into graphene wrapping N-doped porous carbon microspheres derived from chitosan. Such designed structure offer several favorable features for hydrogen evolution application: 1) the ultrasmall size of Mo 2 C affords a large exposed active sites; 2) graphene-wrapping ensures great electrical conductivity; 3) porous structure increases the electrolyte-electrode contact points and lowers the charge transfer resistance; 4) N-dopant interacts with H + better than C atoms and favorably modifies the electronic structures of adjacent Mo and C atoms. As a result, the Mo 2 C/G-NCS demonstrates superior HER activity with a very low overpotential of 70 or 66 mV to achieve current density of 10 mA cm -2 , small Tafel slope of 39 or 37 mV dec -1 , respectively, in acidic and alkaline media, and high stability, indicating that it is a great potential candidate as HER electrocatalyst.

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.

Platinum Monolayer Electrocatalysts for Anodic Oxidation of Alcohols.

PubMed

Li, Meng; Liu, Ping; Adzic, Radoslav R

2012-12-06

The slow, incomplete oxidation of methanol and ethanol on platinum-based anodes as well as the high price and limited reserves of Pt has hampered the practical application of direct alcohol fuel cells. We describe the electrocatalysts consisting of one Pt monolayer (one atom thick layer) placed on extended or nanoparticle surfaces having the activity and selectivity for the oxidation of alcohol molecules that can be controlled with platinum-support interaction. The suitably expanded Pt monolayer (i.e., Pt/Au(111)) exhibits a factor of 7 activity increase in catalyzing methanol electrooxidation relative to Pt(111). Sizable enhancement is also observed for ethanol electrooxidation. Furthermore, a correlation between substrate-induced lateral strain in a Pt monolayer and its activity/selectivity is established and rationalized by experimental and theoretical studies. The knowledge we gained with single-crystal model catalysts was successfully applied in designing real nanocatalysts. These findings for alcohols are likely to be applicable for the oxidation of other classes of organic molecules.

Pt/Mo 2C/C-cp as a highly active and stable catalyst for ethanol electrooxidation

DOE PAGES

Lin, Lili; Sheng, Wenchao; Yao, Siyu; ...

2017-02-09

Here, a Pt/Mo 2C/C-cp electrocatalyst with optimized Pt-Mo 2C chemical bonding is synthesized and evaluated for the ethanol oxidation reaction (EOR). The chemical bonding of Mo 2C to Pt particles renders exceptional EOR activity at low potentials, which is 15 and 2.5 times higher than Pt/C and commercial 40% PtRu/C, respectively, at 0.6 V (vs. RHE). The stability of the Pt/Mo 2C/C-cp electrocatalyst is comparable to the commercial 40% PtRu/C catalyst. CO stripping test demonstrates the existence of highly active sites for CO oxidation on the Pt/Mo 2C/C-cp catalyst. In-situ infrared spectroscopic studies of EOR reveal that the excellent anti-poisoningmore » ability of the Pt/Mo 2C/C-cp catalyst is related to the relatively weak binding of carbonyl intermediates over the Pt/Mo 2C/C-cp catalysts.« less

Pt/Mo 2C/C-cp as a highly active and stable catalyst for ethanol electrooxidation

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

Lin, Lili; Sheng, Wenchao; Yao, Siyu

Here, a Pt/Mo 2C/C-cp electrocatalyst with optimized Pt-Mo 2C chemical bonding is synthesized and evaluated for the ethanol oxidation reaction (EOR). The chemical bonding of Mo 2C to Pt particles renders exceptional EOR activity at low potentials, which is 15 and 2.5 times higher than Pt/C and commercial 40% PtRu/C, respectively, at 0.6 V (vs. RHE). The stability of the Pt/Mo 2C/C-cp electrocatalyst is comparable to the commercial 40% PtRu/C catalyst. CO stripping test demonstrates the existence of highly active sites for CO oxidation on the Pt/Mo 2C/C-cp catalyst. In-situ infrared spectroscopic studies of EOR reveal that the excellent anti-poisoningmore » ability of the Pt/Mo 2C/C-cp catalyst is related to the relatively weak binding of carbonyl intermediates over the Pt/Mo 2C/C-cp catalysts.« less

Copper-Nitrogen-Doped Graphene Hybrid as an Electrochemical Sensing Platform for Distinguishing DNA Bases.

PubMed

Sun, Shu-Wen; Liu, Hai-Ling; Zhou, Yue; Wang, Feng-Bin; Xia, Xing-Hua

2017-10-17

An electrochemical sensor using ultralight and porous copper-nitrogen-doped graphene (CuNRGO) nanocomposite as the electrocatalyst has been constructed to simultaneously determine DNA bases such as guanine (G) and cytosine (C), adenine (A), and thymine (T). The nanocomposite is synthesized by thermally annealing an ice-templated structure of graphene oxide (GO) and Cu(phen) 2 . Because of the unique structure and the presence of Cu 2+ -N active sites, the CuNRGO exhibits outstanding electrocatalytic activity toward the oxidation of free DNA bases. After optimizing the experimental conditions, the CuNRGO-based electrochemical sensor shows good linear responses for the G, A, T, and C bases in the concentration ranges of 0.132-6.62 μM, 0.37-5.18 μM, 198.2-5551 μM, and 270.0-1575 μM, respectively. The results demonstrate that CuNRGO is a promising electrocatalyst for electrochemical sensing devices.

Investigation of catalytic activity towards oxygen reduction reaction of Pt dispersed on boron doped graphene in acid medium.

PubMed

Pullamsetty, Ashok; Sundara, Ramaprabhu

2016-10-01

Boron doped graphene was prepared by a facile method and platinum (Pt) decoration over boron doped graphene was done in various chemical reduction methods such as sodium borohydride (NaBH4), polyol and modified polyol. X-ray diffraction analysis indicates that the synthesized catalyst particles are present in a nanocrystalline structure and transmission and scanning electron microscopy were employed to investigate the morphology and particle distribution. The electrochemical properties were investigated with the help of the rotating disk electrode (RDE) technique and cyclic voltammetry. The results show that the oxygen reduction reaction (ORR) takes place by a four-electron process. The kinetics of the ORR was evaluated using K-L and Tafel plots. The electrocatalyst obtained in modified polyol reduction method has shown the better catalytic activity compared to other two electrocatalysts. Copyright © 2016 Elsevier Inc. All rights reserved.

Electrocatalytic activity of ZnS nanoparticles in direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Bredol, Michael; Kaczmarek, Michał; Wiemhöfer, Hans-Dieter

2014-06-01

Low temperature fuel cells consuming ethanol without reformation would be a major step toward the use of renewable energy sources from biomass. However, the necessary electrodes and electrocatalysts still are far from being perfect and suffer from various poisoning and deactivation processes. This work describes investigations on systems using carbon/ZnS-based electrocatalysts for ethanol oxidation in complete membrane electrode assemblies (MEAs). MEAs were built on Nafion membranes with active masses prepared from ZnS nanoparticles and Vulcan carbon support. Under operation, acetic acid and acetaldehyde were identified and quantified as soluble oxidation products, whereas the amount of CO2 generated could not be quantified directly. Overall conversion efficiencies of up to 25% were estimated from cells operated over prolonged time. From polarization curves, interrupt experiments and analysis of reaction products, mass transport problems (concentration polarization) and breakthrough losses were found to be the main deficiencies of the ethanol oxidation electrodes fabricated so far.

Combined Photoemission Spectroscopy and Electrochemical Study of a Mixture of (Oxy)carbides as Potential Innovative Supports and Electrocatalysts.

PubMed

Calvillo, Laura; Valero-Vidal, Carlos; Agnoli, Stefano; Sezen, Hikmet; Rüdiger, Celine; Kunze-Liebhäuser, Julia; Granozzi, Gaetano

2016-08-03

Active and stable non-noble metal materials, able to substitute Pt as catalyst or to reduce the Pt amount, are vitally important for the extended commercialization of energy conversion technologies, such as fuel cells and electrolyzers. Here, we report a fundamental study of nonstoichiometric tungsten carbide (WxC) and its interaction with titanium oxycarbide (TiOxCy) under electrochemical working conditions. In particular, the electrochemical activity and stability of the WxC/TiOxCy system toward the ethanol electrooxidation reaction (EOR) and hydrogen evolution reaction (HER) are investigated. The chemical changes caused by the applied potential are established by combining photoemission spectroscopy and electrochemistry. WxC is not active toward the ethanol electrooxidation reaction at room temperature but it is highly stable under these conditions thanks to the formation of a passive thin film on the surface, consisting mainly of WO2 and W2O5, which prevents the full oxidation of WxC. In addition, WxC is able to adsorb ethanol, forming ethoxy groups on the surface, which constitutes the first step for the ethanol oxidation. The interaction between WxC and TiOxCy plays an important role in the electrochemical stability of WxC since specific orientations of the substrate are able to stabilize WxC and prevent its corrosion. The beneficial interaction with the substrate and the specific surface chemistry makes tungsten carbide a good electrocatalyst support or cocatalyst for direct ethanol fuel cells. However, WxC is active toward the HER and chemically stable under hydrogen reduction conditions, since no changes in the chemical composition or dissolution of the film are observed. This makes tungsten carbide a good candidate as electrocatalyst support or cocatalyst for the electrochemical production of hydrogen.

Electrodeposition of Nickel Nanoparticles for the Alkaline Hydrogen Evolution Reaction: Correlating Electrocatalytic Behavior and Chemical Composition.

PubMed

Tao, Shasha; Yang, Florent; Schuch, Jona; Jaegermann, Wolfram; Kaiser, Bernhard

2018-03-09

Ni nanoparticles (NPs) consisting of Ni, NiO, and Ni(OH) 2 were formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. Additionally, the deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. The chemical composition of the NPs changed upon using different conditions, and it was found that the catalytic activity increased with an increase in the amount of NiO. From these data, optimized NPs were synthesized; the best sample showed an onset potential of approximately 0 V and an overpotential of 197 mV at a cathodic current density of 10 mA cm -2 as well as a small Tafel slope of 88 mV dec -1 in 1 m KOH, values that are comparable to those of Pt foil. These NPs consist of approximately 25 % Ni and Ni(OH) 2 each, as well as approximately 50 % NiO. This implies that to obtain a successful HER electrocatalyst, active sites with differing compositions have to be close to each other to promote the different reaction steps. Long-time measurements (30 h) showed almost complete transformation of the highly active catalyst compound consisting of Ni 0 , NiO, and Ni(OH) 2 into the less active Ni(OH) 2 phase. Nevertheless, the here-employed electrodeposition of nonprecious metal/metal-oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for water reduction to hydrogen. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical studies of Pt-Ti nanoparticles for potential use as PEMFC electrocatalysts.

PubMed

Jennings, Paul C; Pollet, Bruno G; Johnston, Roy L

2012-03-07

A theoretical investigation is presented of alloying platinum with titanium to form binary Pt-Ti nanoalloys as an alternative to the expensive pure platinum catalysts commonly used for Proton Exchange Membrane Fuel Cell cathode electrocatalysts. Density Functional Theory calculations are performed to investigate compositional effects on structural properties as well as Oxygen Reduction Reaction kinetics and poisoning effects. High symmetry A(32)-B(6) clusters are studied to investigate structural properties. From these structures binding energies of hydroxyl and carbon monoxide are studied on a range of sites on the surface of the clusters. Promising results are obtained suggesting that the bimetallic Pt-Ti nanoalloys may exhibit enhanced properties compared to pure platinum catalysts.

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.

Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst

PubMed Central

Yang, Hong Bin; Miao, Jianwei; Hung, Sung-Fu; Chen, Jiazang; Tao, Hua Bing; Wang, Xizu; Zhang, Liping; Chen, Rong; Gao, Jiajian; Chen, Hao Ming; Dai, Liming; Liu, Bin

2016-01-01

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical to renewable energy conversion and storage technologies. Heteroatom-doped carbon nanomaterials have been reported to be efficient metal-free electrocatalysts for ORR in fuel cells for energy conversion, as well as ORR and OER in metal-air batteries for energy storage. We reported that metal-free three-dimensional (3D) graphene nanoribbon networks (N-GRW) doped with nitrogen exhibited superb bifunctional electrocatalytic activities for both ORR and OER, with an excellent stability in alkaline electrolytes (for example, KOH). For the first time, it was experimentally demonstrated that the electron-donating quaternary N sites were responsible for ORR, whereas the electron-withdrawing pyridinic N moieties in N-GRW served as active sites for OER. The unique 3D nanoarchitecture provided a high density of the ORR and OER active sites and facilitated the electrolyte and electron transports. As a result, the as-prepared N-GRW holds great potential as a low-cost, highly efficient air cathode in rechargeable metal-air batteries. Rechargeable zinc-air batteries with the N-GRW air electrode in a two-electrode configuration exhibited an open-circuit voltage of 1.46 V, a specific capacity of 873 mAh g−1, and a peak power density of 65 mW cm−2, which could be continuously charged and discharged with an excellent cycling stability. Our work should open up new avenues for the development of various carbon-based metal-free bifunctional electrocatalysts of practical significance. PMID:27152333

Enhanced methanol electro-oxidation reaction on Pt-CoOx/MWCNTs hybrid electro-catalyst

NASA Astrophysics Data System (ADS)

Nouralishahi, Amideddin; Rashidi, Ali Morad; Mortazavi, Yadollah; Khodadadi, Abbas Ali; Choolaei, Mohammadmehdi

2015-04-01

The electro-catalytic behavior of Pt-CoOx/MWCNTs in methanol electro-oxidation reaction (MOR) is investigated and compared to that of Pt/MWCNTs. The electro-catalysts were synthesized by an impregnation method using NaBH4 as the reducing agent. The morphological and physical characteristics of samples are examined by XRD, TEM, ICP and EDS techniques. In the presence of CoOx, Pt nanoparticles were highly distributed on the support with an average particle size of 2 nm, an obvious decrease from 5.1 nm for Pt/MWCNTs. Cyclic voltammetry, CO-stripping, Chronoamperometry, and electrochemical impedance spectroscopy (EIS) measurements are used to study the electrochemical behavior of the electro-catalysts. The results revealed a considerable enhancement in the oxidation kinetics of COads on Pt active sites by the participation of CoOx. Compared to Pt/MWCNTs, Pt-CoOx/MWCNTs sample has a larger electrochemical active surface area (ECSA) and higher electro-catalytic activity and stability toward methanol electro-oxidation. According to the results of cyclic voltammetry, the forward anodic peak current density enhances more than 89% at the optimum atomic ratio of Pt:Co = 2:1. Furthermore, inclusion of cobalt oxide species causes the onset potential of methanol electro-oxidation reaction to shift 84 mV to negative values compared to that on Pt/MWCNTs. Based on EIS data, dehydrogenation of methanol is the rate-determining step of MOR on both Pt/MWCNTs and Pt-CoOx/MWCNTs, at small overpotentials. However, at higher overpotentials, the oxidation of adsorbed oxygen-containing groups controls the total rate of MOR process.

A highly durable fuel cell electrocatalyst based on double-polymer-coated carbon nanotubes

PubMed Central

Berber, Mohamed R.; Hafez, Inas H.; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-01-01

Driven by the demand for the commercialization of fuel cell (FC) technology, we describe the design and fabrication of a highly durable FC electrocatalyst based on double-polymer-coated carbon nanotubes for use in polymer electrolyte membrane fuel cells. The fabricated electrocatalyst is composed of Pt-deposited polybenzimidazole-coated carbon nanotubes, which are further coated with Nafion. By using this electrocatalyst, a high FC performance with a power density of 375 mW/cm2 (at 70 ˚C, 50% relative humidity using air (cathode)/H2(anode)) was obtained, and a remarkable durability of 500,000 accelerated potential cycles was recorded with only a 5% loss of the initial FC potential and 20% loss of the maximum power density, which were far superior properties compared to those of the membrane electrode assembly prepared using carbon black in place of the carbon nanotubes. The present study indicates that the prepared highly durable fuel cell electrocatalyst is a promising material for the next generation of PEMFCs. PMID:26594045

A highly durable fuel cell electrocatalyst based on double-polymer-coated carbon nanotubes.

PubMed

Berber, Mohamed R; Hafez, Inas H; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-11-23

Driven by the demand for the commercialization of fuel cell (FC) technology, we describe the design and fabrication of a highly durable FC electrocatalyst based on double-polymer-coated carbon nanotubes for use in polymer electrolyte membrane fuel cells. The fabricated electrocatalyst is composed of Pt-deposited polybenzimidazole-coated carbon nanotubes, which are further coated with Nafion. By using this electrocatalyst, a high FC performance with a power density of 375 mW/cm(2) (at 70 ˚C, 50% relative humidity using air (cathode)/H2(anode)) was obtained, and a remarkable durability of 500,000 accelerated potential cycles was recorded with only a 5% loss of the initial FC potential and 20% loss of the maximum power density, which were far superior properties compared to those of the membrane electrode assembly prepared using carbon black in place of the carbon nanotubes. The present study indicates that the prepared highly durable fuel cell electrocatalyst is a promising material for the next generation of PEMFCs.

Preparation and evaluation of advanced catalysts for phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Stonehart, P.; Baris, J.; Hockmuth, J.; Pagliaro, P.

1984-01-01

The platinum electrocatalysts were characterized for their crystallite sizes and the degree of dispersion on the carbon supports. One application of these electrocatalysts was for anodic oxidation of hydrogen in hot phosphoric acid fuel cells, coupled with the influence of low concentrations of carbon monoxide in the fuel gas stream. In a similar way, these platinum on carbon electrocatalysts were evaluated for oxygen reduction in hot phosphoric acid. Binary noble metal alloys were prepared for anodic oxidation of hydrogen and noble metal-refractory metal mixtures were prepared for oxygen reduction. An exemplar alloy of platinum and palladium (50/50 atom %) was discovered for anodic oxidation of hydrogen in the presence of carbon monoxide, and patent disclosures were submitted. For the cathode, platinum-vanadium alloys were prepared showing improved performance over pure platinum. Preliminary experiments on electrocatalyst utilization in electrode structures showed low utilization of the noble metal when the electrocatalyst loading exceeded one weight percent on the carbon.

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

Combinatorial discovery of new methanol-tolerant non-noble metal cathode electrocatalysts for direct methanol fuel cells.

PubMed

Yu, Jong-Sung; Kim, Min-Sik; Kim, Jung Ho

2010-12-14

Combinatorial synthesis and screening were used to identify methanol-tolerant non-platinum cathode electrocatalysts for use in direct methanol fuel cells (DMFCs). Oxygen reduction consumes protons at the surface of DMFC cathode catalysts. In combinatorial screening, this pH change allows one to differentiate active catalysts using fluorescent acid-base indicators. Combinatorial libraries of carbon-supported catalyst compositions containing Ru, Mo, W, Sn, and Se were screened. Ternary and quaternary compositions containing Ru, Sn, Mo, Se were more active than the "standard" Alonso-Vante catalyst, Ru(3)Mo(0.08)Se(2), when tested in liquid-feed DMFCs. Physical characterization of the most active catalysts by powder X-ray diffraction, gas adsorption, and X-ray photoelectron spectroscopy revealed that the predominant crystalline phase was hexagonal close-packed (hcp) ruthenium, and showed a surface mostly covered with oxide. The best new catalyst, Ru(7.0)Sn(1.0)Se(1.0), was significantly more active than Ru(3)Se(2)Mo(0.08), even though the latter contained smaller particles.

A novel electroless method to prepare a platinum electrocatalyst on diamond for fuel cell applications

NASA Astrophysics Data System (ADS)

Lyu, Xiao; Hu, Jingping; Foord, John S.; Wang, Qiang

2013-11-01

A novel electroless deposition method was demonstrated to prepare a platinum electrocatalyst on boron doped diamond (BDD) substrates without the need for pre-activation. This green method addresses the uniformity and particle size issues associated with electrodeposition and circumvents the pre-activation procedure which is necessary for conventional electroless deposition. The inert BDD substrate formed a galvanic couple with an iron wire, to overcome the activation barrier associated with conventional electroless deposition on diamond, leading to the formation of Pt nanoparticles on the electrode surface in a galvanic process coupled to a chemical process. When sodium hypophosphite was employed as the reducing agent to drive the electroless reaction Pt deposits which were contaminated with iron and phosphorus resulted. In contrast, the reducing agent ascorbic acid gave rise to high purity Pt nanoparticles. Optimal deposition conditions with respect to bath temperature, pH value and stabilizing additives are identified. Using this approach, high purity and uniformly distributed platinum nanoparticles are obtained on the diamond electrode surface, which demonstrate a high electrochemical activity towards methanol oxidation.

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.

Mn-doped NiP2 nanosheets as an efficient electrocatalyst for enhanced hydrogen evolution reaction at all pH values

NASA Astrophysics Data System (ADS)

Wang, Xiaodeng; Zhou, Hongpeng; Zhang, Dingke; Pi, Mingyu; Feng, Jiajia; Chen, Shijian

2018-05-01

Developing stable and high-efficiency hydrogen generation electrocatalysts, particularly for the cathode hydrogen evolution reaction (HER), is an urgent challenge in energy conversion technologies. In this work, we have successfully synthesized Mn-doped NiP2 nanosheets on carbon cloth (Mn-NiP2 NSs/CC), which behaves as a higher efficient three dimensional HER electrocatalyst with better stability at all pH values than pure NiP2. Electrochemical tests demonstrate that the catalytic activity of NiP2 is enhanced by Mn doping. In 0.5 M H2SO4, this Mn-NiP2 NSs/CC catalyst drives 10 mA cm-2 at an overpotential of 69 mV, which is 20 mV smaller than pure NiP2. To achieve the same current density, it demands overpotentials of 97 and 107 mV in 1.0 M KOH and phosphate-buffered saline (PBS), respectively. Compared with pure NiP2, higher HER electrocatalytic performance for Mn-NiP2 NSs/CC can be attributed to its lower thermo-neutral hydrogen adsorption free energy, which is supported by density functional theory calculations.

Oxygen electrodes for rechargeable alkaline fuel cells, 3

NASA Technical Reports Server (NTRS)

Swette, L.; Kackley, N.; Mccatty, S. A.

1991-01-01

The investigation and development of electrocatalysts and supports for the positive electrode of moderate temperature single unit rechargeable alkaline fuel cells is described. Focus is on chemical and electrochemical stability and O2 reduction/evolution activity of the electrode in question.

Relationships between structure and activity of carbon as a multifunctional support for electrocatalysts.

PubMed

Stevanović, Sanja I; Panić, Vladimir V; Dekanski, Aleksandar B; Tripković, Amalija V; Jovanović, Vladislava M

2012-07-14

We report on new insights into the relationships between structure and activity of glassy carbon (GC), as a model material for electrocatalyst support, during its anodization in acid solution. Our investigation strongly confirms the role of CFGs in promotion of Pt activity by the "spill-over" effect related to CO(ads) for methanol electrooxidation (MEO) on a carbon-supported Pt catalyst. Combined analysis of voltammetric and impedance behaviour as well as changes in GC surface morphology induced by intensification of anodizing conditions reveal an intrinsic influence of the carbon functionalization and the structure of a graphene oxide (GO) layer on the electrical and electrocatalytic properties of activated GC. Although GO continuously grows during anodization, it structurally changes from being a graphite inter-layer within graphite ribbons toward a continuous GO surface layer that deteriorates the native structure of GC. As a consequence of the increased distance between GO-spaced graphite layers, the GC conductivity decreases until the case of profound GO exfoliation under drastic anodizing conditions. This exposes the native, yet abundantly functionalized, GC texture. While GC capacitance continuously increases with intensification of anodizing conditions, the surface nano-roughness and GO resistance reach the highest values at modest anodizing conditions, and then decrease upon drastic anodization due to the onset of GO exfoliation. We found for the first time that the activity of a GC-supported Pt catalyst in MEO, as one of the promising half-reactions in polymer electrolyte fuel cells, strictly follows the changes in GC nano-roughness and GO-induced GC resistance. The highest GC/Pt MEO activity is reached when optimal distance between graphite layers and optimal degree of GC functionalization bring the highest amount of CFGs into intimate contact with the Pt surface. This confirms the promoting role of CFGs in MEO catalysis.

In-Situ Anomalous Small-Angle X-ray Scattering Studies of Polymer Electrolyte Membrane Fuel Cell Catalyst Degradation

NASA Astrophysics Data System (ADS)

Gilbert, James Andrew

Polymer electrolyte membrane fuel cells (PEMFCs) are a promising high efficiency energy conversion technology, but their cost effective implementation, especially for automotive power, has been hindered by degradation of the electrochemically-active surface area (ECA) of the Pt nanoparticle electrocatalysts. While numerous studies using ex-situ post-mortem techniques have provided insight into the effect of operating conditions on ECA loss, the governing mechanisms and underlying processes are not fully understood. Toward the goal of elucidating the electrocatalyst degradation mechanisms, we have followed particle size distribution (PSD) growth evolutions of Pt and Pt-alloy nanoparticle catalysts during potential cycling in an aqueous acidic environment (with and without flow of electrolyte) and in a fuel cell environment using in-situ anomalous small-angle X-ray scattering (ASAXS). The results of this thesis show a surface area loss mechanism of Pt nanoparticles supported on carbon to be predominantly controlled by Pt dissolution, the particle size dependence of Pt dissolution, the loss of dissolved Pt into the membrane and electrolyte, and, to a lesser extent, the re-deposition of dissolved Pt onto larger particles. The relative extent of these loss mechanisms are shown to be dependent on the environment, the temperature, and the potential cycling conditions. Correlation of ASAXS-determined particle growth with both calculated and voltammetrically-determined oxide coverages demonstrates that the oxide coverage is playing a key role in the dissolution process and in the corresponding growth of the mean Pt nanoparticle size and loss of ECA. This understanding potentially reduces the complex changes in PSDs and ECA resulting from various voltage profiles to the response to a single variable, oxide coverage. A better understanding of the degradation mechanisms of Pt and Pt-alloy nanoparticle distributions could lead to more stable electrocatalysts while simultaneously reducing the cost of the materials, thereby supporting more durable and lower cost PEMFCs.

A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core–Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

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

Sivanantham, Arumugam; Ganesan, Pandian; Estevez,

2018-01-11

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm−2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core–shell Co@NC–anode water electrolyzer delivers 10more » mA cm−2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2–anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core–shell electrocatalysts with enriched active centers.« less

A Stable Graphitic, Nanocarbon-Encapsulated, Cobalt-Rich Core-Shell Electrocatalyst as an Oxygen Electrode in a Water Electrolyzer

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

Sivanantham, Arumugam; Ganesan, Pandian; Estevez, Luis

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core–shell nanostructured electrocatalysts (core–shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core–shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm-2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core–shell Co@NC–anode water electrolyzer delivers 10more » mA cm-2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2–anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2–anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core–shell Co@NC–anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core–shell electrocatalysts with enriched active centers.« less

Porous carbon supported Fe-N-C composite as an efficient electrocatalyst for oxygen reduction reaction in alkaline and acidic media

NASA Astrophysics Data System (ADS)

Liu, Baichen; Huang, Binbin; Lin, Cheng; Ye, Jianshan; Ouyang, Liuzhang

2017-07-01

In recent years, non-precious metal electrocatalysts for oxygen reduction reaction (ORR) have attracted tremendous attention due to their high catalytic activity, long-term stability and excellent methanol tolerance. Herein, the porous carbon supported Fe-N-C catalysts for ORR were synthesized by direct pyrolysis of ferric chloride, 6-Chloropyridazin-3-amine and carbon black. Variation of pyrolysis temperature during the synthesis process leads to the difference in ORR catalytic activity. High pyrolysis temperature is beneficial to the formation of the "N-Fe" active sites and high electrical conductivity, but the excessive temperature will cause the decomposition of nitrogen-containing active sites, which are revealed by Raman, TGA and XPS. A series of synthesis and characterization experiments with/without nitrogen or iron in carbon black indicate that the coordination of iron and nitrogen plays a crucial role in achieving excellent ORR performances. Electrochemical test results show that the catalyst pyrolyzed at 800 °C (Fe-N-C-800) exhibits excellent ORR catalytic activity, better methanol tolerance and higher stability compared with commercial Pt/C catalyst in both alkaline and acidic conditions.

A nanoporous PdCo alloy as a highly active electrocatalyst for the oxygen-reduction reaction and formic acid electrooxidation.

PubMed

Xu, Caixia; Liu, Yunqing; Zhang, Huan; Geng, Haoran

2013-11-01

A nanoporous (NP) PdCo alloy with uniform structure size and controllable bimetallic ratio was fabricated simply by one-step mild dealloying of a PdCoAl precursor alloy. The as-made alloy consists of a nanoscaled bicontinuous network skeleton with interconnected hollow channels that extend in all three dimensions. With a narrow ligament size distribution around 5 nm, the NP PdCo alloy exhibits much higher electrocatalytic activity towards the oxygen-reduction reaction (ORR) with enhanced specific and mass activities relative to NP Pd and commercial Pt/C catalysts. A long-term stability test demonstrated that NP PdCo has comparable catalytic durability with less loss of ORR activity and electrochemical surface area than Pt/C. The NP PdCo alloy also shows dramatically enhanced catalytic activity towards formic acid electrooxidation relative to NP Pd and Pd/C catalysts. The as-made NP PdCo holds great application potential as a promising cathode as well as an anode electrocatalyst in fuel cells with the advantages of superior catalytic performance and easy preparation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methods and systems for fuel production in electrochemical cells and reactors

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

Marina, Olga A.; Pederson, Larry R.

Methods and systems for fuel, chemical, and/or electricity production from electrochemical cells are disclosed. A voltage is applied between an anode and a cathode of an electrochemical cell. The anode includes a metal or metal oxide electrocatalyst. Oxygen is supplied to the cathode, producing oxygen ions. The anode electrocatalyst is at least partially oxidized by the oxygen ions transported through an electrolyte from the cathode to the anode. A feed gas stream is supplied to the anode electrocatalyst, which is converted to a liquid fuel. The anode electrocatalyst is re-oxidized to higher valency oxides, or a mixture of oxide phases,more » by supplying the oxygen ions to the anode. The re-oxidation by the ions is controlled or regulated by the amount of voltage applied.« less

Cobalt encapsulated N-doped defect-rich carbon nanotube as pH universal hydrogen evolution electrocatalyst

NASA Astrophysics Data System (ADS)

Zhang, Suyun; Xiao, Xinxin; Lv, Taotao; Lv, Xiaomeng; Liu, Botao; Wei, Wei; Liu, Jun

2018-07-01

Exploring efficient and economical Pt-free electrocatalysts is of great significance for the electrocatalytic hydrogen evolution reaction (HER). However, the rational design on an industrial scale is a formidable challenge. Herein, we reported a facile calcination at controlled temperatures to fabricate rationally assembled cobalt nanoparticles embedded in defect-rich N-doped carbon nanotubes (Co-NCNTs), which was derived from low-cost dicyanadiamide thermally polymerized with cobalt precursor forming metal-organic frameworks, then further calculation leading to final products. The as-obtained samples were endowed with high content of N as electrocatalytic active site, defect-rich structure and excellent synergistic effect between cobalt nanoparticles and carbon nanotubes toward electrocatalytic HER. As expected, Co-NCNTs were highly active and long-term stable with onset potentials of c.a. 15 mV in acidic electrolytes (0.5 M H2SO4), 70 mV in alkaline (1 M KOH) and 300 mV in neutral media (pH 7). Specially, to achieve the current density of 10 mA cm-2, the overpotential of 103 mV in acid, 204 mV in alkaline and 337 mV in neutral media was obtained. The enhanced HER performance was discussed in detail by adjusting the molar ratio of precursor and metal species. Moreover, the present synthetic route is easy to scale up and expand to other non-noble metal and alloy.

Controllable Surface Reorganization Engineering on Cobalt Phosphide Nanowire Arrays for Efficient Alkaline Hydrogen Evolution Reaction.

PubMed

Xu, Kun; Cheng, Han; Lv, Haifeng; Wang, Jingyu; Liu, Linqi; Liu, Si; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2018-01-01

Developing highly efficient hydrogen evolution reaction (HER) catalysts in alkaline media is considered significant and valuable for water splitting. Herein, it is demonstrated that surface reorganization engineering by oxygen plasma engraving on electocatalysts successfully realizes a dramatically enhanced alkaline HER activity. Taking CoP nanowire arrays grown on carbon cloth (denoted as CoP NWs/CC) as an example, the oxygen plasma engraving can trigger moderate CoO x species formation on the surface of the CoP NWs/CC, which is visually verified by the X-ray absorption fine structure, high-resolution transmission electron microscopy, and energy-dispersive spectrometer (EDS) mapping. Benefiting from the moderate CoO x species formed on the surface, which can promote the water dissociation in alkaline HER, the surface reorganization of the CoP NWs/CC realizes almost fourfold enhanced alkaline HER activity and a 180 mV decreased overpotential at 100 mA cm -2 , compared with the pristine ones. More interestingly, this surface reorganization strategy by oxygen plasma engraving can also be effective to other electrocatalysts such as free-standing CoP, Co 4 N, O-CoSe 2 , and C-CoSe 2 nanowires, which verifies the universality of the strategy. This work thus opens up new avenues for designing alkaline HER electrocatalysts based on oxygen plasma engraving. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile Synthesis of Vanadium-Doped Ni3S2 Nanowire Arrays as Active Electrocatalyst for Hydrogen Evolution Reaction.

PubMed

Qu, Yuanju; Yang, Mingyang; Chai, Jianwei; Tang, Zhe; Shao, Mengmeng; Kwok, Chi Tat; Yang, Ming; Wang, Zhenyu; Chua, Daniel; Wang, Shijie; Lu, Zhouguang; Pan, Hui

2017-02-22

Ni 3 S 2 nanowire arrays doped with vanadium(V) are directly grown on nickel foam by a facile one-step hydrothermal method. It is found that the doping can promote the formation of Ni 3 S 2 nanowires at a low temperature. The doped nanowires show excellent electrocatalytic performance toward hydrogen evolution reaction (HER), and outperform pure Ni 3 S 2 and other Ni 3 S 2 -based compounds. The stability test shows that the performance of V-doped Ni 3 S 2 nanowires is improved and stabilized after thousands of linear sweep voltammetry test. The onset potential of V-doped Ni 3 S 2 nanowire can be as low as 39 mV, which is comparable to platinum. The nanowire has an overpotential of 68 mV at 10 mA cm -2 , a relatively low Tafel slope of 112 mV dec -1 , good stability and high Faradaic efficiency. First-principles calculations show that the V-doping in Ni 3 S 2 extremely enhances the free carrier density near the Fermi level, resulting in much improved catalytic activities. We expect that the doping can be an effective way to enhance the catalytic performance of metal disulfides in hydrogen evolution reaction and V-doped Ni 3 S 2 nanowire is one of the most promising electrocatalysts for hydrogen production.

Energy efficiency enhancement of ethanol electrooxidation on Pd-CeO(2)/C in passive and active polymer electrolyte-membrane fuel cells.

PubMed

Bambagioni, Valentina; Bianchini, Claudio; Chen, Yanxin; Filippi, Jonathan; Fornasiero, Paolo; Innocenti, Massimo; Lavacchi, Alessandro; Marchionni, Andrea; Oberhauser, Werner; Vizza, Francesco

2012-07-01

Pd nanoparticles have been generated by performing an electroless procedure on a mixed ceria (CeO(2))/carbon black (Vulcan XC-72) support. The resulting material, Pd-CeO(2)/C, has been characterized by means of transmission electron microscopy (TEM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray diffraction (XRD) techniques. Electrodes coated with Pd-CeO(2)/C have been scrutinized for the oxidation of ethanol in alkaline media in half cells as well as in passive and active direct ethanol fuel cells (DEFCs). Membrane electrode assemblies have been fabricated using Pd-CeO(2)/C anodes, proprietary Fe-Co cathodes, and Tokuyama anion-exchange membranes. The monoplanar passive and active DEFCs have been fed with aqueous solutions of 10 wt% ethanol and 2 M KOH, supplying power densities as high as 66 mW cm(-2) at 25 °C and 140 mW cm(-2) at 80 °C. A comparison with a standard anode electrocatalyst containing Pd nanoparticles (Pd/C) has shown that, at even metal loading and experimental conditions, the energy released by the cells with the Pd-CeO(2)/C electrocatalyst is twice as much as that supplied by the cells with the Pd/C electrocatalyst. A cyclic voltammetry study has shown that the co-support ceria contributes to the remarkable decrease of the onset oxidation potential of ethanol. It is proposed that ceria promotes the formation at low potentials of species adsorbed on Pd, Pd(I)-OH(ads), that are responsible for ethanol oxidation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

DOEpatents

Adzic, Radoslav; Zhang, Junliang; Vukmirovic, Miomir

2012-11-13

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates

DOEpatents

Adzic, Radoslav [East Setauket, NY; Zhang, Junliang [Stony Brook, NY; Vukmirovic, Miomir [Port Jefferson Station, NY

2011-11-22

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen.

Single wall carbon nanotube supports for portable direct methanol fuel cells.

PubMed

Girishkumar, G; Hall, Timothy D; Vinodgopal, K; Kamat, Prashant V

2006-01-12

Single-wall and multiwall carbon nanotubes are employed as carbon supports in direct methanol fuel cells (DMFC). The morphology and electrochemical activity of single-wall and multiwall carbon nanotubes obtained from different sources have been examined to probe the influence of carbon support on the overall performance of DMFC. The improved activity of the Pt-Ru catalyst dispersed on carbon nanotubes toward methanol oxidation is reflected as a shift in the onset potential and a lower charge transfer resistance at the electrode/electrolyte interface. The evaluation of carbon supports in a passive air breathing DMFC indicates that the observed power density depends on the nature and source of carbon nanostructures. The intrinsic property of the nanotubes, dispersion of the electrocatalyst and the electrochemically active surface area collectively influence the performance of the membrane electrode assembly (MEA). As compared to the commercial carbon black support, single wall carbon nanotubes when employed as the support for anchoring the electrocatalyst particles in the anode and cathode sides of MEA exhibited a approximately 30% enhancement in the power density of a single stack DMFC operating at 70 degrees C.

Direct synthesis of bimetallic PtCo mesoporous nanospheres as efficient bifunctional electrocatalysts for both oxygen reduction reaction and methanol oxidation reaction

NASA Astrophysics Data System (ADS)

Wang, Hongjing; Yu, Hongjie; Li, Yinghao; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-04-01

The engineering of electrocatalysts with high performance for cathodic and/or anodic catalytic reactions is of great urgency for the development of direct methanol fuel cells. Pt-based bimetallic alloys have recently received considerable attention in the field of fuel cells because of their superior catalytic performance towards both fuel molecule electro-oxidation and oxygen reduction. In this work, bimetallic PtCo mesoporous nanospheres (PtCo MNs) with uniform size and morphology have been prepared by a one-step method with a high yield. The as-made PtCo MNs show superior catalytic activities for both oxygen reduction reaction and methanol oxidation reaction relative to Pt MNs and commercial Pt/C catalyst, attributed to their mesoporous structure and bimetallic composition.

Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH.

PubMed

Bracamonte, M Victoria; Melchionna, Michele; Stopin, Antoine; Giulani, Angela; Tavagnacco, Claudio; Garcia, Yann; Fornasiero, Paolo; Bonifazi, Davide; Prato, Maurizio

2015-09-01

The development of new electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at physiological pH is critical for several fields, including fuel cells and biological applications. Herein, the assembly of an electrode based on carboxyl-functionalised hydrophilic multiwalled carbon nanotubes (MWCNTs) filled with Fe phases and their excellent performance as electrocatalysts for ORR and HER at physiological pH are reported. The encapsulated Fe dramatically enhances the catalytic activity, and the graphitic shells play a double role of efficiently mediating the electron transfer to O2 and H2 O reactants and providing a cocoon that prevents uncontrolled Fe oxidation or leaching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructured Electrocatalysts for PEM Fuel Cells and Redox Flow Batteries: A Selected Review

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

Shao, Yuyan; Cheng, Yingwen; Duan, Wentao

2015-12-04

PEM fuel cells and redox flow batteries are two very similar technologies which share common component materials and device design. Electrocatalysts are the key components in these two devices. In this Review, we discuss recent progress of electrocatalytic materials for these two technologies with a focus on our research activities at Pacific Northwest National Laboratory (PNNL) in the past years. This includes (1) nondestructive functionalization of graphitic carbon as Pt support to improve its electrocatalytic performance, (2) triple-junction of metal–carbon–metal oxides to promote Pt performance, (3) nitrogen-doped carbon and metal-doped carbon (i.e., metal oxides) to improve redox reactions in flowmore » batteries. A perspective on future research and the synergy between the two technologies are also discussed.« less

Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

PubMed

Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

2018-04-04

Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

Layer-by-layer self-assembly in the development of electrochemical energy conversion and storage devices from fuel cells to supercapacitors.

PubMed

Xiang, Yan; Lu, Shanfu; Jiang, San Ping

2012-11-07

As one of the most effective synthesis tools, layer-by-layer (LbL) self-assembly technology can provide a strong non-covalent integration and accurate assembly between homo- or hetero-phase compounds or oppositely charged polyelectrolytes, resulting in highly-ordered nanoscale structures or patterns with excellent functionalities and activities. It has been widely used in the developments of novel materials and nanostructures or patterns from nanotechnologies to medical fields. However, the application of LbL self-assembly in the development of highly efficient electrocatalysts, specific functionalized membranes for proton exchange membrane fuel cells (PEMFCs) and electrode materials for supercapacitors is a relatively new phenomenon. In this review, the application of LbL self-assembly in the development and synthesis of key materials of PEMFCs including polyelectrolyte multilayered proton-exchange membranes, methanol-blocking Nafion membranes, highly uniform and efficient Pt-based electrocatalysts, self-assembled polyelectrolyte functionalized carbon nanotubes (CNTs) and graphenes will be reviewed. The application of LbL self-assembly for the development of multilayer nanostructured materials for use in electrochemical supercapacitors will also be reviewed and discussed (250 references).

Polyethyleneimine functionalized platinum superstructures: enhancing hydrogen evolution performance by morphological and interfacial control† †Electronic supplementary information (ESI) available: Experimental details and additional physical characterization. See DOI: 10.1039/c7sc04109h

PubMed Central

Xu, Guang-Rui; Bai, Juan; Jiang, Jia-Xing

2017-01-01

The electrocatalytic hydrogen evolution reaction (HER) is a highly promising green method for sustainable and efficient hydrogen production. So far, Pt nanocrystals are still the most active electrocatalysts for the HER in acidic media, although a tremendous search for alternatives has been done in the past decade. In this work, we synthesize polyethyleneimine (PEI) functionalized Pt superstructures (Pt-SSs@PEI) with tetragonal, hierarchical, and branched morphologies with a facile wet chemical reduction method. A series of physical characterizations are conducted to investigate the morphology, electronic structure, surface composition, and formation mechanism of Pt-SSs@PEI. Impressively, the as-prepared Pt-SSs@PEI show an unprecedented onset reduction potential (+64.6 mV vs. reversible hydrogen electrode) for the HER in strong acidic media due to the protonation of –NH2 groups in the PEI adlayers on the Pt surface, and they outperform all currently reported HER electrocatalysts. The work highlights a highly effective interface-engineering strategy for improving the electrocatalytic performance of Pt nanocrystals for the HER. PMID:29619188

Cobalt/copper-decorated carbon nanofibers as novel non-precious electrocatalyst for methanol electrooxidation

PubMed Central

2014-01-01

In this study, Co/Cu-decorated carbon nanofibers are introduced as novel electrocatalyst for methanol oxidation. The introduced nanofibers have been prepared based on graphitization of poly(vinyl alcohol) which has high carbon content compared to many polymer precursors for carbon nanofiber synthesis. Typically, calcination in argon atmosphere of electrospun nanofibers composed of cobalt acetate tetrahydrate, copper acetate monohydrate, and poly(vinyl alcohol) leads to form carbon nanofibers decorated by CoCu nanoparticles. The graphitization of the poly(vinyl alcohol) has been enhanced due to presence of cobalt which acts as effective catalyst. The physicochemical characterization affirmed that the metallic nanoparticles are sheathed by thin crystalline graphite layer. Investigation of the electrocatalytic activity of the introduced nanofibers toward methanol oxidation indicates good performance, as the corresponding onset potential was small compared to many reported materials; 310 mV (vs. Ag/AgCl electrode) and a current density of 12 mA/cm2 was obtained. Moreover, due to the graphite shield, good stability was observed. Overall, the introduced study opens new avenue for cheap and stable transition metals-based nanostructures as non-precious catalysts for fuel cell applications. PMID:24387682

Co3O4-x-Carbon@Fe2-yCoyO3 Heterostructural Hollow Polyhedrons for the Oxygen Evolution Reaction.

PubMed

Xu, Wangwang; Xie, Weiwei; Wang, Ying

2017-08-30

Hollow heterostructured nanomaterials have received tremendous interest in new-generation electrocatalyst applications. However, the design and fabrication of such materials remain a significant challenge. In this work, we present Co 3 O 4-x -carbon@Fe 2-y Co y O 3 heterostructural hollow polyhedrons that have been fabricated by facile thermal treatment followed by solution-phase growth for application as efficient oxygen evolution reaction (OER) electrocatalysts. Starting from a single ZIF-67 hollow polyhedron, a novel complex structured composite material constructed from Co 3 O 4-x nanocrystallite-embedded carbon matrix embedded with Fe 2-y Co y O 3 nanowires was successfully prepared. The Co 3 O 4-x nanocrystallite with oxygen vacancies provides both heterogeneous nucleation sites and growth platform for Fe 2-y Co y O 3 nanowires. The resultant heterostructure combines the advantages of Fe 2-y Co y O 3 nanowires with the large surface area and surface defects of Co 3 O 4-x nanocrystallite, resulting in improved electrocatalytic activity and electrical conductivity. As a result, such novel heterostructured OER electrocatalysts exhibit much lower onset potential (1.52 V) and higher current density (70 mA/cm 2 at 1.7 V) than Co 3 O 4-x -carbon hollow polyhedrons (onset 1.55 V, 35 mA/cm 2 at 1.7 V) and pure Co 3 O 4 hollow polyhedrons (onset 1.62 V, 5 mA/cm 2 at 1.7 V). Furthermore, the design and synthesis of metal-organic framework (MOF)-derived nanomaterials in this work offer new opportunities for developing novel and efficient electrocatalysts in electrochemical devices.

ECUT: Energy Conversion and Utilization Technologies program. Chemical Processes project report, FY 1982

NASA Technical Reports Server (NTRS)

Wilcox, R. E. (Compiler)

1983-01-01

Planned research efforts and reorganization of the Project as the Biocatalysis Research Activity are described, including the following topics: electrocatalysts, fluid extraction, ammonia synthesis, biocatalysis, membrane fouling, energy and economic analysis, decarboxylation, microscopic reaction models, plasmid monitoring, and reaction kinetics.

Subnanometer Molybdenum Sulfide on Carbon Nanotubes as a Highly Active and Stable Electrocatalyst for Hydrogen Evolution Reaction.

PubMed

Li, Ping; Yang, Zhi; Shen, Juanxia; Nie, Huagui; Cai, Qiran; Li, Luhua; Ge, Mengzhan; Gu, Cancan; Chen, Xi'an; Yang, Keqin; Zhang, Lijie; Chen, Ying; Huang, Shaoming

2016-02-10

Electrochemically splitting water for hydrogen evolution reaction (HER) has been viewed as a promising approach to produce renewable and clean hydrogen energy. However, searching for cheap and efficient HER electrocatalysts to replace the currently used Pt-based catalysts remains an urgent task. Herein, we develop a one-step carbon nanotube (CNT) assisted synthesis strategy with CNTs' strong adsorbability to mediate the growth of subnanometer-sized MoS(x) on CNTs. The subnanometer MoS(x)-CNT hybrids achieve a low overpotential of 106 mV at 10 mA cm(-2), a small Tafel slope of 37 mV per decade, and an unprecedentedly high turnover frequency value of 18.84 s(-1) at η = 200 mV among all reported non-Pt catalysts in acidic conditions. The superior performance of the hybrid catalysts benefits from the presence of a higher number of active sites and the abundant exposure of unsaturated S atoms rooted in the subnanometer structure, demonstrating a new class of subnanometer-scale catalysts.

Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution.

PubMed

Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

2016-04-01

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution

NASA Astrophysics Data System (ADS)

Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui; Li, Shun-Li; Wang, Yu-Guang; Dong, Long-Zhang; Dai, Zhi-Hui; Li, Ya-Fei; Lan, Ya-Qian

2016-04-01

Electrochemical water splitting is one of the most economical and sustainable methods for large-scale hydrogen production. However, the development of low-cost and earth-abundant non-noble-metal catalysts for the hydrogen evolution reaction remains a challenge. Here we report a two-dimensional coupled hybrid of molybdenum carbide and reduced graphene oxide with a ternary polyoxometalate-polypyrrole/reduced graphene oxide nanocomposite as a precursor. The hybrid exhibits outstanding electrocatalytic activity for the hydrogen evolution reaction and excellent stability in acidic media, which is, to the best of our knowledge, the best among these reported non-noble-metal catalysts. Theoretical calculations on the basis of density functional theory reveal that the active sites for hydrogen evolution stem from the pyridinic nitrogens, as well as the carbon atoms, in the graphene. In a proof-of-concept trial, an electrocatalyst for hydrogen evolution is fabricated, which may open new avenues for the design of nanomaterials utilizing POMs/conducting polymer/reduced-graphene oxide nanocomposites.

Is Ammonium Peroxydisulate Indispensable for Preparation of Aniline-Derived Iron-Nitrogen-Carbon Electrocatalysts?

PubMed

Xie, Nan-Hong; Yan, Xiang-Hui; Xu, Bo-Qing

2016-09-08

Iron and nitrogen co-doped carbon (Fe-N-C) materials are among the most active non-precious metal catalysts that could replace Pt-based electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. The synthesis of the Fe-N-C catalysts often involves the use of aniline as the precursor for both N and C and ammonium peroxydisulfate (APS) as an indispensable oxidative initiator for aniline polymerization. Herein, a detailed structure and catalytic ORR performance comparison of aniline-derived Fe-N-C catalysts synthesized with and without the use of APS is reported. The APS-free preparation, which uses Fe(III) ions as the Fe source as well as the aniline polymerization initiator, results in a simple Fe-N-C catalyst with a high activity for the ORR. We show that APS is not necessary for the preparation and even detrimental to the performance of the catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte

PubMed Central

Gorlin, Yelena; Jaramillo, Thomas F.

2014-01-01

The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide) and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite) in three different electrolytes (sulfuric acid, sodium acetate, and sodium hydroxide). We determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community. PMID:25357131

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

DOE PAGES

Hod, Idan; Deria, Pravas; Bury, Wojciech; ...

2015-09-14

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm −2. In conclusion,more » although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst.« less

Significant advantages of sulfur-doped graphene in neutral media as electrocatalyst for oxygen reduction comparing with Pt/C

NASA Astrophysics Data System (ADS)

Shi, Xinxin; Zhang, Jiaona; Huang, Tinglin

2018-02-01

Sulfur-doped graphene (SDG) has been found to be an efficient electrocatalyst for oxygen reduction reaction. However, previous studies on the catalytic activity of SDG have been mainly confined to O2-saturated alkaline media which is a typical alkaline fuel cell environment. Air-cathode microbial fuel cells (ACMFCs), as a novel energy conversion and wastewater treatment technology, use the oxygen from air as cathodic reactant in neutral media with low concentration of O2. Thus, it is meaningful to explore the catalytic performance of SDG in such ACMFC environment. The result showed that in ACMFC environment, the peak current density of SDG in CV test was surprisingly 4.5 times higher than that of Pt/C, indicating a much stronger catalytic activity of SDG. Moreover, SDG exhibited a stronger tolerance against the crossover of glucose (a typical anodic fuel in ACMFC) and better stability than Pt/C in neutral media.

Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution

DOE PAGES

Lu, Qi; Hutchings, Gregory S.; Yu, Weiting; ...

2015-03-16

One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchicalmore » porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.« less

Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte

DOE PAGES

Benck, Jesse D.; Pinaud, Blaise A.; Gorlin, Yelena; ...

2014-10-30

The selection of an appropriate substrate is an important initial step for many studies of electrochemically active materials. In order to help researchers with the substrate selection process, we employ a consistent experimental methodology to evaluate the electrochemical reactivity and stability of seven potential substrate materials for electrocatalyst and photoelectrode evaluation. Using cyclic voltammetry with a progressively increased scan range, we characterize three transparent conducting oxides (indium tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide) and four opaque conductors (gold, stainless steel 304, glassy carbon, and highly oriented pyrolytic graphite) in three different electrolytes (sulfuric acid, sodium acetate, andmore » sodium hydroxide). Here, we determine the inert potential window for each substrate/electrolyte combination and make recommendations about which materials may be most suitable for application under different experimental conditions. Furthermore, the testing methodology provides a framework for other researchers to evaluate and report the baseline activity of other substrates of interest to the broader community.« less

A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution

PubMed Central

Hod, Idan; Deria, Pravas; Bury, Wojciech; Mondloch, Joseph E.; Kung, Chung-Wei; So, Monica; Sampson, Matthew D.; Peters, Aaron W.; Kubiak, Cliff P.; Farha, Omar K.; Hupp, Joseph T.

2015-01-01

The availability of efficient hydrogen evolution reaction (HER) catalysts is of high importance for solar fuel technologies aimed at reducing future carbon emissions. Even though Pt electrodes are excellent HER electrocatalysts, commercialization of large-scale hydrogen production technology requires finding an equally efficient, low-cost, earth-abundant alternative. Here, high porosity, metal-organic framework (MOF) films have been used as scaffolds for the deposition of a Ni-S electrocatalyst. Compared with an MOF-free Ni-S, the resulting hybrid materials exhibit significantly enhanced performance for HER from aqueous acid, decreasing the kinetic overpotential by more than 200 mV at a benchmark current density of 10 mA cm−2. Although the initial aim was to improve electrocatalytic activity by greatly boosting the active area of the Ni-S catalyst, the performance enhancements instead were found to arise primarily from the ability of the proton-conductive MOF to favourably modify the immediate chemical environment of the sulfide-based catalyst. PMID:26365764

Advancing semiconductor–electrocatalyst systems: application of surface transformation films and nanosphere lithography

DOE PAGES

Brinkert, Katharina; Richter, Matthias H.; Akay, Ömer; ...

2018-01-01

We demonstrate that shadow nanosphere lithography (SNL) is an auspicious tool to systematically create three-dimensional electrocatalyst nanostructures on the semiconductor photoelectrode through controlling their morphology and optical properties.

A New Member of Electrocatalysts Based on Nickel Metaphosphate Nanocrystals for Efficient Water Oxidation.

PubMed

Huang, Jianwen; Sun, Yinghui; Zhang, Yadong; Zou, Guifu; Yan, Chaoyi; Cong, Shan; Lei, Tianyu; Dai, Xiao; Guo, Jun; Lu, Ruifeng; Li, Yanrong; Xiong, Jie

2018-02-01

High-performance electrocatalysts are desired for electrochemical energy conversion, especially in the field of water splitting. Here, a new member of phosphate electrocatalysts, nickel metaphosphate (Ni 2 P 4 O 12 ) nanocrystals, is reported, exhibiting low overpotential of 270 mV to generate the current density of 10 mA cm -2 and a superior catalytic durability of 100 h. It is worth noting that Ni 2 P 4 O 12 electrocatalyst has remarkable oxygen evolution performance operating in basic media. Further experimental and theoretical analyses demonstrate that N dopant boosts the catalytic performance of Ni 2 P 4 O 12 due to optimizing the surface electronic structure for better charge transfer and decreasing the adsorption energy for the oxygenic intermediates. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase-controlled synthesis of polymorphic tungsten diphosphide with hybridization of monoclinic and orthorhombic phases as a novel electrocatalyst for efficient hydrogen evolution

NASA Astrophysics Data System (ADS)

Pi, Mingyu; Wu, Tianli; Guo, Weimeng; Wang, Xiaodeng; Zhang, Dingke; Wang, Shuxia; Chen, Shijian

2017-05-01

The design and development of high-efficiency and non-noble-metal hydrogen evolution reaction (HER) electrocatalysts for future clean and renewable energy system has excited significant research interests over the recent years. In this communication, the polymorphic tungsten diphosphide (p-WP2) nanoparticles with mixed monoclinic (α-) and orthorhombic (β-) phases are synthesized by phase-controlled phosphidation route via vacuum capsulation and explored as a novel efficient electrocatalyst towards HER. The p-WP2 catalyst delivers superior performance with excellent stability under both acidic and alkaline conditions over its single phases of α-WP2 and β-WP2. This finding demonstrates that a highly efficient hybrid electrocatalyst can be achieved via precise composition controlling and may open up exciting opportunities for their practical applications toward energy conversion.

N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

NASA Astrophysics Data System (ADS)

Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

2016-09-01

Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm-2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER.

N-doped graphene layers encapsulated NiFe alloy nanoparticles derived from MOFs with superior electrochemical performance for oxygen evolution reaction

PubMed Central

Feng, Yi; Yu, Xin-Yao; Paik, Ungyu

2016-01-01

Water splitting, an efficient approach for hydrogen production, is often hindered by unfavorable kinetics of oxygen evolution reaction (OER). In order to reduce the overpotential, noble metal oxides-based electrocatalysts like RuO2 and IrO2 are usually utilized. However, due to their scarcity, the development of cost-effective non-precious OER electrocatalysts with high efficiency and good stability is urgently required. Herein, we report a facile one-step annealing of metal-organic frameworks (MOFs) strategy to synthesize N-doped graphene layers encapsulated NiFe alloy nanoparticles (NiFe@C). Through tuning the nanoparticle size and calcination temperature, NiFe@C with an average size of around 16 nm obtained at 700 °C exhibits superior OER performance with an overpotential of only 281 mV at 10 mA cm−2 and high durability. The facile synthesis method and excellent electrochemical performance show great potential of NiFe@C in replacing the precious metal-based electrocatalysts in the OER. PMID:27658968

The Role of Electrode-Catalyst Interactions in Enabling Efficient CO2 Reduction with Mo(bpy)(CO)4 As Revealed by Vibrational Sum-Frequency Generation Spectroscopy.

PubMed

Neri, Gaia; Donaldson, Paul M; Cowan, Alexander J

2017-10-04

Group 6 metal carbonyl complexes ([M(bpy)(CO) 4 ], M = Cr, Mo, W) are potentially promising CO 2 reduction electrocatalysts. However, catalytic activity onsets at prohibitively negative potentials and is highly dependent on the nature of the working electrode. Here we report in situ vibrational SFG (VSFG) measurements of the electrocatalyst [Mo(bpy)(CO) 4 ] at platinum and gold electrodes. The greatly improved onset potential for electrocatalytic CO 2 reduction at gold electrodes is due to the formation of the catalytically active species [Mo(bpy)(CO) 3 ] 2- via a second pathway at more positive potentials, likely avoiding the need for the generation of [Mo(bpy)(CO) 4 ] 2- . VSFG studies demonstrate that the strength of the interaction between initially generated [Mo(bpy)(CO) 4 ] •- and the electrode is critical in enabling the formation of the active catalyst via the low energy pathway. By careful control of electrode material, solvent and electrolyte salt, it should therefore be possible to attain levels of activity with group 6 complexes equivalent to their much more widely studied group 7 analogues.

Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

NASA Astrophysics Data System (ADS)

Tan, Yao

2018-05-01

Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

Fuel cell with Pt/Pd electrocatalyst electrode

DOEpatents

Stonehart, Paul

1983-01-01

An electrode for use in a phosphoric acid fuel cell comprising a graphitized or partially graphitized carbon support having a platinum/palladium electrocatalyst thereon. Preferably, the platinum/palladium catalyst comprises 20 to 65 weight percent palladium.

Enhanced Hydrogen Evolution Reactions on Nanostructured Cu2ZnSnS4 (CZTS) Electrocatalyst

NASA Astrophysics Data System (ADS)

Digraskar, Renuka V.; Mulik, Balaji B.; Walke, Pravin S.; Ghule, Anil V.; Sathe, Bhaskar R.

2017-08-01

A novel and facile one-step sonochemical method is used to synthesize Cu2ZnSnS4 (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer-Emmett-Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density -130 mA/cm2, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm2, excellent stability (> 500 cycles) and lower charge transfer resistance. This sonochemically fabricated CZTSs nanoparticles are leading to significantly reduce cell cost and simplification of preparation process over existing high efficiency Pt and other nobel metal-free cathode electrocatalyst.

Hierarchical cobalt poly-phosphide hollow spheres as highly active and stable electrocatalysts for hydrogen evolution over a wide pH range

NASA Astrophysics Data System (ADS)

Wu, Tianli; Pi, Mingyu; Wang, Xiaodeng; Guo, Weimeng; Zhang, Dingke; Chen, Shijian

2018-01-01

Exploring highly-efficient and low-cost non-noble metal electrocatalyst toward the hydrogen evolution reaction (HER) is highly desired for renewable energy system but remains challenging. In this work, three dimensional hierarchical porous cobalt poly-phosphide hollow spheres (CoP3 HSs) were prepared by topotactic phosphidation of the cobalt-based precursor via vacuum encapsulation technique. As a porous HER cathode, the CoP3 HSs delivers remarkable electrocatalytic performance over the wide pH range. It needs overpotentials of -69 mV and -118 mV with a small Tafel slope of 51 mV dec-1 to obtain current densities of 10 mA cm-2 and 50 mA cm-2, respectively, and maintains its electrocatalytic performance over 30 h in acidic solution. In addition, CoP3 also exhibit superior electrocatalytic performance and stability under neutral and alkaline conditions for the HER. Both experimental measurements and density functional theory (DFT) calculations are performed to explore the mechanism behind the excellent HER performance. The results of our study make the porous CoP3 HSs as a promising electrocatalyst for practical applications toward energy conversion system and present a new way for designing and fabricating HER electrodes through high degree of phosphorization and nano-porous architecture.

Fuel Cells | Hydrogen and Fuel Cells | NREL

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Reduction Reaction for Ultrathin Uniform Pt/C Catalyst Layers without Influence from Nafion, Electrochimica Acta (2016) Suppression of Oxygen Reduction Reaction Activity on Pt-Based Electrocatalysts from Ionomer Durability of Iridium Nanoparticles in the Oxygen Evolution Reaction, Journal of the Electrochemical Society

Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

DOEpatents

Adzic, Radoslav; Mo, Yibo; Vukmirovic, Miomir; Zhang, Junliang

2010-12-21

The invention relates to platinum-coated particles useful as fuel cell electrocatalysts. The particles are composed of a noble metal or metal alloy core at least partially encapsulated by an atomically thin surface layer of platinum atoms. The invention particularly relates to such particles having a palladium, palladium alloy, gold alloy, or rhenium alloy core encapsulated by an atomic monolayer of platinum. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

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

Surface Immobilization of Molecular Electrocatalysts for Energy Conversion

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

Bullock, R. Morris; Das, Atanu K.; Appel, Aaron M.

2017-03-22

Electrocatalysts are critically important for a secure energy future, as they facilitate the conversion between electrical energy and chemical energy. Molecular catalysts offer precise control of their structure, and the ability to modify the substituents to understand structure-reactivity relationships that are more difficult to achieve with heterogeneous catalysts. Molecular electrocatalysts can be immobilized on surfaces by covalent bonds or through non-covalent interactions. Advantages of surface immobilization include the need for less catalyst, avoidance of bimolecular decomposition pathways, and easier determination of catalyst lifetime. Copper-catalyzed click reactions are often used to form covalent bonds to surfaces, and pi-pi stacking of pyrenemore » substituents appended to the ligand of a molecular complex is a frequently used method to achieve non-covalent surface immobilization. This mini-review highlights surface confinement of molecular electrocatalysts for reduction of O2, oxidation of H2O, production of H2, and reduction of CO2.« less

Synthesis of flower-like molybdenum sulfide/graphene hybrid as an efficient oxygen reduction electrocatalyst for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Arunchander, A.; Peera, S. Gouse; Sahu, A. K.

2017-06-01

Nanostructured transition metal chalcogenides (TMCs) have significant interest towards electrochemical devices such as fuel cells, metal-ion batteries, due to their unique physical and electrochemical properties. Herein, we report a facile hydrothermal synthesis of flower-like nanostructured molybdenum sulphide and its incorporation on to graphene as a potential oxygen reduction reaction catalyst in alkaline medium. The phase purity and morphological evolution of MoS2 is systematically studied through X-ray diffraction and scanning electron microscopic techniques. The electronic states of metal and non-metallic species are deeply studied by X-ray photoelectron spectroscopy. The effect of annealing temperatures and TMC concentrations are also investigated by electrochemical techniques such as cyclic and linear sweep voltammograms. The optimised electrocatalyst (MoS2/G-500) delivers significant ORR activity with onset and half-wave potentials of 0.91 and 0.80 V (vs. RHE), respectively. Superior durability compared to state-of-art Pt/C catalyst is ascertained by repeating potential cycles for about 5000 times and also by chronoamperometric technique. Finally, the hybrid catalyst is evaluated in AEMFC as cathode catalyst which delivers peak power density of about 29 mW cm-2 under ambient temperature and pressure. The present findings emphasis that MoS2/G catalyst is promising as cost-effective and alternative to noble metal-based catalysts for fuel cell applications.

Boron and oxygen-codoped porous carbon as efficient oxygen reduction catalysts

NASA Astrophysics Data System (ADS)

Lei, Zhidan; Chen, Hongbiao; Yang, Mei; Yang, Duanguang; Li, Huaming

2017-12-01

A low-cost boron- and oxygen-codoped porous carbon electrocatalyst towards oxygen reduction reaction (ORR) has been fabricated by a facile one-step pyrolysis approach, while a boron- and oxygen-rich polymer network was used as precursor. The boron- and oxygen-codoped carbon catalyst with high ORR electrocatalytic activity is comparable to that of Pt/C and is superior to that of catalysts doped solely with boron atoms or with oxygen atoms. Furthermore, the optimized boron- and oxygen-codoped carbon catalyst possesses excellent methanol tolerance and long-term durability in alkaline media. The high electrocatalytic activity of the dual-doped carbon catalysts can be attributed to the synergistic effects of high surface area, predominant mesostructure, abundant active oxygen-containing groups, and effective boron doping. The present results show that this boron- and oxygen-codoping strategy could be as a promising way for the preparation of highly efficient ORR catalysts.

Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions

NASA Astrophysics Data System (ADS)

Qi, Chunling; Zhang, Li; Xu, Guancheng; Sun, Zhipeng; Zhao, Aihua; Jia, Dianzeng

2018-01-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play crucial roles in efficient energy conversion and storage solutions. Here, Co@Co3O4 nanoparticle embedded nitrogen-doped carbon architectures (denoted as Co@Co3O4/NCs) are prepared via a simple two-step and in situ approach by carbonization and subsequent oxidation of Co-MOF containing high contents of carbon and nitrogen. When evaluated as electrocatalyst towards both ORR and OER in a KOH electrolyte solution, the as-fabricated Co@Co3O4/NC-2 exhibits similar ORR catalytic activity to the commercial Pt/C catalyst, but superior stability and good methanol tolerance. Furthermore, the as-fabricated catalysts also show promising catalytic activity for OER. The effective catalytic activities originate from the synergistic effects between well wrapped Co@Co3O4 nanoparticles and nitrogen doped carbon structures.

Facile Synthesis of N-Doped Graphene-Like Carbon Nanoflakes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction

NASA Astrophysics Data System (ADS)

Gu, Daguo; Zhou, Yao; Ma, Ruguang; Wang, Fangfang; Liu, Qian; Wang, Jiacheng

2018-06-01

A series of N-doped carbon materials (NCs) were synthesized by using biomass citric acid and dicyandiamide as renewable raw materials via a facile one-step pyrolysis method. The characterization of microstructural features shows that the NCs samples are composed of few-layered graphene-like nanoflakes with controlled in situ N doping, which is attributed to the confined pyrolysis of citric acid within the interlayers of the dicyandiamide-derived g-C3N4 with high nitrogen contents. Evidently, the pore volumes of the NCs increased with the increasing content of dicyandiamide in the precursor. Among these samples, the NCs nanoflakes prepared with the citric acid/dicyandiamide mass ratio of 1:6, NC-6, show the highest N content of 6.2 at%, in which pyridinic and graphitic N groups are predominant. Compared to the commercial Pt/C catalyst, the as-prepared NC-6 exhibits a small negative shift of 66 mV at the half-wave potential, demonstrating excellent electrocatalytic activity in the oxygen reduction reaction. Moreover, NC-6 also shows better long-term stability and resistance to methanol crossover compared to Pt/C. The efficient and stable performance are attributed to the graphene-like microstructure and high content of pyridinic and graphitic doped nitrogen in the sample, which creates more active sites as well as facilitating charge transfer due to the close four-electron reaction pathway. The superior electrocatalytic activity coupled with the facile synthetic method presents a new pathway to cost-effective electrocatalysts for practical fuel cells or metal-air batteries.

Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting

NASA Astrophysics Data System (ADS)

Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias; Cheng, Xi; Kim, Bae-Jung; Durst, Julien; Bozza, Francesco; Graule, Thomas; Schäublin, Robin; Wiles, Luke; Pertoso, Morgan; Danilovic, Nemanja; Ayers, Katherine E.; Schmidt, Thomas J.

2017-09-01

The growing need to store increasing amounts of renewable energy has recently triggered substantial R&D efforts towards efficient and stable water electrolysis technologies. The oxygen evolution reaction (OER) occurring at the electrolyser anode is central to the development of a clean, reliable and emission-free hydrogen economy. The development of robust and highly active anode materials for OER is therefore a great challenge and has been the main focus of research. Among potential candidates, perovskites have emerged as promising OER electrocatalysts. In this study, by combining a scalable cutting-edge synthesis method with time-resolved X-ray absorption spectroscopy measurements, we were able to capture the dynamic local electronic and geometric structure during realistic operando conditions for highly active OER perovskite nanocatalysts. Ba0.5Sr0.5Co0.8Fe0.2O3-δ as nano-powder displays unique features that allow a dynamic self-reconstruction of the material’s surface during OER, that is, the growth of a self-assembled metal oxy(hydroxide) active layer. Therefore, besides showing outstanding performance at both the laboratory and industrial scale, we provide a fundamental understanding of the operando OER mechanism for highly active perovskite catalysts. This understanding significantly differs from design principles based on ex situ characterization techniques.

One-Pot Anchoring of Pd Nanoparticles on Nitrogen-Doped Carbon through Dopamine Self-Polymerization and Activity in the Electrocatalytic Methanol Oxidation Reaction.

PubMed

Li, Xin; Niu, Xiangheng; Zhang, Wenchi; He, Yanfang; Pan, Jianming; Yan, Yongsheng; Qiu, Fengxian

2017-03-09

Exploration of advanced electrocatalysts to promote the sluggish methanol oxidation reaction (MOR) is of vital importance for developing high efficiency and low-cost direct methanol fuel cells. Highly dispersed palladium nanoparticles (Pd NPs) anchored on a nitrogen-doped carbon support were fabricated using a facile one-pot dopamine self-polymerization mediated redox strategy, in which dopamine not only acted as a moderate reductant to induce the formation of Pd NPs during self-polymerization but was also the precursor of the nitrogen-doped carbon support for Pd. The synthesized hybrid features the following characteristics: 1) High dispersity of Pd NPs, which exposed a high abundance of active surfaces and sites for heterogeneous electrocatalysis; 2) metal-support interactions, which may affect the surface chemistry and electron distribution of active Pd NPs; 3) the Pd NPs were partially imbedded or encapsulated into the support, thus reducing the possible agglomeration of Pd NPs during cyclic measurements. The electrocatalyst with such favorable features provided higher mass activity (2.2 times that of commercial Pd/C) and better durability (reduced loss of activity during simulated frequent startup-shutdown operations) for the MOR in alkaline media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

One-Pot and Facile Fabrication of Hierarchical Branched Pt-Cu Nanoparticles as Excellent Electrocatalysts for Direct Methanol Fuel Cells.

PubMed

Cao, Yanqin; Yang, Yong; Shan, Yufeng; Huang, Zhengren

2016-03-09

Hierarchical branched nanoparticles are one promising nanostructure with three-dimensional open porous structure composed of integrated branches for superior catalysis. We have successfully synthesized Pt-Cu hierarchical branched nanoparticles (HBNDs) with small size of about 30 nm and composed of integrated ultrathin branches by using a modified polyol process with introduction of poly(vinylpyrrolidone) and HCl. This strategy is expected to be a general strategy to prepare various metallic nanostructures for catalysis. Because of the special open porous structure, the as-prepared Pt-Cu HBNDs exhibit greatly enhanced specific activity toward the methanol oxidation reaction as much as 2.5 and 1.7 times compared with that of the commercial Pt-Ru and Pt-Ru/C catalysts, respectively. Therefore, they are potentially applicable as electrocatalysts for direct methanol fuel cells.

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

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala

Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

Facile synthesis of porous Pt-Pd nanospheres supported on reduced graphene oxide nanosheets for enhanced methanol electrooxidation

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Lv, Jing-Jing; Hu, Yuan-Yuan; Zheng, Jie-Ning; Chen, Jian-Rong; Wang, Ai-Jun; Feng, Jiu-Ju

2014-02-01

In this study, a simple, facile, and effective wet-chemical strategy was developed in the synthesis of uniform porous Pt-Pd nanospheres (Pt-Pd NSs) supported on reduced graphene oxide nanosheets (RGOs) under ambient temperature, where octylphenoxypolye thoxyethanol (NP-40) is used as a soft template, without any seed, organic solvent or special instruments. The as-prepared nanocomposites display enhanced electrocatalytic activity and good stability toward methanol oxidation, compared with commercial Pd/C and Pt/C catalysts. This strategy may open a new route to design and prepare advanced electrocatalysts for fuel cells.

Boosting ORR Catalytic Activity by Integrating Pyridine-N Dopants, a High Degree of Graphitization, and Hierarchical Pores into a MOF-Derived N-Doped Carbon in a Tandem Synthesis.

PubMed

Liu, Dandan; Li, Liangjun; Xu, Huanfei; Dai, Pengcheng; Wang, Ying; Gu, Xin; Yan, Liting; Zhao, Guoming; Zhao, Xuebo

2018-05-18

N-doped carbon materials represent promising metal-free electrocatalysts for the oxygen reduction reaction (ORR), the cathode reaction in fuel cells, metal-air batteries, and so on. A challenge for optimizing the ORR catalytic activities of these electrocatalysts is to tune their local structures and chemical compositions in a rational and controlled way that can achieve the synergistic function of each factor. Herein, we report a tandem synthetic strategy that integrates multiple contributing factors into an N-doped carbon. With an N-containing MOF (ZIF-8) as the precursor, carbonization at higher temperatures leads to a higher degree of graphitization. Subsequent NH 3 etching of this highly graphitic carbon enabled the introduction of a higher content of pyridine-N sites and higher porosity. By optimizing these three factors, the resultant carbon materials displayed ORR activity that was far superior to that of carbon derived from a one-step pyrolysis. The onset potential of 0.955 V versus a reversible hydrogen electrode (RHE) and the half-wave potential of 0.835 V versus RHE are among the top ranks of metal-free ORR catalysts and are comparable to commercial Pt/C (20 wt %) catalysts. Kinetic studies revealed lower H 2 O 2 yields, higher electron-transfer numbers, and lower Tafel slopes for these carbon materials compared with that derived from a one-step carbonization. These findings verify the effectiveness of this tandem synthetic strategy to enhance the ORR activity of N-doped carbon materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tracking Catalyst Redox States and Reaction Dynamics in Ni-Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH.

PubMed

Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike; Bernsmeier, Denis; Dresp, Sören; Gliech, Manuel; Jusys, Zenonas; Chernev, Petko; Kraehnert, Ralph; Dau, Holger; Strasser, Peter

2017-02-08

Ni-Fe oxyhydroxides are the most active known electrocatalysts for the oxygen evolution reaction (OER) in alkaline electrolytes and are therefore of great scientific and technological importance in the context of electrochemical energy conversion. Here we uncover, investigate, and discuss previously unaddressed effects of conductive supports and the electrolyte pH on the Ni-Fe(OOH) catalyst redox behavior and catalytic OER activity, combining in situ UV-vis spectro-electrochemistry, operando electrochemical mass spectrometry (DEMS), and in situ cryo X-ray absorption spectroscopy (XAS). Supports and pH > 13 strongly enhanced the precatalytic voltammetric charge of the Ni-Fe oxyhydroxide redox peak couple, shifted them more cathodically, and caused a 2-3-fold increase in the catalytic OER activity. Analysis of DEMS-based faradaic oxygen efficiency and electrochemical UV-vis traces consistently confirmed our voltammetric observations, evidencing both a more cathodic O 2 release and a more cathodic onset of Ni oxidation at higher pH. Using UV-vis, which can monitor the amount of oxidized Ni +3/+4 in situ, confirmed an earlier onset of the redox process at high electrolyte pH and further provided evidence of a smaller fraction of Ni +3/+4 in mixed Ni-Fe centers, confirming the unresolved paradox of a reduced metal redox activity with increasing Fe content. A nonmonotonic super-Nernstian pH dependence of the redox peaks with increasing Fe content-displaying Pourbaix slopes as steep as -120 mV/pH-suggested a two proton-one electron transfer. We explain and discuss the experimental pH effects using refined coupled (PCET) and decoupled proton transfer-electron transfer (PT/ET) schemes involving negatively charged oxygenate ligands generated at Fe centers. Together, we offer new insight into the catalytic reaction dynamics and associated catalyst redox chemistry of the most important class of alkaline OER catalysts.

Stabilized metal nanoparticles from organometallic precursors for low temperature fuel cells.

PubMed

Ramirez-Meneses, E; Dominguez-Crespo, M A; Torres-Huerta, A M

2013-01-01

In this work, a review of articles and patents related to the utilization of colloidal metal nanoparticles produced by the decomposition of organometallic precursors as supported electrocatalysts in different electrochemical reactions including hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is discussed. In the case of stabilized metal nanoparticles, the kind of functional group contained in the stabilizer as well as the metal/stabilizer ratio, to evaluate the effect of particle size on the electrochemical performance, were also debated. Potential applications and perspectives of these electrocatalysts in proton exchange membrane fuel cells (PEMFC) are contended with reference to the role played by the coordination compounds and costs.

2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

2016-08-01

Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr04073j

Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

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

Cha, Jennifer N.; Wang, Joseph

2014-08-31

The overall objective of the proposed research is to use fundamental advances in bionanotechnology to design powerful platinum nanocrystal electrocatalysts for fuel cell applications. The new economically-viable, environmentally-friendly, bottom-up biochemical synthetic strategy will produce platinum nanocrystals with tailored size, shape and crystal orientation, hence leading to a maximum electrochemical reactivity. There are five specific aims to the proposed bio-inspired strategy for synthesizing efficient electrocatalytic platinum nanocrystals: (1) isolate peptides that both selectively bind particular crystal faces of platinum and promote the nucleation and growth of particular nanocrystal morphologies, (2) pattern nanoscale 2-dimensional arrays of platinum nucleating peptides from DNA scaffolds,more » (3) investigate the combined use of substrate patterned peptides and soluble peptides on nanocrystal morphology and growth (4) synthesize platinum crystals on planar and large-area carbon electrode supports, and (5) perform detailed characterization of the electrocatalytic behavior as a function of catalyst size, shape and morphology. Project Description and Impact: This bio-inspired collaborative research effort will address key challenges in designing powerful electrocatalysts for fuel cell applications by employing nucleic acid scaffolds in combination with peptides to perform specific, environmentally-friendly, simultaneous bottom-up biochemical synthesis and patterned assembly of highly uniform and efficient platinum nanocrystal catalysts. Bulk synthesis of nanoparticles usually produces a range of sizes, accessible catalytic sites, crystal morphologies, and orientations, all of which lead to inconsistent catalytic activities. In contrast, biological systems routinely demonstrate exquisite control over inorganic syntheses at neutral pH and ambient temperature and pressures. Because the orientation and arrangement of the templating biomolecules can be precisely controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.« less

Carbon monoxide tolerant electrocatalyst with low platinum loading and a process for its preparation

DOEpatents

Adzic, Radoslav; Brankovic, Stanko; Wang, Jia

2003-12-30

An electrocatalyst is provided for use in a fuel cell that has low platinum loading and a high tolerance to carbon monoxide poisoning. The fuel cell anode includes an electrocatalyst that has a conductive support material, ruthenium nanoparticles reduced in H.sub.2 and a Group VIII noble metal in an amount of between about 0.1 and 25 wt % of the ruthenium nanoparticles, preferably between about 0.5 and 15 wt %. The preferred Group VIII noble metal is platinum. In one embodiment, the anode can also have a perfluorinated polymer membrane on its surface.

Nano-engineered intrapores in nanoparticles of PtNi networks for increased oxygen reduction reaction activity

NASA Astrophysics Data System (ADS)

Ding, Jieting; Ji, Shan; Wang, Hui; Key, Julian; Brett, Dan J. L.; Wang, Rongfang

2018-01-01

Network-like metallic alloys of solid nanoparticles have been frequently reported as promising electrocatalysts for fuel cells. The three-dimensional structure of such networks is rich in pores in the form of voids between nanoparticles, which collectively expose a large surface area for catalytic activity. Herein, we present a novel solution to this problem using a precursor comprising a flocculent core-shell PtNi@Ni to produce PtNi network catalysts with nanoparticle intraporosity after carefully controlled electrochemical dealloying. Physical characterization shows a hierarchical level of nanoporosity (intrapores within nanoparticles and pores between them) evolves during the controlled electrochemical dealloying, and that a Pt-rich surface also forms after 22 cycles of Ni leaching. In ORR cycling, the PtNi networks gain 4-fold activity in both jECSA and jmass over a state of the art Pt/C electrocatalyst, and also significantly exceed previously reported PtNi networks. In ORR degradation tests, the PtNi networks also proved stable, dropping by 30.4% and 62.6% in jECSA and jmass respectively. The enhanced performance of the catalyst is evident, and we also propose that the presented synthesis procedure can be generally applied to developing other metallic networks.

Spherical α-MnO₂ Supported on N-KB as Efficient Electrocatalyst for Oxygen Reduction in Al-Air Battery.

PubMed

Chen, Kui; Wang, Mei; Li, Guangli; He, Quanguo; Liu, Jun; Li, Fuzhi

2018-04-13

Traditional noble metal platinum (Pt) is regarded as a bifunctional oxygen catalyst due to its highly catalytic efficiency, but its commercial availability and application is often restricted by high cost. Herein, a cheap and effective catalyst mixed with α-MnO₂ and nitrogen-doped Ketjenblack (N-KB) (denoted as MnO₂-SM150-0.5) is examined as a potential electrocatalyst in oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). This α-MnO₂ is prepared by redox reaction between K₂S₂O₈ and MnSO₄ in acid conditions with a facile hydrothermal process (named the SM method). As a result, MnO₂-SM150-0.5 exhibits a good catalytic performance for ORR in alkaline solution, and this result is comparable to a Pt/C catalyst. Moreover, this catalyst also shows superior durability and methanol tolerance compared with a Pt/C catalyst. It also displays a discharge voltage (~1.28 V) at a discharge density of 50 mA cm -2 in homemade Al-air batteries that is higher than commercial 20% Pt/C (~1.19 V). The superior electrocatalytic performance of MnO₂-SM150-0.5 could be attributed to its higher Mn 3+ /Mn 4+ ratio and the synergistic effect between MnO₂ and the nitrogen-doped KB. This study provides a novel strategy for the preparation of an MnO₂-based composite electrocatalyst.

Gold-supported cerium-doped NiO x catalysts for water oxidation

DOE PAGES

Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; ...

2016-04-29

Here, the development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highlymore » active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeO x–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.« less

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.

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.

Hollow microspheres with a tungsten carbide kernel for PEMFC application.

PubMed

d'Arbigny, Julien Bernard; Taillades, Gilles; Marrony, Mathieu; Jones, Deborah J; Rozière, Jacques

2011-07-28

Tungsten carbide microspheres comprising an outer shell and a compact kernel prepared by a simple hydrothermal method exhibit very high surface area promoting a high dispersion of platinum nanoparticles, and an exceptionally high electrochemically active surface area (EAS) stability compared to the usual Pt/C electrocatalysts used for PEMFC application.

Iron vs. cobalt clathrochelate electrocatalysts of HER: the first example on a cage iron complex.

PubMed

Dolganov, Alexander V; Belov, Alexander S; Novikov, Valentin V; Vologzhanina, Anna V; Mokhir, Andriy; Bubnov, Yurii N; Voloshin, Yan Z

2013-04-07

New macrobicyclic 2-thiopheneboron-capped iron and cobalt(II) tris-dioximates showed high electrocatalytic activity for hydrogen production from H(+) ions. This is the first example of the hydrogen evolution reaction electrocatalyzed by a clathrochelate iron complex, which catalyzes the hydrogen production at low overpotential.

A Facile Synthesis of Nitrogen-Doped Highly Porous Carbon Nanoplatelets: Efficient Catalysts for Oxygen Electroreduction

NASA Astrophysics Data System (ADS)

Zhang, Yaqing; Zhang, Xianlei; Ma, Xiuxiu; Guo, Wenhui; Wang, Chunchi; Asefa, Tewodros; He, Xingquan

2017-02-01

The oxygen reduction reaction (ORR) is of great importance for various renewable energy conversion technologies such as fuel cells and metal-air batteries. Heteroatom-doped carbon nanomaterials have proven to be robust metal-free electrocatalysts for ORR in the above-mentioned energy devices. Herein, we demonstrate the synthesis of novel highly porous N-doped carbon nanoplatelets (N-HPCNPs) derived from oatmeal (or a biological material) and we show the materials’ high-efficiency as electrocatalyst for ORR. The obtained N-HPCNPs hybrid materials exhibit superior electrocatalytic activities towards ORR, besides excellent stability and good methanol tolerance in both basic and acidic electrolytes. The unique nanoarchitectures with rich micropores and mesopores, as well as the high surface area-to-volume ratios, present in the materials significantly increase the density of accessible catalytically active sites in them and facilitate the transport of electrons and electrolyte within the materials. Consequently, the N-HPCNPs catalysts hold a great potential to serve as low-cost and highly efficient cathode materials in direct methanol fuel cells (DMFCs).

Enhancing Electrode Performance by Exsolved Nanoparticles: A Superior Cobalt-Free Perovskite Electrocatalyst for Solid Oxide Fuel Cells.

PubMed

Yang, Guangming; Zhou, Wei; Liu, Meilin; Shao, Zongping

2016-12-28

The successful development of low-cost, durable electrocatalysts for oxygen reduction reaction (ORR) at intermediate temperatures is critical for broad commercialization of solid oxide fuel cells. Here, we report our findings in design, fabrication, and characterization of a cobalt-free SrFe 0.85 Ti 0.1 Ni 0.05 O 3-δ cathode decorated with NiO nanoparticles. Exsolved from and well bonded to the parent electrode under well-controlled conditions, the NiO nanoparticles uniformly distributed on the surface of the parent electrode greatly enhance cathode performance, demonstrating ORR activity better than that of the benchmark cobalt-based Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ . Further, a process for regeneration of the NiO nanoparticles was also developed to mitigate potential performance degradation due to coarsening of NiO particles under practical operating conditions. As a general approach, this exsolution-dissolution of electrocatalytically active nanoparticles on an electrode surface may be applicable to the development of other high-performance cobalt-free cathodes for fuel cells and other electrochemical systems.

Versatile Three-Dimensional Porous Cu@Cu2 O Aerogel Networks as Electrocatalysts and Mimicking Peroxidases.

PubMed

Ling, Pinghua; Zhang, Qiang; Cao, Tingting; Gao, Feng

2018-06-04

A facile strategy is presented to form 3D porous Cu@Cu 2 O aerogel networks by self-assembling Cu@Cu 2 O nanoparticles with the diameters of ca. 40 nm for constructing catalytic interfaces. Unexpectedly, the prepared Cu@Cu 2 O aerogel networks display excellent electrocatalytic activity to glucose oxidation at a low onset potential of ca. 0.25 V. Moreover, the Cu@Cu 2 O aerogels also can act as mimicking-enzymes including horseradish peroxidase and NADH peroxidase, and show obvious enzymatic catalytic activities to the oxidation of dopamine (DA), o-phenyldiamine (OPD), 3,3,5,5-tetramethylbenzidine (TMB), and dihydronicotinamide adenine dinucleotide (NADH) in the presence of H 2 O 2 . These 3D Cu@Cu 2 O aerogel networks are a new class of porous catalytic materials as mimic peroxidases and electrocatalysts and offer a novel platform to construct catalytic interfaces for promising applications in electrochemical sensors and artificial enzymatic catalytic systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid NiCoOx adjacent to Pd nanoparticles as a synergistic electrocatalyst for ethanol oxidation

NASA Astrophysics Data System (ADS)

Wang, Wei; Yang, Yan; Liu, Yanqin; Zhang, Zhe; Dong, Wenkui; Lei, Ziqiang

2015-01-01

To improve the electrocatalytic activity of Pd for ethanol oxidation, hybrid NiCoOx adjacent to Pd catalyst (Pd-NiCoOx/C) is successfully synthesized. Physical characterization shows NiCoOx is closely adjacent to Pd nanoparticles in Pd-NiCoOx/C catalyst, which leads to Strong Metal-Support Interactions (SMSI) between the NiCoOx and Pd nanoparticles, in favor of the electrocatalytic properties. The Pd-NiCoOx/C catalyst is estimated to own larger electrochemically active surface area than Pd/C and Pd-NiO/C catalysts. Moreover, compared to Pd/C catalyst, the onset potential of Pd-NiCoOx/C catalyst is negative 40 mV for ethanol oxidation. Noticeably, the current density of Pd-NiCoOx/C catalyst is 2.05 and 1.43 times higher contrasted to Pd/C and Pd-NiO/C catalysts accordingly. Importantly, the Pd-NiCoOx/C catalyst exhibits better stability during ethanol oxidation, which is a promising electrocatalyst for application in direct alkaline alcohol fuel cells.

Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts.

PubMed

Cheng, Fangyi; Shen, Jian; Peng, Bo; Pan, Yuede; Tao, Zhanliang; Chen, Jun

2011-01-01

Spinels can serve as alternative low-cost bifunctional electrocatalysts for oxygen reduction/evolution reactions (ORR/OER), which are the key barriers in various electrochemical devices such as metal-air batteries, fuel cells and electrolysers. However, conventional ceramic synthesis of crystalline spinels requires an elevated temperature, complicated procedures and prolonged heating time, and the resulting product exhibits limited electrocatalytic performance. It has been challenging to develop energy-saving, facile and rapid synthetic methodologies for highly active spinels. In this Article, we report the synthesis of nanocrystalline M(x)Mn(3-x)O(4) (M = divalent metals) spinels under ambient conditions and their electrocatalytic application. We show rapid and selective formation of tetragonal or cubic M(x)Mn(3-x)O(4) from the reduction of amorphous MnO(2) in aqueous M(2+) solution. The prepared Co(x)Mn(3-x)O(4) nanoparticles manifest considerable catalytic activity towards the ORR/OER as a result of their high surface areas and abundant defects. The newly discovered phase-dependent electrocatalytic ORR/OER characteristics of Co-Mn-O spinels are also interpreted by experiment and first-principle theoretical studies.

Highly efficient photocatalytic H2 evolution using TiO2 nanoparticles integrated with electrocatalytic metal phosphides as cocatalysts

NASA Astrophysics Data System (ADS)

Song, Rui; Zhou, Wu; Luo, Bing; Jing, Dengwei

2017-09-01

In this work, electrocatalysts like the metal phosphides Ni2P, NiCoP, and FeP, can serve as cocatalysts of TiO2 to form efficient composite photocatalysts for hydrogen generation from an aqueous methanol solution. On comparing Ni2P, NiCoP, and FeP and optimizing their proportions, the NiCoP(1 wt%)/TiO2 composite was found to exhibit the highest activity toward photocatalytic H2 production (1.54 μmol h-1 mg-1), which is about thirteen times that of the naked TiO2 nanoparticles. Mott-Schottky (MS) analysis indicated that the large upward shift or band bending of the Fermi energy level (EF) in metal phosphides was responsible for the enhanced activity of the composites. The steady-state photoluminescence (PL) spectra and photocurrent transient response further confirmed that the enhanced photoinduced charge transfer and band separation after TiO2 was integrated with the metal phosphides. Thus, these electrocatalysts were shown to be efficient cocatalysts that can replace noble metals as low-cost photocatalytic H2 production.

Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

PubMed Central

2013-01-01

A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too. PMID:24229351

Nitrogen Doped Graphene Supported Pt Nanoflowers as Electrocatalysts for Oxidation of Formaldehyde.

PubMed

Xie, Aijuan; Zhou, Wenting; Luo, Shiping; Chen, Yu; Zhou, Xiaoqing; Chao, Yao

2017-02-01

A facile Pt nanoflowers/nitrogen-doped graphene (PtNFs/NG) electrocatalyst was prepared via depositing Pt nanoflowers (PtNFs) onto the nitrogen-doped graphene (NG) matrix with urea as the nitrogen source and PtNFs/NG modified glassy carbon electrode (GCE) was prepared by electro-chemical method. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Raman spectroscope, X-ray photoelectron spectroscopy (XPS) and Scanning electron microscope (SEM) were used to characterize the resulting composites. Also oxidation of formaldehyde on the resulting PtNFs/NG modified electrode was investigated. The influence of deposition time, electrodeposition potential and formaldehyde concentration on electrooxidation of formaldehyde was detected, the experimental results indicate the high performance of PtNFs/NG catalyst for formaldehyde oxidation is at electrodeposition time of 300 s with the applied potential of −0.3 V. Electrochemical process, electrocatalytic stability and chronoamperometry were also inspected, it was indicated that formalde-hyde oxidation reaction on the PtNFs/NG electrode is diffusion-controlled and PtNFs/NG exhibits a high catalytic activity, stability as well as excellent poisoning-tolerance towards formaldehyde oxidation, which is attributed to the synergistic effect of PtNFs and NG. It turns out that PtNFs/NG can be used in direct liquid-feed fuel cells as a promising alternative catalyst.

Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts.

PubMed

Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

2015-04-14

The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the "I(+)X(-)S(+)" mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.

Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction

DOE PAGES

Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; ...

2014-07-09

The role of Cu-ion doping in α-MnO 2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO 2 nanowires (Cu-α-MnO 2) were prepared with varying amounts of Cu 2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO 2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO 2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn 3+ content for the Cu-α-MnO 2 nanowires. The Mn 3+/Mn 4+ couple is themediator for the rate-limiting redoxmore » driven O 2 -/OH - exchange. It is proposed that O 2 adsorbs viaan axial site (the e g orbital on the Mn 3+ d 4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O 2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn 3+ character of the oxide.« less

In Situ Synthesis Strategy for Hierarchically Porous Ni2P Polyhedrons from MOFs Templates with Enhanced Electrochemical Properties for Hydrogen Evolution.

PubMed

Yan, Liting; Dai, Pengcheng; Wang, Ying; Gu, Xin; Li, Liangjun; Cao, Lei; Zhao, Xuebo

2017-04-05

The development of highly active and stable noble metal-free electrocatalysts of hydrogen evolution reaction (HER) under both acidic and basic conditions for renewable-energy conversion techniques is of great significance. Herein, a practical in situ synthesis strategy for a three-dimensional Ni 2 P polyhedron with a hierarchically porous structure was presented, which was efficiently obtained from a nickel centered metal-organic frameworks (MOF-74-Ni) by direct low-temperature phosphorization. The as-prepared Ni 2 P polyhedron showed a high BET surface area (175.0 m 2 ·g -1 ), hierarchically porous property, and outstanding metal dispersion, which well inherited the morphology and porosity of its MOF precursor. Compared with Ni 2 P particles obtained from a nonporous precursor, the as-prepared Ni 2 P polyhedron used as electrocatalyst exhibited excellent electrocatalytic performance toward the HER, with a low overpotential of 158 mV to produce the cathodic current density of 10 mA cm -2 . A small Tafel slope of 73 mV per decade is obtained for Ni 2 P polyhedron, which revealed a Volmer-Heyrovsky mechanism during the HER. In addition, benefiting from the structural stability, the porous Ni 2 P polyhedron used as a electrocatalyst showed satisfactory long-term durability for the HER in acidic media.

Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles.

PubMed

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-07

We report a unique and highly stable electrocatalyst-platinum (Pt) supported on titanium-ruthenium oxide (TRO)-for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile-namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst-Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm(-2) at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm(-2) for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern.

Reactive template synthesis of nitrogen-doped graphene-like carbon nanosheets derived from hydroxypropyl methylcellulose and dicyandiamide as efficient oxygen reduction electrocatalysts

NASA Astrophysics Data System (ADS)

Hu, Chun; Zhou, Yao; Ma, Ruguang; Liu, Qian; Wang, Jiacheng

2017-03-01

Oxygen reduction reaction (ORR) plays a dominant role in proton exchange membrane fuel cells (PEMFCs). Thus, the design and preparation of efficient ORR electrocatalysts is of high importance. In this work, we successfully prepared a series of nitrogen-doped graphene-like carbon nanosheets (NCNSs) with large pore volumes of up to 1.244 cm3 g-1 and high level of N dopants (5.3-6.8 at%) via a one-step, in-situ reactive template strategy by co-pyrolysis of hydroxypropyl methylcellulose (HPMC) and dicyandiamide (DICY) as the precursors at 1000 °C. The DICY-derived graphitic carbon nitride (g-C3N4) nanosheets could act as the hard template for the confined growth of 2D carbon nanosheets, and the further increase in the pyrolysis temperature could directly remove off the g-C3N4 template by complete decomposition and simultaneously dope N atoms within the carbon nanosheets. The pyridinic and graphitic nitrogen groups are dominant among various N functional groups in the NCNSs. The NCNS_1:10 prepared with the HPMC/DICY mass ratio of 1/10 can be used as the metal-free ORR electrocatalysts with optimal activity (onset potential: -0.1 V vs. SCE; limiting current density: 4.8 mA cm-2) in O2-saturated 0.1 M KOH electrolyte among the NCNSs. Moreover, the NCNS_1:10 demonstrates a dominant four-electron reduction process, as well as excellent long-term operation stability and outstanding methanol crossover resistance. The excellent ORR activity of the NCNS_1:10 should be mainly owing to high contents of pyridinic and graphitic N dopants, large pore volume, hierarchical structures, and microstructural defects.

A high-performance electrochemical sensor for biologically meaningful l-cysteine based on a new nanostructured l-cysteine electrocatalyst.

PubMed

Cao, Fei; Huang, Yikun; Wang, Fei; Kwak, Dongwook; Dong, Qiuchen; Song, Donghui; Zeng, Jie; Lei, Yu

2018-08-17

As a new class of l-cysteine electrocatalyst explored in this study, Au/CeO 2 composite nanofibers (CNFs) were employed to modify the screen printed carbon electrode (SPCE) to fabricate a novel l-cysteine (CySH) electrochemical sensor with high performance. Its electrochemical behavior and the roles of Au and CeO 2 in the composite toward electro-oxidation of CySH were elucidated and demonstrated using cyclic voltammetry and amperometry techniques for the first time through the comparison with pure CeO 2 NFs. More specifically, the Au/CeO 2 CNFs modified SPCE possessed greatly enhanced electrocatalytic activity toward CySH oxidation. An ultra high sensitivity of 321 μA mM -1 cm -2 was obtained, which is almost 2.7 times higher than that of pure CeO 2 NFs, revealing that the presence of Au imposed an important influence on the electrocatalytic activity toward CySH. The detailed reasons on such high performance were also discussed. In addition, the as-prepared sensor showed a low detection limit of 10 nM (signal to noise ratio of 3), a wide linear range up to 200 μM for the determination of CySH, an outstanding reproducibility and good long-term stability, as well as an excellent selectivity against common interferents such as tryptophan, tyrosine, methionine, ascorbic acid and uric acid. All these features indicate that the Au/CeO 2 composite nanofiber is a promising candidate as a new class of l-cysteine electrocatalyst in the development of highly sensitive and selective CySH electrochemical sensor. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrodeposited Co-doped NiSe2 nanoparticles film: a good electrocatalyst for efficient water splitting

NASA Astrophysics Data System (ADS)

Liu, Tingting; Asiri, Abdullah M.; Sun, Xuping

2016-02-01

In this communication, we report that a Co-doped NiSe2 nanoparticles film electrodeposited on a conductive Ti plate (Co0.13Ni0.87Se2/Ti) behaves as a robust electrocatalyst for both HER and OER in strongly basic media, with good activity over a NiSe2/Ti counterpart. This Co0.13Ni0.87Se2/Ti catalytic electrode delivers 10 mA cm-2 at an overpotential of 64 mV for HER and 100 mA cm-2 at an overpotential of 320 mV for OER in 1.0 M KOH. A voltage of only 1.62 V is required to drive 10 mA cm-2 for the two-electrode alkaline water electrolyzer using Co0.13Ni0.87Se2/Ti as an anode and cathode.In this communication, we report that a Co-doped NiSe2 nanoparticles film electrodeposited on a conductive Ti plate (Co0.13Ni0.87Se2/Ti) behaves as a robust electrocatalyst for both HER and OER in strongly basic media, with good activity over a NiSe2/Ti counterpart. This Co0.13Ni0.87Se2/Ti catalytic electrode delivers 10 mA cm-2 at an overpotential of 64 mV for HER and 100 mA cm-2 at an overpotential of 320 mV for OER in 1.0 M KOH. A voltage of only 1.62 V is required to drive 10 mA cm-2 for the two-electrode alkaline water electrolyzer using Co0.13Ni0.87Se2/Ti as an anode and cathode. Electronic supplementary information (ESI) available: Experimental section and supplementary figures. See DOI: 10.1039/c5nr07170d

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

PubMed

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pulse electrodeposited nickel-indium tin oxide nanocomposite as an electrocatalyst for non-enzymatic glucose sensing.

PubMed

Sivasakthi, P; Ramesh Bapu, G N K; Chandrasekaran, Maruthai

2016-01-01

Nickel and nickel-ITO nanocomposite on mild steel substrate were prepared by pulse electrodeposition method from nickel sulphamate electrolyte and were examined as electrocatalysts for non-enzymatic glucose sensing. The surface morphology, chemical composition, preferred orientation and oxidation states of the nickel metal ion in the deposits were characterized by SEM, EDAX, XRD and XPS. Electrochemical sensing of glucose was studied by cyclic voltammetry and amperometry. The modified Ni-ITO nanocomposite electrode showed higher electrocatalytic activity for the oxidation of glucose in alkaline medium and exhibited a linear range from 0.02 to 3.00 mM with a limit of detection 3.74 μM at a signal-to-noise ratio of 3. The higher selectivity, longer stability and better reproducibility of this electrode compared to nickel in the sensing of glucose are pointers for exploitation in practical clinical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Asymmetric 3d Electronic Structure for Enhanced Oxygen Evolution Catalysis.

PubMed

Liu, Yang; Yin, Shibin; Shen, Pei Kang

2018-06-27

The oxygen evolution reaction (OER) is an essential process for renewable energy, and designing a bifunctional oxygen electrocatalyst with high catalytic performance plays a significant role. In this work, FeS, Ni 3 S 2 , Fe 5 Ni 4 S 8 , and N, O, S-doped meshy carbon base were successfully synthesized. The sample containing Fe 5 Ni 4 S 8 exhibited excellent OER performance. The density functional theory calculations indicate that the partial density of states for 3d electrons (3d-PDOS) of Fe and Ni atoms are changed from monometallic sulfide to bimetallic sulfide at the sulfur vacancy. The asymmetric 3d electronic structure optimizes the 3d-PDOS of Fe and Ni atoms, and leads to an enhanced OER activity. This work provides a new strategy to prepare a low-cost electrocatalyst for oxygen evolution with high-efficiency.

Single-Atom Electrocatalysts.

PubMed

Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong; Du, Dan; Lin, Yuehe

2017-11-06

Recent years have witnessed a dramatic increase in the production of sustainable and renewable energy. However, the electrochemical performances of the various systems are limited, and there is an intensive search for highly efficient electrocatalysts by more rational control over the size, shape, composition, and structure. Of particular interest are the studies on single-atom catalysts (SACs), which have sparked new interests in electrocatalysis because of their high catalytic activity, stability, selectivity, and 100 % atom utilization. In this Review, we introduce innovative syntheses and characterization techniques for SACs, with a focus on their electrochemical applications in the oxygen reduction/evolution reaction, hydrogen evolution reaction, and hydrocarbon conversion reactions for fuel cells (electrooxidation of methanol, ethanol, and formic acid). The electrocatalytic performance is further considered at an atomic level and the underlying mechanisms are discussed. The ultimate goal is the tailoring of single atoms for electrochemical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Reconstitution of Biomolecules for Applications as Electrocatalysts for the Bionanofuel Cell

NASA Technical Reports Server (NTRS)

Kim, Jae-Woo; Choi, Sang H.; Lillehei, Peter T.; King, Glen C.; Watt, Gerald D.; Chu, Sang-Hyon; Park, Yeonjoon; Thibeault, Sheila

2004-01-01

Platinum-cored ferritins were synthesized as electrocatalysts by electrochemical biomineralization of immobilized apoferritin with platinum. The platinum cored ferritin was fabricated by exposing the immobilized apoferritin to platinum ions at a reduction potential. On the platinum-cored ferritin, oxygen is reduced to water with four protons and four electrons generated from the anode. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This results in a smaller catalyst loading of the electrodes for fuel cells or other electrochemical devices. In addition, the catalytic activity of the ferritin-stabilized platinum nanoparticles is enhanced by the large surface area and particle size phenomena. The work presented herein details the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritin with different inorganic cores, and the fabrication of self-assembled 2-D arrays with thiolated ferritin.

Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

DOE PAGES

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala; ...

2017-09-05

Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

Synthesis of metal-metal oxide catalysts and electrocatalysts using a metal cation adsorption/reduction and adatom replacement by more noble ones

DOEpatents

Adzic, Radoslav; Vukmirovic, Miomir; Sasaki, Kotaro

2010-04-27

The invention relates to platinum-metal oxide composite particles and their use as electrocatalysts in oxygen-reducing cathodes and fuel cells. The invention particularly relates to methods for preventing the oxidation of the platinum electrocatalyst in the cathodes of fuel cells by use of these platinum-metal oxide composite particles. The invention additionally relates to methods for producing electrical energy by supplying such a fuel cell with an oxidant, such as oxygen, and a fuel source, such as hydrogen. The invention also relates to methods of making the metal-metal oxide composites.

Non-noble electrocatalysts for alkaline fuel cells

NASA Technical Reports Server (NTRS)

Sarangapani, S.; Lessner, P.; Manoukian, M.; Giner, J.

1989-01-01

Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.

Platinum Monolayer Shell on Non-Noble Metal Core Electrocatalysts for the Hydrogen Oxidation Reaction

NASA Astrophysics Data System (ADS)

Teeluck, Krishani Malini

According to the United States Environmental Protection Agency, as of 2015, transportation accounted for 32% of the carbon dioxide emissions in the United States (and all carbon dioxide emissions in the U.S. accounted for 82.2% of all greenhouse gases from human activity). A hydrogen fuel cell is a device that efficiently produces electrical energy directly from a chemical reaction, with zero carbon emissions, and therefore holds great promise in alleviating our dependence on harmful use of energy sources. Due to their clean emissions and high efficiencies, there has been focus on the hydrogen fuel cell for vehicle applications using proton exchange membrane and alkaline fuel cells. Although the proton exchange membrane fuel cell is currently being used in vehicles, their high cost limits their feasibility in the market. This has inspired the development of the alkaline fuel cell whose efficiency and simplicity suggest the possibility of manufacturing high power fuel cell vehicles at a low cost, since the electrocatalysts in the alkaline fuel cell can be made from non-noble metals. Although the hydrogen oxidation reaction is one of the fastest electrochemical reactions in acidic media, it is two orders of magnitude slower in alkaline media, which hinders the overall efficiency of the alkaline fuel cell. Pure platinum is currently the best catalyst for the hydrogen oxidation reaction, but platinum’s high cost and rarity yields economic issues, rendering the technology futile if it cannot be commercialized. Furthermore, platinum’s hydrogen binding energy is slightly stronger than the optimal hydrogen binding energy. As the hydrogen oxidation reaction happens only on the surface of the catalyst, there is no need for platinum content beyond the exterior. Since tungsten and nickel are cheap, as well as abundant, they are ideal elements to replace the core of the catalyst with, while leaving a platinum shell surrounding this core. The activity of the hydrogen oxidation reaction when using a platinum monolayer shell on a nickel tungsten core electrocatalyst is explored, and it was found that the novel catalyst created here exhibits kinetics that rival pure platinum, but at less than half the platinum content, suggesting that nickel and tungsten modify the electronic properties of platinum in a way that enhances its activity for the hydrogen oxidation reaction. Furthermore, the hydrogen binding energy of this novel electrocatalyst was found to be weaker than the optimal binding energy (rather than stronger, as seen in pure platinum), indicating the possibility of modifying the electronic properties of platinum for a more optimal hydrogen binding energy.

On direct and indirect methanol fuel cells for transportation applications

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

Gottesfield, S.

1996-04-01

Research on direct oxidation methanol fuel cells (DMFCs) and polymer electrolyte fuel cells (PEFCs) is discussed. Systems considered for transportation applications are addressed. The use of platinum/ruthenium anode electrocatalysts and platinum cathode electrocatalysts in polymer electrolyte DMFCs has resulted in significant performance enhancements.

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability.

PubMed

Jackson, Ariel; Strickler, Alaina; Higgins, Drew; Jaramillo, Thomas Francisco

2018-01-12

Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications. The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1 ), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.

Macroscale cobalt-MOFs derived metallic Co nanoparticles embedded in N-doped porous carbon layers as efficient oxygen electrocatalysts

NASA Astrophysics Data System (ADS)

Lu, Hai-Sheng; Zhang, Haimin; Liu, Rongrong; Zhang, Xian; Zhao, Huijun; Wang, Guozhong

2017-01-01

Metal-organic frameworks (MOFs) materials have aroused great research interest in different areas owing to their unique properties, such as high surface area, various composition, well-organized framework and controllable porous structure. Controllable fabrication of MOFs materials at macro-scale may be more promising for their large-scale practical applications. Here we report the synthesis of macro-scale Co-MOFs crystals using 1,3,5-benzenetricarboxylic acid (H3BTC) linker in the presence of Co2+, triethylamine (TEA) and nonanoic acid by a facile solvothermal reaction. Further, the as-fabricated Co-MOFs as precursor was pyrolytically treated at different temperatures in N2 atmosphere to obtain metallic Co nanoparticles embedded in N-doped porous carbon layers (denoted as Co@NPC). The results demonstrate that the Co-MOFs derived sample obtained at 900 °C (Co@NPC-900) shows a porous structure (including micropore and mesopore) with a surface area of 110.8 m2 g-1 and an N doping level of 1.62 at.% resulted from TEA in the pyrolysis process. As electrocatalyst, the Co@NPC-900 exhibits bifunctional electrocatalytic activities toward the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media which are key reactions in some renewable energy technologies such as fuel cells and rechargeable metal-air batteries. The results indicate that the Co@NPC-900 can afford an onset potential of 1.50 V (vs. RHE) and a potential value of 1.61 V (vs. RHE) at a current density of 10 mA cm-2 for ORR and OER with high applicable stability, respectively. The efficient catalytic activity of Co@NPC-900 as bifunctional oxygen electrocatalyst can be ascribed to N doping and embedded metallic Co nanoparticles in carbon structure providing catalytic active sites and porous structure favourable for electrocatalysis-related mass transport.

Toward High-Performance and Low-Cost Hydrogen Evolution Reaction Electrocatalysts: Nanostructuring Cobalt Phosphide (CoP) Particles on Carbon Fiber Paper.

PubMed

Yu, Shu Hearn; Chua, Daniel H C

2018-05-02

In this communication, we facily fabricated nanostructured CoP particles (150 to 200 nm) on carbon fiber paper (CFP) for hydrogen evolution reaction (HER) by a simple two-step process via a green route. In the first step, crystalline Co 3 O 4 nanocubes (150-200 nm) were loaded on CFP through a hydrothermal process at low temperature (120 °C). Interestingly, crystalline Co 3 O 4 nanocubes with a size 150-200 nm exhibited different growth mechanisms in contrast to the crystalline Co 3 O 4 nanocubes with a size <100 nm reported earlier. In the second step, these crystalline Co 3 O 4 nanocubes were converted to catalytically active CoP particles through chemical vapor deposition (CVD) phosphorization (denoted as CoP/CFP-H). Remarkably, CoP/CFP-H exhibited a low Tafel slope of 49.7 mV/dec and only required overpotentials of 128.1, 144.4, and 190.8 mV to drive geometric current densities of -10, -20, and -100 mA cm -2 , respectively. Besides, the CoP/CFP-H also demonstrated an excellent durability in an acidic environment under 2000 sweeps at a high scan rate (100 mV s -1 ) and a 24 h chronopotentiometry testing. For comparison, CoP was also fabricated through the electrodeposition method, followed by CVD phosphorization (denoted as CoP/CFP-E). It was found that the latter had exhibited inferior activity compared to CoP/CFP-H. The good performances of CoP/CFP-H are essentially due to the rational designs of electrode: (i) the applications of highly HER active CoP electrocatalyst, (ii) the intimate contact of nanostructured CoP on carbon fibers, and (iii) the large electrochemical surface area at electrocatalyst/electrolyte interface due to the large retaining of particles features after phosphorization. Notably, the intermediate Co 3 O 4 /CFP can serve as a platform to develop other cobalt-based functional materials.

Well-Coupled Nanohybrids Obtained by Component-Controlled Synthesis and in Situ Integration of Mn xPd y Nanocrystals on Vulcan Carbon for Electrocatalytic Oxygen Reduction.

PubMed

Lu, Yanan; Zhao, Shulin; Yang, Rui; Xu, Dongdong; Yang, Jing; Lin, Yue; Shi, Nai-En; Dai, Zhihui; Bao, Jianchun; Han, Min

2018-03-07

Development of cheap, highly active, and robust bimetallic nanocrystal (NC)-based nanohybrid (NH) electrocatalysts for oxygen reduction reaction (ORR) is helpful for advancing fuel cells or other renewable energy technologies. Here, four kinds of well-coupled Mn x Pd y (MnPd 3 , MnPd-Pd, Mn 2 Pd 3 , Mn 2 Pd 3 -Mn 11 Pd 21 )/C NHs have been synthesized by in situ integration of Mn x Pd y NCs with variable component ratios on pretreated Vulcan XC-72 C using the solvothermal method accompanied with annealing under Ar/H 2 atmosphere and used as electrocatalysts for ORR. Among them, the MnPd 3 /C NHs possess the unique "half-embedded and half-encapsulated" interfaces and exhibit the highest catalytic activity, which can compete with some currently reported non-Pt catalysts (e.g., Ag-Co nanoalloys, Pd 2 NiAg NCs, PdCo/N-doped porous C, G-Cu 3 Pd nanocomposites, etc.), and close to commercial Pt/C. Electrocatalytic dynamic measurements disclose that their ORR mechanism abides by the direct 4e - pathway. Moreover, their durability and methanol-tolerant capability are much higher than that of Pt/C. As revealed by spectroscopic and electrochemical analyses, the excellent catalytic performance of MnPd 3 /C NHs results from the proper component ratio of Mn and Pd and the strong interplay of their constituents, which not only facilitate to optimize the d-band center or the electronic structure of Pd but also induce the phase transformation of MnPd 3 active components and enhance their conductivity or interfacial electron transfer dynamics. This work demonstrates that MnPd 3 /C NHs are promising methanol-tolerant cathode electrocatalysts that may be employed in fuel cells or other renewable energy option.

Direct N2H4/H2O2 Fuel Cells Powered by Nanoporous Gold Leaves

PubMed Central

Yan, Xiuling; Meng, Fanhui; Xie, Yun; Liu, Jianguo; Ding, Yi

2012-01-01

Dealloyed nanoporous gold leaves (NPGLs) are found to exhibit high electrocatalytic properties toward both hydrazine (N2H4) oxidation and hydrogen peroxide (H2O2) reduction. This observation allows the implementation of a direct hydrazine-hydrogen peroxide fuel cell (DHHPFC) based on these novel porous membrane catalysts. The effects of fuel and oxidizer flow rate, concentration and cell temperature on the performance of DHHPFC are systematically investigated. With a loading of ~0.1 mg cm−2 Au on each side, an open circuit voltage (OCV) of 1.2 V is obtained at 80°C with a maximum power density 195 mW cm−2, which is 22 times higher than that of commercial Pt/C electrocatalyst at the same noble metal loading. NPGLs thus hold great potential as effective and stable electrocatalysts for DHHPFCs. PMID:23230507

Microparticles with hierarchical porosity

DOEpatents

Petsev, Dimiter N; Atanassov, Plamen; Pylypenko, Svitlana; Carroll, Nick; Olson, Tim

2012-12-18

The present disclosure provides oxide microparticles with engineered hierarchical porosity and methods of manufacturing the same. Also described are structures that are formed by templating, impregnating, and/or precipitating the oxide microparticles and method for forming the same. Suitable applications include catalysts, electrocatalysts, electrocatalysts support materials, capacitors, drug delivery systems, sensors and chromatography.

Palladium-cobalt particles as oxygen-reduction electrocatalysts

DOEpatents

Adzic, Radoslav [East Setauket, NY; Huang, Tao [Manorville, NY

2009-12-15

The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

Tuning the Activity of Carbon for Electrocatalytic Hydrogen Evolution via an Iridium-Cobalt Alloy Core Encapsulated in Nitrogen-Doped Carbon Cages.

PubMed

Jiang, Peng; Chen, Jitang; Wang, Changlai; Yang, Kang; Gong, Shipeng; Liu, Shuai; Lin, Zhiyu; Li, Mengsi; Xia, Guoliang; Yang, Yang; Su, Jianwei; Chen, Qianwang

2018-03-01

Graphene, a 2D material consisting of a single layer of sp 2 -hybridized carbon, exhibits inert activity as an electrocatalyst, while the incorporation of heteroatoms (such as N) into the framework can tune its electronic properties. Because of the different electronegativity between N and C atoms, electrons will transfer from C to N in N-doped graphene nanosheets, changing inert C atoms adjacent to the N-dopants into active sites. Notwithstanding the achieved progress, its intrinsic activity in acidic media is still far from Pt/C. Here, a facile annealing strategy is adopted for Ir-doped metal-organic frameworks to synthesize IrCo nanoalloys encapsulated in N-doped graphene layers. The highly active electrocatalyst, with remarkably reduced Ir loading (1.56 wt%), achieves an ultralow Tafel slope of 23 mV dec -1 and an overpotential of only 24 mV at a current density of 10 mA cm -2 in 0.5 m sulfuric acid solution. Such superior performance is even superior to the noble-metal catalyst Pt. Surface structural and computational studies reveal that the superior behavior originates from the decreased ΔG H* for HER induced by the electrons transferred from the alloy core to the graphene layers, which is beneficial for enhancing CH binding. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction.

PubMed

Deng, Xiaohui; Öztürk, Secil; Weidenthaler, Claudia; Tüysüz, Harun

2017-06-28

Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co 3 O 4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm 2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH) 2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry.

Flexible nitrogen-doped graphene/carbon nanotube/Co3O4 paper and its oxygen reduction activity

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Cong, Huai-Ping; Wang, Ping; Yu, Shu-Hong

2014-06-01

Due to the demand of an efficient, inexpensive and scalable synthesis of oxygen reduction reaction (ORR) catalyst for practical application in fuel cell, we demonstrate a facile strategy to fabricate the flexible nitrogen-doped graphene/carbon nanotube/Co3O4 (NG/CNT/Co3O4) paper catalyst. In the hydrothermal process, the in situ formation of Co3O4 nanoparticles, reduction of GO and doping of nitrogen species occur simultaneously in the assembled paper in ammonia solution. Because of the synergistic effects of three active components and the spacing effect of CNTs and Co3O4 nanoparticles on avoiding the re-aggregation of assembled graphene nanosheets, the free-standing NG/CNT/Co3O4 paper exhibits an enhanced ORR catalytic performance with stable durability and strong methanol-tolerant capability, indicating promising potential as ORR electrocatalyst in practical applications.Due to the demand of an efficient, inexpensive and scalable synthesis of oxygen reduction reaction (ORR) catalyst for practical application in fuel cell, we demonstrate a facile strategy to fabricate the flexible nitrogen-doped graphene/carbon nanotube/Co3O4 (NG/CNT/Co3O4) paper catalyst. In the hydrothermal process, the in situ formation of Co3O4 nanoparticles, reduction of GO and doping of nitrogen species occur simultaneously in the assembled paper in ammonia solution. Because of the synergistic effects of three active components and the spacing effect of CNTs and Co3O4 nanoparticles on avoiding the re-aggregation of assembled graphene nanosheets, the free-standing NG/CNT/Co3O4 paper exhibits an enhanced ORR catalytic performance with stable durability and strong methanol-tolerant capability, indicating promising potential as ORR electrocatalyst in practical applications. Electronic supplementary information (ESI) available: XRD patterns, elemental mapping images, DSC-TGA curves and XPS spectrum of NG/CNT/Co3O4 paper; SEM images and XPS spectra of NG/Co3O4 paper; RDE curves and corresponding K-L plots of different catalysts. See DOI: 10.1039/c4nr02101k

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

NASA Astrophysics Data System (ADS)

Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

2017-11-01

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

Hierarchical Pd-Sn alloy nanosheet dendrites: an economical and highly active catalyst for ethanol electrooxidation.

PubMed

Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

2013-01-01

Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures.

Hierarchical Pd-Sn Alloy Nanosheet Dendrites: An Economical and Highly Active Catalyst for Ethanol Electrooxidation

PubMed Central

Ding, Liang-Xin; Wang, An-Liang; Ou, Yan-Nan; Li, Qi; Guo, Rui; Zhao, Wen-Xia; Tong, Ye-Xiang; Li, Gao-Ren

2013-01-01

Hierarchical alloy nanosheet dendrites (ANSDs) are highly favorable for superior catalytic performance and efficient utilization of catalyst because of the special characteristics of alloys, nanosheets, and dendritic nanostructures. In this paper, we demonstrate for the first time a facile and efficient electrodeposition approach for the controllable synthesis of Pd-Sn ANSDs with high surface area. These synthesized Pd-Sn ANSDs exhibit high electrocatalytic activity and superior long-term cycle stability toward ethanol oxidation in alkaline media. The enhanced electrocataytic activity of Pd-Sn ANSDs may be attributed to Pd-Sn alloys, nanosheet dendrite induced promotional effect, large number of active sites on dendrite surface, large surface area, and good electrical contact with the base electrode. Because of the simple implement and high flexibility, the proposed approach can be considered as a general and powerful strategy to synthesize the alloy electrocatalysts with high surface areas and open dendritic nanostructures. PMID:23383368

Hierarchical CoP/Ni 5 P 4 /CoP microsheet arrays as a robust pH-universal electrocatalyst for efficient hydrogen generation

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

Mishra, Ishwar Kumar; Zhou, Haiqing; Sun, Jingying

Exceptional Pt-like electrocatalytic activity was achieved in a sandwich-like catalyst of CoP/Ni 5 P 4 /CoP microsheet arrays for pH-universal hydrogen evolution through simply wrapping Ni 5 P 4 nanosheet arrays in CoP nanoparticles.

One-step electrochemical synthesis of nitrogen and sulfur co-doped, high-quality graphene oxide.

PubMed

Parvez, Khaled; Rincón, Rosalba A; Weber, Nils-Eike; Cha, Kitty C; Venkataraman, Shyam S

2016-04-28

High-quality graphene oxide (GO) with high crystallinity and electrical conductivity as well as in situ doped with nitrogen and sulfur is obtained via the electrochemical exfoliation of graphite. Furthermore, iron incorporated GO sheets show promising catalytic activity and stable methanol tolerance durability when used as electrocatalysts for the oxygen reduction reaction.

Hierarchical CoP/Ni 5 P 4 /CoP microsheet arrays as a robust pH-universal electrocatalyst for efficient hydrogen generation

DOE PAGES

Mishra, Ishwar Kumar; Zhou, Haiqing; Sun, Jingying; ...

2018-01-01

Exceptional Pt-like electrocatalytic activity was achieved in a sandwich-like catalyst of CoP/Ni 5 P 4 /CoP microsheet arrays for pH-universal hydrogen evolution through simply wrapping Ni 5 P 4 nanosheet arrays in CoP nanoparticles.

Nitrogen and sulfur co-doping of partially exfoliated MWCNTs as 3-D structured electrocatalysts for the oxygen reduction reaction

DOE PAGES

Wang, Jie; Wu, Zexing; Han, Lili; ...

2016-03-14

Preventing the stacking of graphene sheets is of vital importance for highly efficient and stable fuel cell electrocatalysts. Here, we report a 3-D structured carbon nanotube intercalated graphene nanoribbon with N/S co-doping. The nanocomposite is obtained by using high temperature heat-treated thiourea with partially unzipped multi-walled carbon nanotubes. This unique structure preserves both the properties of carbon nanotubes and graphene, exhibiting excellent catalytic performance for the ORR with similar onset and half-wave potentials to those of Pt/C electrocatalysts. Furthermore, the stereo structured composite exhibits distinct advantages in long-term stability and methanol poisoning tolerance in comparison to Pt/C.

Improved ethanol electrooxidation performance by shortening Pd-Ni active site distance in Pd-Ni-P nanocatalysts

NASA Astrophysics Data System (ADS)

Chen, Lin; Lu, Lilin; Zhu, Hengli; Chen, Yueguang; Huang, Yu; Li, Yadong; Wang, Leyu

2017-01-01

Incorporating oxophilic metals into noble metal-based catalysts represents an emerging strategy to improve the catalytic performance of electrocatalysts in fuel cells. However, effects of the distance between the noble metal and oxophilic metal active sites on the catalytic performance have rarely been investigated. Herein, we report on ultrasmall (~5 nm) Pd-Ni-P ternary nanoparticles for ethanol electrooxidation. The activity is improved up to 4.95 A per mgPd, which is 6.88 times higher than commercial Pd/C (0.72 A per mgPd), by shortening the distance between Pd and Ni active sites, achieved through shape transformation from Pd/Ni-P heterodimers into Pd-Ni-P nanoparticles and tuning the Ni/Pd atomic ratio to 1:1. Density functional theory calculations reveal that the improved activity and stability stems from the promoted production of free OH radicals (on Ni active sites) which facilitate the oxidative removal of carbonaceous poison and combination with CH3CO radicals on adjacent Pd active sites.

Synthesis and x-ray characterization of cobalt phosphide (Co₂P) nanorods for the oxygen reduction reaction

DOE PAGES

Doan-Nguyen, Vicky V.T.; Su, Dong; Zhang, Sen; ...

2015-07-14

Low temperature fuel cells are clean, effective alternative fuel conversion technology. Oxygen reduction reaction (ORR) at the fuel cell cathode has required Pt as the electrocatalyst for high activity and selectivity of the four-electron reaction pathway. Targeting a less expensive, earth abundant alternative, we have developed the synthesis of cobalt phosphide (Co₂P) nanorods for ORR. Characterization techniques that include total X-ray scattering and extended X-ray absorption fine structure revealed a deviation of the nanorods from bulk crystal structure with a contraction along the b orthorhombic lattice parameter. The carbon supported nanorods have comparable activity but are remarkably more stable thanmore » conventional Pt catalysts for the oxygen reduction reaction in alkaline environments.« less

Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

PubMed

Yin, Huajie; Zhao, Shenlong; Zhao, Kun; Muqsit, Abdul; Tang, Hongjie; Chang, Lin; Zhao, Huijun; Gao, Yan; Tang, Zhiyong

2015-03-02

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.

Role of Surface Chemistry on Catalyst/Ionomer Interactions for Transition Metal–Nitrogen–Carbon Electrocatalysts

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

Artyushkova, Kateryna; Workman, Michael J.; Matanovic, Ivana

The role of the interaction between doped carbon-based materials and ionic conductors is essential in multiple technologies, from fuel cells and energy storage devices to conductive polymer composites. In this paper, we report how the surface chemistry of transition metal–nitrogen–carbon (MNC) electrocatalysts affects catalyst–ionomer interaction and the resulting structure of cathodes. The cathode structure resulting from these interactions is directly related to the performance in membrane electrode assembly (MEA) fuel cells. To advance the development of platinum group metal (PGM)-free electrodes for the oxygen reduction reaction it is necessary to understand the structure of the catalyst layers with focus onmore » chemistry and distribution of active sites and ionomer morphology. To assess catalyst interaction with an ionomer, X-ray photoelectron spectroscopy is applied to study the chemistry of catalyst layers while density functional theory (DFT) is used to calculate adsorption energies of the ionomer side chain on different nitrogen species. We report that a high surface concentration of hydrogenated nitrogen at the surface of MNC catalysts causes inefficient ionomer morphology, while an abundance of surface oxides promotes both an efficient distribution of active sites and an optimal ionomer–catalyst interface. The critical role of protonation of nitrogen within catalytic layers in inhibiting proton transport during fuel cell operation is also suggested. As a result, this is the first report of the effect the surface chemistry of MNC catalysts, in the presence of the ionomer, has on the structure and performance of MEA electrodes.« less

Role of Surface Chemistry on Catalyst/Ionomer Interactions for Transition Metal–Nitrogen–Carbon Electrocatalysts

DOE PAGES

Artyushkova, Kateryna; Workman, Michael J.; Matanovic, Ivana; ...

2017-12-18

The role of the interaction between doped carbon-based materials and ionic conductors is essential in multiple technologies, from fuel cells and energy storage devices to conductive polymer composites. In this paper, we report how the surface chemistry of transition metal–nitrogen–carbon (MNC) electrocatalysts affects catalyst–ionomer interaction and the resulting structure of cathodes. The cathode structure resulting from these interactions is directly related to the performance in membrane electrode assembly (MEA) fuel cells. To advance the development of platinum group metal (PGM)-free electrodes for the oxygen reduction reaction it is necessary to understand the structure of the catalyst layers with focus onmore » chemistry and distribution of active sites and ionomer morphology. To assess catalyst interaction with an ionomer, X-ray photoelectron spectroscopy is applied to study the chemistry of catalyst layers while density functional theory (DFT) is used to calculate adsorption energies of the ionomer side chain on different nitrogen species. We report that a high surface concentration of hydrogenated nitrogen at the surface of MNC catalysts causes inefficient ionomer morphology, while an abundance of surface oxides promotes both an efficient distribution of active sites and an optimal ionomer–catalyst interface. The critical role of protonation of nitrogen within catalytic layers in inhibiting proton transport during fuel cell operation is also suggested. As a result, this is the first report of the effect the surface chemistry of MNC catalysts, in the presence of the ionomer, has on the structure and performance of MEA electrodes.« less

Regulating the active species of Ni(OH)2 using CeO2: 3D CeO2/Ni(OH)2/carbon foam as an efficient electrode for the oxygen evolution reaction.

PubMed

Liu, Zhengqing; Li, Na; Zhao, Hongyang; Zhang, Yi; Huang, Yunhui; Yin, Zongyou; Du, Yaping

2017-04-01

Three dimensional (3D) N, O and S doped carbon foam (NOSCF) is prepared as a substrate for in situ vertically grown Ni(OH) 2 nanosheets. As designed Ni(OH) 2 /NOSCF possesses strong electrostatic interactions with OH - ions due to many C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O groups existing in NOSCF, which can facilitate the formation of crucial NiOOH intermediates during the OER process. CeO 2 nanoparticles (NPs) of ∼3.3 nm in size are decorated on Ni(OH) 2 nanosheets to design a highly efficient CeO 2 /Ni(OH) 2 /NOSCF electrocatalyst for the oxygen evolution reaction (OER). The CeO 2 NP decorated Ni(OH) 2 /NOSCF not only exhibits a remarkably improved OER performance with an onset potential of 240 mV, outperforming most reported non-noble metal based OER electrocatalysts, but also possesses a small Tafel slope of 57 mV dec -1 and excellent stability under different overpotentials. The synergistic effect of producing more active species of Ni III/IV and accelerating the charge transfer for Ni(OH) 2 /NOSCF by the introduction of CeO 2 NPs is also investigated. These results demonstrate the possibility of designing energy efficient OER catalysts with the assistance of earth abundant CeO 2 -based catalysts.

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst

PubMed Central

2016-01-01

Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni–Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources. PMID:27610415

Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst.

PubMed

Dai, Lei; Qin, Qing; Zhao, Xiaojing; Xu, Chaofa; Hu, Chengyi; Mo, Shiguang; Wang, Yu Olivia; Lin, Shuichao; Tang, Zichao; Zheng, Nanfeng

2016-08-24

Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni-Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources.

Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2.

PubMed

Ju, Wen; Bagger, Alexander; Hao, Guang-Ping; Varela, Ana Sofia; Sinev, Ilya; Bon, Volodymyr; Roldan Cuenya, Beatriz; Kaskel, Stefan; Rossmeisl, Jan; Strasser, Peter

2017-10-16

Direct electrochemical reduction of CO 2 to fuels and chemicals using renewable electricity has attracted significant attention partly due to the fundamental challenges related to reactivity and selectivity, and partly due to its importance for industrial CO 2 -consuming gas diffusion cathodes. Here, we present advances in the understanding of trends in the CO 2 to CO electrocatalysis of metal- and nitrogen-doped porous carbons containing catalytically active M-N x moieties (M = Mn, Fe, Co, Ni, Cu). We investigate their intrinsic catalytic reactivity, CO turnover frequencies, CO faradaic efficiencies and demonstrate that Fe-N-C and especially Ni-N-C catalysts rival Au- and Ag-based catalysts. We model the catalytically active M-N x moieties using density functional theory and correlate the theoretical binding energies with the experiments to give reactivity-selectivity descriptors. This gives an atomic-scale mechanistic understanding of potential-dependent CO and hydrocarbon selectivity from the M-N x moieties and it provides predictive guidelines for the rational design of selective carbon-based CO 2 reduction catalysts.Inexpensive and selective electrocatalysts for CO 2 reduction hold promise for sustainable fuel production. Here, the authors report N-coordinated, non-noble metal-doped porous carbons as efficient and selective electrocatalysts for CO 2 to CO conversion.

Nano-molybdenum carbide/carbon nanotubes composite as bifunctional anode catalyst for high-performance Escherichia coli-based microbial fuel cell.

PubMed

Wang, Yaqiong; Li, Bin; Cui, Dan; Xiang, Xingde; Li, Weishan

2014-01-15

A novel electrode, carbon felt-supported nano-molybdenum carbide (Mo2C)/carbon nanotubes (CNTs) composite, was developed as platinum-free anode of high performance microbial fuel cell (MFC). The Mo2C/CNTs composite was synthesized by using the microwave-assisted method with Mo(CO)6 as a single source precursor and characterized by using X-ray diffraction and transmission electron microscopy. The activity of the composite as anode electrocatalyst of MFC based on Escherichia coli (E. coli) was investigated with cyclic voltammetry, chronoamperometry, and cell discharge test. It is found that the carbon felt electrode with 16.7 wt% Mo Mo2C/CNTs composite exhibits a comparable electrocatalytic activity to that with 20 wt% platinum as anode electrocatalyst. The superior performance of the developed platinum-free electrode can be ascribed to the bifunctional electrocatalysis of Mo2C/CNTs for the conversion of organic substrates into electricity through bacteria. The composite facilitates the formation of biofilm, which is necessary for the electron transfer via c-type cytochrome and nanowires. On the other hand, the composite exhibits the electrocatalytic activity towards the oxidation of hydrogen, which is the common metabolite of E. coli. © 2013 Elsevier B.V. All rights reserved.

A highly active PtCu3 intermetallic core-shell, multilayered Pt-skin, carbon embedded electrocatalyst produced by a scale-up sol-gel synthesis.

PubMed

Bele, M; Jovanovič, P; Pavlišič, A; Jozinović, B; Zorko, M; Rečnik, A; Chernyshova, E; Hočevar, S; Hodnik, N; Gaberšček, M

2014-11-07

We present a novel, scaled-up sol-gel synthesis which enables one to produce 20 g batches of highly active and stable carbon supported PtCu3 nanoparticles as cathode materials for low temperature fuel cell application. We confirm the presence of an ordered intermetallic phase underneath a multilayered Pt-skin together with firm embedment of nanoparticles in the carbon matrix.

O-, N-Atoms-Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts.

PubMed

Yang, Yang; Mao, Kaitian; Gao, Shiqi; Huang, Hao; Xia, Guoliang; Lin, Zhiyu; Jiang, Peng; Wang, Changlai; Wang, Hui; Chen, Qianwang

2018-05-28

Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese-containing enzymes can catalyze oxygen-evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme-copper oxidases superfamily. Unlike previous single-metal catalysts with general M-N-C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc-air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn-N 3 O 1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

DOE PAGES

Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

2016-12-28

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specificmore » and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.« less

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability

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

Jackson, Ariel; Strickler, Alaina; Higgins, Drew

Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications.more » The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.« less

Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability

DOE PAGES

Jackson, Ariel; Strickler, Alaina; Higgins, Drew; ...

2018-01-12

Improving the performance of oxygen reduction reaction (ORR) electrocatalysts is essential for the commercial efficacy of many renewable energy technologies, including low temperature polymer electrolyte fuel cells (PEFCs). Herein, we report highly active and stable carbon-supported Ru@Pt core-shell nanoparticles (Ru@Pt/C) prepared by a wet chemical synthesis technique. Through rotating disc electrode testing, the Ru@Pt/C achieves an ORR Pt mass-based activity of 0.50 A mg Pt -1 at 0.9 V versus the reversible hydrogen electrode (RHE), which exceeds the activity of the state-of-the-art commercial Pt/C catalyst as well as the Department of Energy 2020 PEFC electrocatalyst activity targets for transportation applications.more » The impact of various synthetic parameters, including Pt to Ru ratios and catalyst pretreatments (i.e., annealing) are thoroughly explored. Pt-based mass activity of all prepared Ru@Pt/C catalysts was found to exceed 0.4 mg Pt -1 across the range of compositions investigated, with the maximum activity catalyst having a Ru:Pt ratio of 1:1. This optimized composition of Ru@Pt/C catalyst demonstrated remarkable stability after 30,000 accelerated durability cycles (0.6 to 1.0 V vs. RHE at 125 mV s -1), maintaining 85% of its initial mass activity. Scanning transmission electron microscopy energy dispersive spectroscopy (STEM-EDS) analysis at various stages of electrochemical testing demonstrated that the Pt shell can provide sufficient protection against the dissolution of the otherwise unstable Ru core.« less

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

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

Zhang, Lulu; Su, Dong; Zhu, Shangqian

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Tuning Nb–Pt Interactions To Facilitate Fuel Cell Electrocatalysis

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

Ghoshal, Shraboni; Jia, Qingying; Bates, Michael K.

High stability, availability of multiple oxidation states, and accessibility within a wide electrochemical window are the prime features of Nb that make it a favorable candidate for electrocatalysis, especially when it is combined with Pt. However, Nb has been used as a support in the form of oxides in all previously reported Pt–Nb electrocatalysts, and no Pt–Nb alloying phase has been demonstrated hitherto. Herein, we report a multifunctional Pt–Nb composite (PtNb/NbOx-C) where Nb exists both as an alloying component with Pt and as an oxide support and is synthesized by means of a simple wet chemical method. In this work,more » the Pt–Nb alloy phase has been firmly verified with the help of multiple spectroscopic methods. This allows for the experimental evidence of the theoretical prediction that Pt–Nb alloy interactions improve the oxygen reduction reaction (ORR) activity of Pt. In addition, such a combination of multiphase Nb brings up myriad features encompassing increased ORR durability, immunity to phosphate anion poisoning, enhanced hydrogen oxidation reaction (HOR) activity, and oxidative carbon monoxide (CO) stripping, making this electrocatalyst useful in multiple fuel cell systems.« less

Palladium nanoparticles supported on vertically oriented reduced graphene oxide for methanol electro-oxidation.

PubMed

Yang, Liming; Tang, Yanhong; Luo, Shenglian; Liu, Chengbin; Song, Hejie; Yan, Dafeng

2014-10-01

Reduced graphene oxide (rGO) is a promising support material for nanosized electrocatalysts. However, the conventional stacking arrangement of rGO sheets confines the electrocatalysts between rGO layers, which decreases the number of catalytic sites substantially. We report here a facile synthesis of vertically oriented reduced graphene oxide (VrGO) through cyclic voltammetric electrolysis of graphene oxide (GO) in the presence of Na2 PdCl4 . Experiments without Pd nanoparticles or with a low loading amount of Pd nanoparticles results in the deposition of rGO parallel to the electrodes. The vertical orientation of Pd/rGO nanoflakes causes a remarkable enhancement of the catalytic activity toward methanol electro-oxidation. The mass activity (620.1 A gPd (-1) ) of Pd/VrGO is 1.9 and 6.2 times that of Pd/flat-lying rGO (331.8 A gPd (-1) ) and commercial Pd/C (100.5 A gPd (-1) ), respectively. Furthermore, the Pd/VrGO catalyst shows excellent resistance to CO poisoning. This work provides a simple wet-chemical method for VrGO preparation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions.

PubMed

Mahmood, Nasir; Yao, Yunduo; Zhang, Jing-Wen; Pan, Lun; Zhang, Xiangwen; Zou, Ji-Jun

2018-02-01

Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state-of-the-art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active-sites with improved electrochemical efficiencies in future.

Palladium-platinum core-shell electrocatalysts for oxygen reduction reaction prepared with the assistance of citric acid

DOE PAGES

Zhang, Lulu; Su, Dong; Zhu, Shangqian; ...

2016-04-26

Core–shell structure is a promising alternative to solid platinum (Pt) nanoparticles as electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). A simple method of preparing palladium (Pd)–platinum (Pt) core–shell catalysts (Pd@Pt/C) in a gram-batch was developed with the assistance of citric acid. The Pt shell deposition involves three different pathways: galvanic displacement reaction between Pd atoms and Pt cations, chemical reduction by citric acid, and reduction by negative charges on Pd surfaces. The uniform ultrathin (~0.4 nm) Pt shell was characterized by in situ X-ray diffraction (XRD) and high-angle annular dark-field scanning transmission electron microscopymore » (HAADF-STEM) images combined with electron energy loss spectroscopy (EELS). Compared with state-of-the-art Pt/C, the Pd@Pt/C core–shell catalyst showed 4 times higher Pt mass activity and much better durability upon potential cycling. As a result, both the mass activity and durability were comparable to that of Pd@Pt/C synthesized by a Cu-mediated-Pt-displacement method, which is more complicated and difficult for mass production.« less

Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst.

PubMed

Chen, Shiming; Perathoner, Siglinda; Ampelli, Claudio; Mebrahtu, Chalachew; Su, Dangsheng; Centi, Gabriele

2017-03-01

Ammonia is synthesized directly from water and N 2 at room temperature and atmospheric pressure in a flow electrochemical cell operating in gas phase (half-cell for the NH 3 synthesis). Iron supported on carbon nanotubes (CNTs) was used as the electrocatalyst in this half-cell. A rate of ammonia formation of 2.2×10 -3  gNH3  m -2  h -1 was obtained at room temperature and atmospheric pressure in a flow of N 2 , with stable behavior for at least 60 h of reaction, under an applied potential of -2.0 V. This value is higher than the rate of ammonia formation obtained using noble metals (Ru/C) under comparable reaction conditions. Furthermore, hydrogen gas with a total Faraday efficiency as high as 95.1 % was obtained. Data also indicate that the active sites in NH 3 electrocatalytic synthesis may be associated to specific carbon sites formed at the interface between iron particles and CNT and able to activate N 2 , making it more reactive towards hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and electrochemical characterization of carbon supported Pt-Pr catalysts for direct ethanol fuel cells prepared using a modified formic acid method in a CO atmosphere.

PubMed

Corradini, Patricia Gon; Antolini, Ermete; Perez, Joelma

2013-07-28

Pt-Pr/C electrocatalysts were prepared using a modified formic acid method, and their activity for carbon monoxide and ethanol oxidation was compared to Pt/C. No appreciable alloy formation was detected by XRD analysis. By TEM measurements it was found that Pt particle size increases with an increasing Pr content in the catalysts and with decreasing metal precursor addition time. XPS measurements indicated Pt segregation on the catalyst surface and the presence of Pr2O3 and PrO2 oxides. The addition of Pr increased the electro-catalytic activity of Pt for both CO and CH3CH2OH oxidation. The enhanced activity of Pt-Pr/C catalysts was ascribed to both an electronic effect, caused by the presence of Pr2O3, and the bi-functional mechanism, caused by the presence of PrO2.

The Effect of Surface Site Ensembles on the Activity and Selectivity of Ethanol Electrooxidation by Octahedral PtNiRh Nanoparticles.

PubMed

Erini, Nina; Beermann, Vera; Gocyla, Martin; Gliech, Manuel; Heggen, Marc; Dunin-Borkowski, Rafal E; Strasser, Peter

2017-06-01

Direct ethanol fuel cells are attractive power sources based on a biorenewable, high energy-density fuel. Their efficiency is limited by the lack of active anode materials which catalyze the breaking of the C-C bond coupled to the 12-electron oxidation to CO 2 . We report shape-controlled PtNiRh octahedral ethanol oxidation electrocatalysts with excellent activity and previously unachieved low onset potentials as low as 0.1 V vs. RHE, while being highly selective to complete oxidation to CO 2 . Our comprehensive characterization and in situ electrochemical ATR studies suggest that the formation of a ternary surface site ensemble around the octahedral Pt 3 Ni 1 Rh x nanoparticles plays a crucial mechanistic role for this behavior. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of carbon supported PtW catalysts as CO tolerant anodes at high temperature in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Hassan, Ayaz; Paganin, Valdecir A.; Ticianelli, Edson A.

2016-09-01

The CO tolerance mechanism and the stability of carbon supported PtW electrocatalysts are evaluated in the anode of a proton exchange membrane fuel cell (PEMFC) at two different temperatures. The electrocatalysts are characterized by energy dispersive spectroscopy, X-ray diffraction, and transmission electron spectroscopy. Employed electrochemical techniques include cyclic voltammetry, CO stripping, fuel cell polarization, and online mass spectrometry. At a cell temperature of 85 °C, the PtW/C catalyst shows higher CO tolerance compared to Pt/C due an electronic effect of WOx in the Pt 5d band, which reduces the CO adsorption. An increase in hydrogen oxidation activity in the presence of CO is observed for both the catalysts at a higher temperature, due to the decrease of the Pt-CO coverage. A reduction in the current densities occurs for the PtW/C catalyst in both polarization curves and cyclic voltammograms after 5000 cycles of the anode in the range of 0.1-0.7 V vs. RHE at 50 mVs-1. This decrease in performance is assigned to the dissolution of W, with a consequent increase in the membrane resistivity. However, the observed decline of performance is small either in the presence of pure H2 or in the presence of H2/CO.