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Sample records for enhanced metal organic

  1. Metallic nanoparticle deposition techniques for enhanced organic photovoltaic cells

    NASA Astrophysics Data System (ADS)

    Cacha, Brian Joseph Gonda

    Energy generation via organic photovoltaic (OPV) cells provide many advantages over alternative processes including flexibility and price. However, more efficient OPVs are required in order to be competitive for applications. One way to enhance efficiency is through manipulation of exciton mechanisms within the OPV, for example by inserting a thin film of bathocuproine (BCP) and gold nanoparticles between the C60/Al and ZnPc/ITO interfaces, respectively. We find that BCP increases efficiencies by 330% due to gains of open circuit voltage (Voc) by 160% and short circuit current (Jsc) by 130%. However, these gains are complicated by the anomalous photovoltaic effect and an internal chemical potential. Exploration in the tuning of metallic nanoparticle deposition on ITO was done through four techniques. Drop casting Ag nanoparticle solution showed arduous control on deposited morphology. Spin-coating deposited very low densities of nanoparticles. Drop casting and spin-coating methods showed arduous control on Ag nanoparticle morphology due to clustering and low deposition density, respectively. Sputtered gold on glass was initially created to aid the adherence of Ag nanoparticles but instead showed a quick way to deposit aggregated gold nanoparticles. Electrodeposition of gold nanoparticles (AuNP) proved a quick method to tune nanoparticle morphology on ITO substrates. Control of deposition parameters affected AuNP size and distribution. AFM images of electrodeposited AuNPs showed sizes ranging from 39 to 58 nm. UV-Vis spectroscopy showed the presence of localized plasmon resonance through absorption peaks ranging from 503 to 614 nm. A linear correlation between electrodeposited AuNP size and peak absorbance was seen with a slope of 3.26 wavelength(nm)/diameter(nm).

  2. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

    PubMed Central

    Yang, Qiu; Liu, Wenxian; Wang, Bingqing; Zhang, Weina; Zeng, Xiaoqiao; Zhang, Cong; Qin, Yongji; Sun, Xiaoming; Wu, Tianpin; Liu, Junfeng; Huo, Fengwei; Lu, Jun

    2017-01-01

    Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface. PMID:28195131

  3. Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency

    NASA Astrophysics Data System (ADS)

    Yang, Qiu; Liu, Wenxian; Wang, Bingqing; Zhang, Weina; Zeng, Xiaoqiao; Zhang, Cong; Qin, Yongji; Sun, Xiaoming; Wu, Tianpin; Liu, Junfeng; Huo, Fengwei; Lu, Jun

    2017-02-01

    Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.

  4. Optical design of transparent metal grids for plasmonic absorption enhancement in ultrathin organic solar cells.

    PubMed

    Kim, Inho; Lee, Taek Seong; Jeong, Doo Seok; Lee, Wook Seong; Kim, Won Mok; Lee, Kyeong-Seok

    2013-07-01

    Transparent metal grid combining with plasmonic absorption enhancement is a promising replacement to indium tin oxide thin films. We numerically demonstrate metal grids in one or two dimension lead to plasmonic absorption enhancements in ultrathin organic solar cells. In this paper, we study optical design of metal grids for plasmonic light trapping and identify different plasmonic modes of the surface plasmon polaritons excited at the interfaces of glass/metal grids, metal grids/active layers, and the localized surface plasmon resonance of the metal grids using numerical calculations. One dimension metal grids with the optimal design of a width and a period lead to the absorption enhancement in the ultrathin active layers of 20 nm thickness by a factor of 2.6 under transverse electric polarized light compared to the case without the metal grids. Similarly, two dimensional metal grids provide the absorption enhancement by a factor of 1.8 under randomly polarized light.

  5. The emerging multiple metal nanostructures for enhancing the light trapping of thin film organic photovoltaic cells.

    PubMed

    Choy, Wallace C H

    2014-10-18

    Recently, various metal nanostructures have been introduced into organic solar cells (OSCs) for performance enhancement. Here, we review the recent progress in OSCs incorporated with multiple metal nanostructures including various metal nanopatterns and metal nanomaterials. Multiple physical effects arise from these incorporated nanostructures, which require careful distinction. Changes induced by the metal nanostructures are examined in detail from the optical and electrical aspects. With the comprehensive understanding of the physical mechanisms for various metal nanostructures, further improvement in device performance and emerging applications can be expected for the new class of nanostructure-incorporated OSCs.

  6. Nanoscale Fluorescent Metal-Organic Framework@Microporous Organic Polymer Composites for Enhanced Intracellular Uptake and Bioimaging.

    PubMed

    Wang, Lei; Wang, Weiqi; Zheng, Xiaohua; Li, Zhensheng; Xie, Zhigang

    2017-01-26

    Polymer-modified metal-organic frameworks combine the advantages of both soft polymers and crystalline metal-organic frameworks (MOFs). It is a big challenge to develop simple methods for surface modification of MOFs. In this work, MOF@microporous organic polymer (MOP) hybrid nanoparticles (UNP) have been synthesized by epitaxial growth of luminescent boron-dipyrromethene (BODIPYs)-imine MOPs on the surface of UiO-MOF seeds, which exhibit low cytotoxicity, smaller size distribution, well-retained pore integrity, and available functional sites. After folic acid grafting, the enhanced intracellular uptake and bioimaging was validated.

  7. Mechanism of optical absorption enhancement in thin film organic solar cells with plasmonic metal nanoparticles.

    PubMed

    Qu, Di; Liu, Fang; Huang, Yidong; Xie, Wanlu; Xu, Qi

    2011-11-21

    The optical absorption enhancement in thin film organic solar cells (OSCs) with plasmonic metal nanoparticles (NPs) has been studied by means of finite element method with a three-dimension model. It is found that significant plasmonic enhancement of above 100% can be obtained by introducing Ag-NPs at the interface between P3HT:PCBM active layer and PEDOT:PSS anode layer. This enhancement is even larger than that with Ag-NPs totally embedded in the P3HT:PCBM active layer of thin film OSCs. Furthermore, the enhancement mechanism of Ag-NPs at different positions of thin film OSCs is investigated.

  8. Suppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials

    NASA Astrophysics Data System (ADS)

    Kwon, Min Sang; Yu, Youngchang; Coburn, Caleb; Phillips, Andrew W.; Chung, Kyeongwoon; Shanker, Apoorv; Jung, Jaehun; Kim, Gunho; Pipe, Kevin; Forrest, Stephen R.; Youk, Ji Ho; Gierschner, Johannes; Kim, Jinsang

    2015-12-01

    Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin-orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels-Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage.

  9. Suppressing molecular motions for enhanced room-temperature phosphorescence of metal-free organic materials

    PubMed Central

    Kwon, Min Sang; Yu, Youngchang; Coburn, Caleb; Phillips, Andrew W.; Chung, Kyeongwoon; Shanker, Apoorv; Jung, Jaehun; Kim, Gunho; Pipe, Kevin; Forrest, Stephen R.; Youk, Ji Ho; Gierschner, Johannes; Kim, Jinsang

    2015-01-01

    Metal-free organic phosphorescent materials are attractive alternatives to the predominantly used organometallic phosphors but are generally dimmer and are relatively rare, as, without heavy-metal atoms, spin–orbit coupling is less efficient and phosphorescence usually cannot compete with radiationless relaxation processes. Here we present a general design rule and a method to effectively reduce radiationless transitions and hence greatly enhance phosphorescence efficiency of metal-free organic materials in a variety of amorphous polymer matrices, based on the restriction of molecular motions in the proximity of embedded phosphors. Covalent cross-linking between phosphors and polymer matrices via Diels–Alder click chemistry is devised as a method. A sharp increase in phosphorescence quantum efficiency is observed in a variety of polymer matrices with this method, which is ca. two to five times higher than that of phosphor-doped polymer systems having no such covalent linkage. PMID:26626796

  10. Broadband absorption enhancement of organic solar cells with interstitial lattice patterned metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Luzhou; Choy, Wallace C. H.; Sha, Wei E. I.

    2013-06-01

    Light blocking induced by top patterned nanostructures is a fundamental limit in solar cells absorption. Here we propose an interstitial lattice patterned organic solar cell which can improve the light blocking of traditional square lattice and achieve broadband absorption enhancement. Compared to square lattice design, the plasmonic mode couplings between individual metallic nanoparticles in the interstitial lattice are more versatile and much stronger. Moreover, plasmonic modes can couple to the guided modes, resulting in large enhancement factor at some wavelengths. The interstitial lattice concept will be a broad interest and great help for high-performance photovoltaics.

  11. Fluorous Metal-Organic Frameworks with Enhanced Stability and High H2/CO2 Storage Capacities

    PubMed Central

    Zhang, Da-Shuai; Chang, Ze; Li, Yi-Fan; Jiang, Zhong-Yi; Xuan, Zhi-Hong; Zhang, Ying-Hui; Li, Jian-Rong; Chen, Qiang; Hu, Tong-Liang; Bu, Xian-He

    2013-01-01

    A new class of metal-organic frameworks (MOFs) has been synthesized by ligand-functionalization strategy. Systematic studies of their adsorption properties were performed at low and high pressure. Importantly, when fluorine was introduced into the framework via the functionalization, both the framework stabilities and adsorption capacities towards H2/CO2 were enhanced significantly. This consequence can be well interpreted by theoretical studies of these MOFs structures. In addition, one of these MOFs TKL-107 was used to fabricate mixed matrix membranes, which exhibit great potential for the application of CO2 separation. PMID:24264725

  12. Metallated metal-organic frameworks

    DOEpatents

    Bury, Wojciech; Farha, Omar K.; Hupp, Joseph T.; Mondloch, Joseph E.

    2017-02-07

    Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

  13. Electron accumulation on metal nanoparticles in plasmon-enhanced organic solar cells.

    PubMed

    Salvador, Michael; MacLeod, Bradley A; Hess, Angela; Kulkarni, Abhishek P; Munechika, Keiko; Chen, Jennifer I L; Ginger, David S

    2012-11-27

    Plasmonic metal nanoparticles have been used to enhance the performance of thin-film devices such as organic photovoltaics based on polymer/fullerene blends. We show that silver nanoprisms accumulate long-lived negative charges when they are in contact with a photoexcited bulk heterojunction blend composed of poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM). We report both the charge modulation and electroabsorption spectra of silver nanoprisms in solid-state devices and compare these spectra with the photoinduced absorption spectra of P3HT/PCBM blends containing silver nanoprisms. We assign a previously unidentified peak in the photoinduced absorption spectra to the presence of photoinduced electrons on the silver nanoprisms. We show that coating the nanoprisms with a 2.5 nm thick insulating layer can completely inhibit this charging. These results may inform methods for limiting metal-mediated losses in plasmonic solar cells.

  14. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals

    NASA Astrophysics Data System (ADS)

    Bachman, Jonathan E.; Smith, Zachary P.; Li, Tao; Xu, Ting; Long, Jeffrey R.

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

  15. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal-organic framework nanocrystals.

    PubMed

    Bachman, Jonathan E; Smith, Zachary P; Li, Tao; Xu, Ting; Long, Jeffrey R

    2016-08-01

    The implementation of membrane-based separations in the petrochemical industry has the potential to reduce energy consumption significantly relative to conventional separation processes. Achieving this goal, however, requires the development of new membrane materials with greater selectivity, permeability and stability than available at present. Here, we report composite materials consisting of nanocrystals of metal-organic frameworks dispersed within a high-performance polyimide, which can exhibit enhanced selectivity for ethylene over ethane, greater ethylene permeability and improved membrane stability. Our results suggest that framework-polymer interactions reduce chain mobility of the polymer while simultaneously boosting membrane separation performance. The increased stability, or plasticization resistance, is expected to improve membrane utility under real process conditions for petrochemical separations and natural gas purification. Furthermore, this approach can be broadly applied to numerous polymers that encounter aggressive environments, potentially making gas separations possible that were previously inaccessible to membranes.

  16. Enhanced surface losses of organic solar cells induced by efficient polaron pair dissociation at the metal/organic interface

    NASA Astrophysics Data System (ADS)

    Yang, Wenchao; Li, De-Li; Yao, Yao; Hou, Xiaoyuan; Wu, Chang-Qin

    2012-08-01

    As a growing importance is placed on developing more efficient organic solar cells, understanding the behavior of free charge carriers at the metal/organic (M/O) interface is critical. One of the current challenges is understanding surface losses, essentially the loss of free charge carriers at the electrode/organic interface. In this paper, we use device model simulations to study such phenomena and we pay particular attention to the role of polaron pair (PP) M/O interfacial dissociation. The origin of surface losses is through the extraction of free charge carriers from the wrong electrodes, or direct surface recombination of PPs. Through simulation, we find that a high injection barrier leads to a large surface loss. In addition, surface loss increases with both the interfacial dissociation rate and PP diffusivity. Efficient interfacial dissociation can significantly enhance surface losses if the PP diffusivity is relatively large. Furthermore, current voltage characteristics reveal that surface losses undermine the device operating parameters and efficiency. Interlayers inserted at the M/O interface could block wrong electrode carriers, suppress the interfacial dissociation and reduce surface losses.

  17. Tuning Metal-Organic Frameworks with Open-Metal Sites and Its Origin for Enhancing CO2 Affinity by Metal Substitution.

    PubMed

    Park, Joonho; Kim, Heejin; Han, Sang Soo; Jung, Yousung

    2012-04-05

    Reducing anthropogenic carbon emission is a problem that requires immediate attention. Metal-organic frameworks (MOFs) have emerged as a promising new materials platform for carbon capture, of which Mg-MOF-74 offers chemospecific affinity toward CO2 because of the open Mg sites. Here we tune the binding affinity of CO2 for M-MOF-74 by metal substitution (M = Mg, Ca, and the first transition metal elements) and show that Ti- and V-MOF-74 can have an enhanced affinity compared to Mg-MOF-74 by 6-9 kJ/mol. Electronic structure calculations suggest that the origin of the major affinity trend is the local electric field effect of the open metal site that stabilizes CO2, but forward donation from the lone-pair electrons of CO2 to the empty d-levels of transition metals as in a weak coordination bond makes Ti and V have an even higher binding strength than Mg, Ca, and Sc.

  18. Functionalization of Metal-Organic Frameworks for Enhanced Stability under Humid Carbon Dioxide Capture Conditions.

    PubMed

    Andirova, Dinara; Lei, Yu; Zhao, Xiaodan; Choi, Sunho

    2015-10-26

    Metal-organic frameworks (MOFs) have been highlighted recently as promising materials for CO2 capture. However, in practical CO2 capture processes, such as capture from flue gas or ambient air, the adsorption properties of MOFs tend to be harmed by the presence of moisture possibly because of the hydrophilic nature of the coordinatively unsaturated sites (CUSs) within their framework. In this work, the CUSs of the MOF framework are functionalized with amine-containing molecules to prevent structural degradation in a humid environment. Specifically, the framework of the magnesium dioxybenzenedicarboxylate (Mg/DOBDC) MOF was functionalized with ethylenediamine (ED) molecules to make the overall structure less hydrophilic. Structural analysis after exposure to high-temperature steam showed that the ED-functionalized Mg/DOBDC (ED-Mg/DOBDC) is more stable under humid conditions, than Mg/DOBDC, which underwent drastic structural changes. ED-Mg/DOBDC recovered its CO2 adsorption capacity and initial adsorption rate quite well as opposed to the original Mg/DOBDC, which revealed a significant reduction in its capture capacity and kinetics. These results suggest that the amine-functionalization of the CUSs is an effective way to enhance the structural stability of MOFs as well as their capture of humid CO2 .

  19. Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases

    PubMed Central

    Pawar, Vijay; Naik, Prashant; Giridhar, Rajani; Yadav, Mange Ram

    2015-01-01

    In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanolamine, and diethylamine) had lowered melting points while the alkali metal salt (sodium) had a higher melting point than BPA. The in vitro study showed that salt formation improves the physicochemical properties of BPA, leading to improved permeability through the skin. Amongst all the prepared salts, ethanolamine salt (1b) showed 7.2- and 5.4-fold higher skin permeation than the parent drug at pH 7.4 and 5.0, respectively, using rat skin. PMID:26839810

  20. One-pot synthesis of protein-embedded metal-organic frameworks with enhanced biological activities.

    PubMed

    Lyu, Fengjiao; Zhang, Yifei; Zare, Richard N; Ge, Jun; Liu, Zheng

    2014-10-08

    Protein molecules were directly embedded in metal-organic frameworks (MOFs) by a coprecipitation method. The protein molecules majorly embedded on the surface region of MOFs display high biological activities. As a demonstration of the power of such materials, the resulting Cyt c embedded in ZIF-8 showed a 10-fold increase in peroxidase activity compared to free Cyt c in solution and thus gave convenient, fast, and highly sensitive detection of trace amounts of explosive organic peroxides in solution.

  1. Analysis and optimization of surface plasmon-enhanced organic solar cells with a metallic crossed grating electrode.

    PubMed

    Lee, Eungkyu; Kim, Changsoon

    2012-09-10

    We perform a systematic analysis of enhanced short-circuit current density (J(sc) in organic solar cells (OSCs) where one metallic electrode is optically thick and the other consists of a two-dimensional metallic crossed grating. By examining a model device representative of such surface plasmon (SP)-enhanced OSCs by the Fourier modal and finite-element methods for electromagnetic and exciton diffusion calculations, respectively, we provide general guidelines to maximize J(sc) of the SP-enhanced OSCs. Based on this study, we optimize the performance of a small-molecule OSC employing a copper phthalocyanine-fullerene donor-acceptor pair, demonstrating that the optimized SP-enhanced device has J(sc) that is 75 % larger than that of the optimized device with an ITO-based conventional structure.

  2. Revisited design optimization of metallic gratings for plasmonic light-trapping enhancement in thin organic solar cells

    NASA Astrophysics Data System (ADS)

    Toan Dang, Phuc; Nguyen, Truong Khang; Le, Khai Q.

    2017-01-01

    We revisit previous studies of metallic gratings for optical absorption enhancement in an organic solar cell with a thin active layer. Our device geometry is designed for a real solar cell with full of functional layers. Various metallic gratings calibrated to generate periodic scatterers and low reflectors for broadband light account for increases in short circuit current density of up to 47% when compared to its flat counterpart. We found that the tapered grating has greater performance than the regular rectangular grating for transverse magnetic (TM) polarization while the latter shows better performance for transverse electric (TE) polarization. The overall metallic grating induced absorption enhancement was found at all angles of incidence. The best configuration was realized for the tapered grating-based solar cell at 25° of inclination.

  3. Simple way to engineer metal-semiconductor interface for enhanced performance of perovskite organic lead iodide solar cells.

    PubMed

    Xu, Yuzhuan; Shi, Jiangjian; Lv, Songtao; Zhu, Lifeng; Dong, Juan; Wu, Huijue; Xiao, Yin; Luo, Yanhong; Wang, Shirong; Li, Dongmei; Li, Xianggao; Meng, Qingbo

    2014-04-23

    A thin wide band gap organic semiconductor N,N,N',N'-tetraphenyl-benzidine layer has been introduced by spin-coating to engineer the metal-semiconductor interface in the hole-conductor-free perovskite solar cells. The average cell power conversion efficiency (PCE) has been enhanced from 5.26% to 6.26% after the modification and a highest PCE of 6.71% has been achieved. By the aid of electrochemical impedance spectroscopy and dark current analysis, it is revealed that this modification can increase interfacial resistance of CH3NH3PbI3/Au interface and retard electron recombination process in the metal-semiconductor interface.

  4. Ligand Symmetry Modulation for Designing a Mesoporous Metal-Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization.

    PubMed

    Du, Miao; Wang, Xi; Chen, Min; Li, Cheng-Peng; Tian, Jia-Yue; Wang, Zhuo-Wei; Liu, Chun-Sen

    2015-06-26

    A promising alternative strategy for designing mesoporous metal-organic frameworks (MOFs) has been proposed, by modifying the symmetry rather than expanding the length of organic linkers. By means of this approach, a unique MOF material based on the target [Zn8(ad)4] (ad = adeninate) clusters and C3-symmetric organic linkers can be obtained, with trigonal microporous (ca., 0.8 nm) and hexagonal mesoporous (ca., 3.0 nm) 1D channels. Moreover, the resulting 446-MOF shows distinct reactivity to transition and lanthanide metal ions. Significantly, the transmetalation of Co(II) or Ni(II) on the Zn(II) centers in 446-MOF can enhance the sorption capacities of CO2 and CH4 (16-21%), whereas the impregnation of Eu(III) and Tb(III) in the channels of 446-MOF will result in adjustable light-emitting behaviors.

  5. Removal of heavy metals from contaminated soil by electrodialytic remediation enhanced with organic acids.

    PubMed

    Merdoud, Ouarda; Cameselle, Claudio; Boulakradeche, Mohamed Oualid; Akretche, Djamal Eddine

    2016-11-09

    The soil from an industrial area in Algeria was contaminated with Cr (8370 mg kg(-1)), Ni (1135 mg kg(-1)) and zinc (1200 mg kg(-1)). The electrodialytic remediation of this soil was studied using citric acid and EDTA as facilitating agents. 0.1 M citric acid or EDTA was added directly to the soil before it was introduced in an electrodialytic cell in an attempt to enhance the heavy metal solubility in the interstitial fluid. The more acidic pH in the soil when citric acid was used as the facilitating agent was not enough to mobilize and remove the metals from the soil. Only 7.2% of Ni and 6.7% of Zn were removed from the soil in the test with citric acid. The best results were found with EDTA, which was able to solubilize and complex Zn and Ni forming negatively charged complexes that were transported and accumulated in the anolyte. Complete removal was observed for Ni and Zn in the electrodialytic treatment with EDTA. Minor amounts of Cr were removed with both EDTA and citric acid.

  6. Performance Enhancement of Organic Light-Emitting Diodes Using Electron-Injection Materials of Metal Carbonates

    NASA Astrophysics Data System (ADS)

    Shin, Jong-Yeol; Kim, Tae Wan; Kim, Gwi-Yeol; Lee, Su-Min; Shrestha, Bhanu; Hong, Jin-Woong

    2016-05-01

    Performance of organic light-emitting diodes was investigated depending on the electron-injection materials of metal carbonates (Li2CO3 and Cs2CO3 ); and number of layers. In order to improve the device efficiency, two types of devices were manufactured by using the hole-injection material (Teflon-amorphous fluoropolymer -AF) and electron-injection materials; one is a two-layer reference device ( ITO/Teflon-AF/Alq3/Al ) and the other is a three-layer device (ITO/Teflon-AF/Alq3/metal carbonate/Al). From the results of the efficiency for the devices with hole-injection layer and electron-injection layer, it was found that the electron-injection layer affects the electrical properties of the device more than the hole-injection layer. The external-quantum efficiency for the three-layer device with Li2CO3 and Cs2CO3 layer is improved by approximately six and eight times, respectively, compared with that of the two-layer reference device. It is thought that a use of electron-injection layer increases recombination rate of charge carriers by the active injection of electrons and the blocking of holes.

  7. Metal Insertion in a Methylamine-Functionalized Zirconium Metal-Organic Framework for Enhanced Carbon Dioxide Capture.

    PubMed

    Gómora-Figueroa, A Paulina; Mason, Jarad A; Gonzalez, Miguel I; Bloch, Eric D; Meihaus, Katie R

    2017-03-27

    The reaction of ZrCl4 with 2',3',5',6'-tetramethylamino-p-terphenyl-4,4″-dicarboxylic acid (H2tpdc-4CH2NH2·3HCl) in the presence of NaF affords Zr6O4(OH)2.1F1.9(tpdc-4CH2NH2·3HCl)6 (1), which is a new member of the Zr6O4(OH)4(dicarboxylate linker)12 or UiO-68 family, and exhibits high porosity with BET and Langmuir surface areas of 1910 m(2)/g and 2220 m(2)/g, respectively. Remarkably, fluoride ion incorporation in the zirconium clusters results in increased thermal stability, marking the first example of enhancement in the stability of a UiO framework by this defect-restoration approach. Although material 1 features four alkylamine groups on each organic linker, the framework does not exhibit the high CO2 uptake that would be expected for reaction between CO2 and the amine groups to form carbamic acid or ammonium carbamate species. The absence of strong CO2 adsorption can likely be attributed to protonation at some of the amine sites and the presence of counterions. Indeed, exposure of material 1 to acetonitrile solutions of the organic bases 1,8-bis(dimethylamino)naphthalene (DMAN) or trimethylamine, affords a partially deprotonated material, which exhibits enhanced CO2 uptake. Exposure of basic amine sites also facilitates the postsynthetic chelation of copper(I) ([Cu(MeCN)4]·CF3SO3) to yield material 2 with an enhanced CO2 uptake of 4 wt % at 0.15 bar, which is double that of the parent framework 1.

  8. Electrocatalytic oxidation of small organic molecules in acid medium: enhancement of activity of noble metal nanoparticles and their alloys by supporting or modifying them with metal oxides

    PubMed Central

    Kulesza, Pawel J.; Pieta, Izabela S.; Rutkowska, Iwona A.; Wadas, Anna; Marks, Diana; Klak, Karolina; Stobinski, Leszek; Cox, James A.

    2013-01-01

    Different approaches to enhancement of electrocatalytic activity of noble metal nanoparticles during oxidation of small organic molecules (namely potential fuels for low-temperature fuel cells such as methanol, ethanol and formic acid) are described. A physical approach to the increase of activity of catalytic nanoparticles (e.g. platinum or palladium) involves nanostructuring to obtain highly dispersed systems of high surface area. Recently, the feasibility of enhancing activity of noble metal systems through the formation of bimetallic (e.g. PtRu, PtSn, and PdAu) or even more complex (e.g. PtRuW, PtRuSn) alloys has been demonstrated. In addition to possible changes in the electronic properties of alloys, specific interactions between metals as well as chemical reactivity of the added components have been postulated. We address and emphasize here the possibility of utilization of noble metal and alloyed nanoparticles supported on robust but reactive high surface area metal oxides (e.g. WO3, MoO3, TiO2, ZrO2, V2O5, and CeO2) in oxidative electrocatalysis. This paper concerns the way in which certain inorganic oxides and oxo species can act effectively as supports for noble metal nanoparticles or their alloys during electrocatalytic oxidation of hydrogen and representative organic fuels. Among important issues are possible changes in the morphology and dispersion, as well as specific interactions leading to the improved chemisorptive and catalytic properties in addition to the feasibility of long time operation of the discussed systems. PMID:24443590

  9. ENVIROMETAL TECHNOLOGIES, INC., METAL-ENHANCED DECHLORINATION OF VOLATILE ORGANIC COMPOUNDS USING AN IN-SITU REACTIVE IRON WALL

    EPA Science Inventory

    This report summarizes the results of a field demonstration conducted under the SITE program. The technology that was demonstrated was a metal-enhanced dechlorination process developed by EnviroMetal Technologies, Inc. to treat groundwater contaminated with chlorinated volatile ...

  10. Fabrication of gold nanoparticle-embedded metal-organic framework for highly sensitive surface-enhanced Raman scattering detection.

    PubMed

    Hu, Yuling; Liao, Jia; Wang, Dongmei; Li, Gongke

    2014-04-15

    Surface-enhanced Raman scattering (SERS) signals strongly rely on the interactions and distance between analyte molecules and metallic nanostructures. In this work, the use of a gold nanoparticle (AuNP)-embedded metal-organic framework was introduced for the highly sensitive SERS detection. The AuNPs were in situ grown and encapsulated within the host matrix of MIL-101 by a solution impregnation strategy. The as-synthesized AuNPs/MIL-101 nanocomposites combined the localized surface plasmon resonance properties of the gold nanoparticles and the high adsorption capability of metal-organic framework, making them highly sensitive SERS substrates by effectively preconcentrating analytes in close proximity to the electromagnetic fields at the SERS-active metal surface. We discussed the fabrication, physical characterization, and SERS activity of our novel substrates by measuring the Raman signals of a variety of model analytes. The SERS substrate was found to be highly sensitive, robust, and amiable to several different target analytes. A SERS detection limit of 41.75 and 0.54 fmol for Rhodamine 6G and benzadine, respectively, was demonstrated. The substrate also showed high stability and reproducibility, as well as molecular sieving effect thanks to the protective shell of the metal-organic framework. Subsequently, the potential practical application of the novel SERS substrate was evaluated by quantitative analysis of organic pollutant p-phenylenediamine in environmental water and tumor marker alpha-fetoprotein in human serum. The method showed good linearity between 1.0 and 100.0 ng/mL for p-phenylenediamine and 1.0-130.0 ng/mL for alpha-fetoprotein with the correlation coefficients of 0.9950 and -0.9938, respectively. The recoveries ranged from 80.5% to 114.7% for p-phenylenediamine in environmental water and 79.3% to 107.3% for alpha-fetoprotein in human serum. These results foresee promising application of the novel metal-organic framework based composites as

  11. Enhanced photochemical hydrogen production by a molecular diiron catalyst incorporated into a metal-organic framework.

    PubMed

    Pullen, Sonja; Fei, Honghan; Orthaber, Andreas; Cohen, Seth M; Ott, Sascha

    2013-11-13

    A molecular proton reduction catalyst [FeFe](dcbdt)(CO)6 (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal-organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)3](2+) as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)6 catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1(-) and 1(2-) from undesirable charge recombination with oxidized ascorbate.

  12. Facile synthesis of glucoamylase embedded metal-organic frameworks (glucoamylase-MOF) with enhanced stability.

    PubMed

    Nadar, Shamraja S; Rathod, Virendra K

    2017-02-01

    The self-assembled glucoamylase metal-organic framework (glucoamylase-MOF) was synthesized by facile one-step method within 20min by simply mixing aqueous solution of 2-methylimidazole (160mM), glucoamylase (5mg/mL) and zinc acetate (40mM) at room temperature (28±2°C). The prepared glucoamylase-MOF was characterized by using FT-IR, confocal scanning laser microscopy, XRD and SEM. The robustness and thermal stability of glucoamylase embedded MOF was evaluated in terms of half-life (in the range of 60-80°C) which showed 6 folds increment as against free form. Further, in Michaelis-Menten kinetics studies, glucoamylase entrapped MOF exhibited higher Km value and lower Vmax value as compared to native enzyme. Moreover, the immobilized glucoamylase exhibited up to 57% of residual activity after six consecutive cycles of reuse, whereas it retained 91% of residual activity till 25days of storage. Finally, the conformational changes occurred after the encapsulation of glucoamylase in the interior of MOF, which was analyzed by using FT-IR data analysis tools.

  13. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A.; Rosay, Melanie; Johnson, Duane D.; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt²⁺ and Cu²⁺) and a zirconium metal–organic framework (UiO-66-NH₂) was explored using dynamic nuclear polarization-enhanced ¹⁵N{¹H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt²⁺ coordinates with two NH₂ groups from the MOF and two Cl⁻ from the metal precursor, whereas Cu²⁺ do not form chemical bonds with the NH₂ groups of the MOF framework. Density functional calculations reveal that Pt²⁺ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  14. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A; Rosay, Melanie; Johnson, Duane D; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt2+ and Cu2+) and a zirconium metal–organic framework (UiO-66-NH2) was explored using dynamic nuclear polarization-enhanced 15N{1H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt2+ coordinates with two NH2 groups from the MOF and two Cl- from the metal precursor, whereas Cu2+ do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt2+ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  15. Novel enhancement of thin-form-factor galvanic cells: Probing halogenated organic oxidizers and metal anodes

    NASA Astrophysics Data System (ADS)

    Cardenas-Valencia, Andres M.; Adornato, Lori; Short, R. Timothy; Langebrake, Larry

    The work reported herein demonstrates a novel method to improve the overall performance of thin-form-factor galvanic cells, fabricated via micro-electromechanical systems (MEMS) processes. Use of solid, low cost, cyclic-halogenated, organic catholyte materials permits water activation of cells consisting of metal anode and catalytic platinum positive electrodes. Similar cells, employing aluminum and zinc anodes, have been activated using sodium hypochlorite (NaClO) solutions, i.e. bleach, in the past. The oxidizers chosen for this study (bromo-, chloro- and iodo-succinimides, and sodium dichloroisocyanuric acid) supply the cathode's oxy-halogenated ions when in contact with water. Zinc, magnesium and aluminum anodes are utilized to fabricate galvanic cells. A comparison between these anodes, coupled with various oxidizers, is included herein. Results using aluminum anode cells show that, even though the utilization efficiency of the catholyte reagents is low (faradic efficiencies between 16 and 19%), the performance of the new water-activated cells (6 cm × 6 cm × 0.25 cm) is superior when compared to those activated with bleach. For instance, operational lives of 6 h (activation with 10% NaClO solution) increase to more than 30 h using the new approach, with a 100-ohm-load. It is also shown that specific energies of 90-110 Wh kg -1 (calculated to include both reagent and packaging mass) could be obtained using the described approach with current draws between 10 and 20 mA. The specific energies obtained suggest that novel MEMS-type cells could have much broader application than low-current, bleach-activated cells.

  16. Enhanced CO oxidation on CeO2/Co3O4 nanojunctions derived from annealing of metal organic frameworks.

    PubMed

    Wang, Changlai; Wang, Dongdong; Yang, Yang; Li, Ren; Chen, Changle; Chen, Qianwang

    2016-12-01

    The interface of nanojunctions plays an important role in the performance of heterogeneous catalysts. However, it is highly challenging to construct nanojunctions which are usually prepared by complex multistep processes. Metal-organic frameworks (MOFs), with designable metal centers and tunable organic ligands, are promising precursors for the one-step synthesis of nanojunctions. Herein, we prepared porous CeO2/Co3O4 nanojunctions by direct annealing of MOFs in air. These unique nanojunctions exhibit remarkable catalytic activity for CO oxidation, which can achieve complete oxidization of CO to CO2 at 110 °C. In contrast, the temperature required for 100% CO oxidation is 190 °C for pure Co3O4. Moreover, the nanojunctions can maintain complete CO conversion after 16 h at 110 °C. Density functional theory calculations revealed that the enhancement in the catalytic activity of CeO2/Co3O4 nanojunctions can be attributed to the charge transfer through the interfaces of the nanojunctions.

  17. Metal Oxide Assisted Preparation of Core-Shell Beads with Dense Metal-Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants.

    PubMed

    Del Rio, Mateo; Palomino Cabello, Carlos; Gonzalez, Veronica; Maya, Fernando; Parra, Jose B; Cerdà, Victor; Turnes Palomino, Gemma

    2016-08-08

    Dense and homogeneous metal-organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core-shell beads. The ZnO@PS beads are reactive in the presence of 2-methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework-8 (ZIF-8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF-8@ZnO@PS beads can be easily packed in column format for flow-through applications, such as the solid-phase extraction of trace priority-listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4-tert-octylphenol and 4-n-nonylphenol), facilitating their analysis when present at very low levels (<1 μg L(-1) ) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF-8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF-8 on the surface of the PS beads in the absence of metal oxide intermediate coatings.

  18. Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

    SciTech Connect

    Wei, ZW; Gu, ZY; Arvapally, RK; Chen, YP; McDougald, RN; Ivy, JF; Yakovenko, AA; Feng, DW; Omary, MA; Zhou, HC

    2014-06-11

    We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 +/- 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

  19. Plasmonic core-shell metal-organic nanoparticles enhanced dye-sensitized solar cells.

    PubMed

    Xu, Qi; Liu, Fang; Meng, Weisi; Huang, Yidong

    2012-11-05

    We present an investigation on introducing core-shell Au@PVP nanoparticles (NPs) into dye-sensitized solar cells. As a novel core-shell NPs structure, Au@PVP present not only the chemical stability to iodide/triiodide electrolyte, but also the adhesiveness to dye molecules, which could help to localize most of dye molecules around plasmonic NPs, hence increasing the optical absorption consequently the power conversion efficiency (PCE) of the device. We obtain a PCE enhancement of 30% from 3.3% to 4.3% with incorporation of Au@PVP NPs. Moreover, the device performance with different concentration of Au@PVP NPs from 0 to 12.5 wt% has been studied, and we draw the conclusion that the performance of DSCs could be well improved through enhancing the light absorption by local surface plasmon (LSP) effect from Au@PVP NPs with an optimized concentration.

  20. Enhanced H2 uptake in solvents confined in mesoporous metal-organic framework.

    PubMed

    Clauzier, Stephanie; Ho, Linh Ngoc; Pera-Titus, Marc; Coasne, Benoit; Farrusseng, David

    2012-10-24

    Hydrogen uptake at 298 K and 30 bar in hybrid sorbents consisting of n-hexane confined in MIL-101 is found to be 22 times larger than in sole n-hexane. The enhanced solubility in MIL-101, found to be 3 times larger than in mesoporous silica of similar pore size, highlights the key roles played by surface chemistry and accessible surface area.

  1. Enhancing gas adsorption and separation capacity through ligand functionalization of microporous metal-organic framework structures.

    PubMed

    Zhao, Yonggang; Wu, Haohan; Emge, Thomas J; Gong, Qihan; Nijem, Nour; Chabal, Yves J; Kong, Lingzhu; Langreth, David C; Liu, Hui; Zeng, Heping; Li, Jing

    2011-04-26

    Hydroxyl- and amino- functionalized [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O leads to two new structures, [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O (BDC=terephthalic acid, TED=triethylenediamine, BDC-OH=2-hydroxylterephthalic acid, BDC-NH(2)=2-aminoterephthalic acid). Single-crystal X-ray diffraction and powder X-ray diffraction studies confirmed that the structures of both functionalized compounds are very similar to that of their parent structure. Compound [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O can be considered a 3D porous structure with three interlacing 1D channels, whereas both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O contain only 1D open channels as a result of functionalization of the BDC ligand by the OH and NH(2) groups. A notable decrease in surface area and pore size is thus observed in both compounds. Consequently, [Zn(BDC)(TED)(0.5)]·2DMF·0.2H(2)O takes up the highest amount of H(2) at low temperatures. Interestingly, however, both [Zn(BDC-OH)(TED)(0.5)]·1.5DMF·0.3H(2)O and [Zn(BDC-NH(2))(TED)(0.5)]·xDMF·yH(2)O show significant enhancement in CO(2) uptake at room temperature, suggesting that the strong interactions between CO(2) and the functionalized ligands, indicating that surface chemistry, rather than porosity, plays a more important role in CO(2) adsorption. A comparison of single-component CO(2), CH(4), CO, N(2), and O(2) adsorption isotherms demonstrates that the adsorption selectivity of CO(2) over other small gases is considerably enhanced through functionalization of the frameworks. Infrared absorption spectroscopic measurements and theoretical calculations are also carried out to assess the effect of functional groups on CO(2) and H(2) adsorption potentials.

  2. Enhanced Photochemical Hydrogen Production by a Molecular Diiron Catalyst Incorporated into a Metal-Organic Framework

    SciTech Connect

    Pullen, Sonja; Fei, Honghan; Orthaber, Andreas; Cohen, Seth M.; Ott, Sascha

    2013-12-04

    A molecular proton reduction catalyst [FeFe](dcbdt)(CO)6 (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal–organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)3]2+ as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)6 catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1 and 12– from undesirable charge recombination with oxidized ascorbate.

  3. Comparison of the ability of organic acids and EDTA to enhance the phytoextraction of metals from a multi-metal contaminated soil.

    PubMed

    Kim, Sung-Hyun; Lee, In-Sook

    2010-02-01

    Chelates have been shown to enhance the phytoextraction of metal from contaminated soil. In this study, we evaluated the ability of chelates to enhance the phytoextraction of metals by barnyard grass (Echinochloa crus-galli) from soils contaminated with multiple metals. The results revealed that EDTA increased the ability of barnyard grass to take up Cd, Cu and Pb, but that it resulted in increased soil leaching. Conversely, citric acid induced the removal of Cd, Cu and Pb from soil without increasing the risk of leaching. Furthermore, E.crus-galli showed no signs of phytotoxicity in response to treatment with citric acid, whereas its shoot growth decreased in response to treatment with EDTA (p < 0.05). Taken together, these results demonstrate that citric acid is a good agent for the enhancement of the phytoextraction of metals.

  4. Introduction of functionality, selection of topology, and enhancement of gas adsorption in multivariate metal-organic framework-177.

    PubMed

    Zhang, Yue-Biao; Furukawa, Hiroyasu; Ko, Nakeun; Nie, Weixuan; Park, Hye Jeong; Okajima, Satoshi; Cordova, Kyle E; Deng, Hexiang; Kim, Jaheon; Yaghi, Omar M

    2015-02-25

    Metal-organic framework-177 (MOF-177) is one of the most porous materials whose structure is composed of octahedral Zn4O(-COO)6 and triangular 1,3,5-benzenetribenzoate (BTB) units to make a three-dimensional extended network based on the qom topology. This topology violates a long-standing thesis where highly symmetric building units are expected to yield highly symmetric networks. In the case of octahedron and triangle combinations, MOFs based on pyrite (pyr) and rutile (rtl) nets were expected instead of qom. In this study, we have made 24 MOF-177 structures with different functional groups on the triangular BTB linker, having one or more functionalities. We find that the position of the functional groups on the BTB unit allows the selection for a specific net (qom, pyr, and rtl), and that mixing of functionalities (-H, -NH2, and -C4H4) is an important strategy for the incorporation of a specific functionality (-NO2) into MOF-177 where otherwise incorporation of such functionality would be difficult. Such mixing of functionalities to make multivariate MOF-177 structures leads to enhancement of hydrogen uptake by 25%.

  5. Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

    PubMed Central

    DeCoste, Jared B.; Peterson, Gregory W.

    2013-01-01

    Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials. PMID:24145623

  6. Toward Metal-Organic Framework-Based Solar Cells: Enhancing Directional Exciton Transport by Collapsing Three-Dimensional Film Structures.

    PubMed

    Goswami, Subhadip; Ma, Lin; Martinson, Alex B F; Wasielewski, Michael R; Farha, Omar K; Hupp, Joseph T

    2016-11-16

    Owing to their ability to act as light-harvesting scaffolds, porphyrin-containing metal-organic frameworks (MOFs) are in the forefront of research on the application of highly ordered molecular materials to problems in solar-energy conversion. In this work, solvent-assisted linker exchange (SALE) is performed on a pillared paddlewheel porphyrin containing MOF thin film to collapse a 3D framework to a 2D framework. The change in dimensionality of the framework is confirmed by a decrease in the film thickness, the magnitude of which is in agreement with crystallographic parameters for related bulk materials. Furthermore, NMR spectroscopy performed on the digested sample suggests a similar change in geometry is achieved in bulk MOF samples. The decreased distance between the porphyrin chromophores in the 2D MOF film compared to the 3D film results in enhanced energy transfer through the film. The extent of energy transport was probed by assembling MOF thin film where the outermost layers are palladium porphyrin (P2) units, which act as energy traps and fluorescence quenchers. Steady-state emission spectroscopy together with time-resolved emission spectroscopy indicates that excitons can travel through about 9-11 layers (porphyrin layers) in 2D films, whereas in 3D films energy transfer occurs through no more than about 6-8 layers. The results are difficult to understand if only changes in MOF interlayer spacing are considered but become much more understandable if dipole-dipole coupling distances are considered.

  7. Encapsulation of curcumin in cyclodextrin-metal organic frameworks: Dissociation of loaded CD-MOFs enhances stability of curcumin.

    PubMed

    Moussa, Zeinab; Hmadeh, Mohamad; Abiad, Mohamad G; Dib, Omar H; Patra, Digambara

    2016-12-01

    Curcumin has been successfully encapsulated in cyclodextrin-metal organic frameworks (CD-MOFs) without altering their crystallinity. The interaction between curcumin and CD-MOFs is strong through hydrogen bond type interaction between the OH group of cyclodextrin of CD-MOFs and the phenolic hydroxyl group of the curcumin. Interestingly, dissolving the curcumin loaded CD-MOFs crystals in water results in formation of a unique complex between curcumin, γCD and potassium cations. In fact, the initial interaction between curcumin and CD-MOF is crucial for the formation of the latter. This new complex formed in alkaline media at pH 11.5 has maximum absorbance at 520nm and emittance at 600nm. Most importantly, the stability of curcumin in this complex was enhanced by at least 3 orders of magnitude compared to free curcumin and curcumin:γ-CD at pH 11.5. These results suggest a promising benign system of CD-MOFs, which can be used to store and stabilize curcumin for food applications.

  8. Forming heterojunction: an effective strategy to enhance the photocatalytic efficiency of a new metal-free organic photocatalyst for water splitting.

    PubMed

    Li, Hengshuai; Hu, Haiquan; Bao, Chunjiang; Guo, Feng; Zhang, Xiaoming; Liu, Xiaobiao; Hua, Juan; Tan, Jie; Wang, Aizhu; Zhou, Hongcai; Yang, Bo; Qu, Yuanyuan; Liu, Xiangdong

    2016-07-29

    Photocatalytic water splitting is a new technology for the conversion and utilization of solar energy and has a potential prospect. One important aspect of enhancing the photocatalytic efficiency is how to improve the electron-hole separation. Up to now, there is still no ideal strategy to improve the electron-hole separation. In this article, for metal-free organic photocatalysts, we propose a good strategy- forming heterojunction, which can effectively improve the electron-hole separation. We provide a metal-free organic photocatalyst g-C12N7H3 for water splitting. The stability of g-C12N7H3 has been investigated, the X-ray diffraction spectra has been simulated. Using first-principles calculations, we have systematically studied the electronic structure, band edge alignment, and optical properties for the g-C12N7H3. The results demonstrated that g-C12N7H3 is a new organocatalyst material for water splitting. In order to enhance the photocatalytic efficiency, we provided four strategies, i.e., multilayer stacking, raising N atoms, forming g-C9N10/g-C12N7H3 heterojunction, and forming graphene/g-C12N7H3 heterojunction. Our research is expected to stimulate experimentalists to further study novel 2D metal-free organic materials as visible light photocatalysts. Our strategies, especially forming heterojunction, will substantially help to enhance the photocatalytic efficiency of metal-free organic photocatalyst.

  9. Synergistic concurrent enhancement of charge generation, dissociation, and transport in organic solar cells with plasmonic metal-carbon nanotube hybrids.

    PubMed

    Lee, Ju Min; Lim, Joonwon; Lee, Nayeun; Park, Hyung Il; Lee, Kyung Eun; Jeon, Taewoo; Nam, Soo Ah; Kim, Jehan; Shin, Jonghwa; Kim, Sang Ouk

    2015-03-04

    Plasmonic nanostructures are synthesized by decorating B- or N-doped carbon nanotubes (CNTs) with Au nanoparticles. While the plasmonic nanoparticles promote exciton generation and dissociation, the B- and N-doped CNTs enable charge-selective transport enhancement in the organic active layer. Such concurrent enhancements of all the principal energy-harvesting steps improve the device efficiency up to 9.98% for organic single-junction solar cells.

  10. A metal-organic framework/α-alumina composite with a novel geometry for enhanced adsorptive separation.

    PubMed

    Wang, Chenghong; Lee, Melanie; Liu, Xinlei; Wang, Bo; Paul Chen, J; Li, Kang

    2016-07-07

    The development of a metal-organic framework/α-alumina composite leads to a novel concept: efficient adsorption occurs within a plurality of radial micro-channels with no loss of the active adsorbents during the process. This composite can effectively remediate arsenic contaminated water producing potable water recovery, whereas the conventional fixed bed requires eight times the amount of active adsorbents to achieve a similar performance.

  11. Forming heterojunction: an effective strategy to enhance the photocatalytic efficiency of a new metal-free organic photocatalyst for water splitting

    PubMed Central

    Li, Hengshuai; Hu, Haiquan; Bao, Chunjiang; Guo, Feng; Zhang, Xiaoming; Liu, Xiaobiao; Hua, Juan; Tan, Jie; Wang, Aizhu; Zhou, Hongcai; Yang, Bo; Qu, Yuanyuan; Liu, Xiangdong

    2016-01-01

    Photocatalytic water splitting is a new technology for the conversion and utilization of solar energy and has a potential prospect. One important aspect of enhancing the photocatalytic efficiency is how to improve the electron-hole separation. Up to now, there is still no ideal strategy to improve the electron-hole separation. In this article, for metal-free organic photocatalysts, we propose a good strategy- forming heterojunction, which can effectively improve the electron-hole separation. We provide a metal-free organic photocatalyst g-C12N7H3 for water splitting. The stability of g-C12N7H3 has been investigated, the X-ray diffraction spectra has been simulated. Using first-principles calculations, we have systematically studied the electronic structure, band edge alignment, and optical properties for the g-C12N7H3. The results demonstrated that g-C12N7H3 is a new organocatalyst material for water splitting. In order to enhance the photocatalytic efficiency, we provided four strategies, i.e., multilayer stacking, raising N atoms, forming g-C9N10/g-C12N7H3 heterojunction, and forming graphene/g-C12N7H3 heterojunction. Our research is expected to stimulate experimentalists to further study novel 2D metal-free organic materials as visible light photocatalysts. Our strategies, especially forming heterojunction, will substantially help to enhance the photocatalytic efficiency of metal-free organic photocatalyst. PMID:27470223

  12. Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells.

    PubMed

    Mendes, Manuel J; Hernández, Estela; López, Esther; García-Linares, Pablo; Ramiro, Iñigo; Artacho, Irene; Antolín, Elisa; Tobías, Ignacio; Martí, Antonio; Luque, Antonio

    2013-08-30

    A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude.In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance.The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

  13. Self-organized colloidal quantum dots and metal nanoparticles for plasmon-enhanced intermediate-band solar cells

    NASA Astrophysics Data System (ADS)

    Mendes, Manuel J.; Hernández, Estela; López, Esther; García-Linares, Pablo; Ramiro, Iñigo; Artacho, Irene; Antolín, Elisa; Tobías, Ignacio; Martí, Antonio; Luque, Antonio

    2013-08-01

    A colloidal deposition technique is presented to construct long-range ordered hybrid arrays of self-assembled quantum dots and metal nanoparticles. Quantum dots are promising for novel opto-electronic devices but, in most cases, their optical transitions of interest lack sufficient light absorption to provide a significant impact in their implementation. A potential solution is to couple the dots with localized plasmons in metal nanoparticles. The extreme confinement of light in the near-field produced by the nanoparticles can potentially boost the absorption in the quantum dots by up to two orders of magnitude. In this work, light extinction measurements are employed to probe the plasmon resonance of spherical gold nanoparticles in lead sulfide colloidal quantum dots and amorphous silicon thin-films. Mie theory computations are used to analyze the experimental results and determine the absorption enhancement that can be generated by the highly intense near-field produced in the vicinity of the gold nanoparticles at their surface plasmon resonance. The results presented here are of interest for the development of plasmon-enhanced colloidal nanostructured photovoltaic materials, such as colloidal quantum dot intermediate-band solar cells.

  14. Carbon-coated rutile titanium dioxide derived from titanium-metal organic framework with enhanced sodium storage behavior

    NASA Astrophysics Data System (ADS)

    Zou, Guoqiang; Chen, Jun; Zhang, Yan; Wang, Chao; Huang, Zhaodong; Li, Simin; Liao, Hanxiao; Wang, Jufeng; Ji, Xiaobo

    2016-09-01

    Carbon-coated rutile titanium dioxide (CRT) was fabricated through an in-situ pyrolysis of titanium-based metal organic framework (Ti8O8(OH)4[O2CC6H4CO2]6) crystals. Benefiting from the Tisbnd Osbnd C skeleton structure of titanium-based metal organic framework, the CRT possesses abundant channels and micro/mesopores with the diameters ranging from 1.06 to 4.14 nm, shows larger specific surface area (245 m2 g-1) and better electronic conductivity compared with pure titanium dioxide (12.8 m2 g-1). When applied as anode material for sodium-ion batteries, the CRT electrode exhibits a high cycling performance with a reversible capacity of ∼175 mAh g-1 at 0.5 C-rate after 200 cycles, and obtains an excellent rate capability of ∼70 mAh g-1 after 2000 cycles even at a specific current of 3360 mA g-1(20 C-rate). The outstanding rate capability can be attributed to the carbon-coated structure, which may effectively prevent aggregation of the titanium dioxide nanoparticles, accelerate the mass transfer of Na+ and speed up the charge transfer rate. Considering these advantages of this particular framework structure, the CRT can serve as an alternative anode material for the industrial application of SIBs.

  15. Organic Superconductor, Made without Metals.

    ERIC Educational Resources Information Center

    Science News, 1980

    1980-01-01

    The discovery of a superconducting organic compound is reported. The compound, (TMTSF)-2, has no metal in its composition, and the author believes that it is the precursor of a family of superconducting organics. (Author/SA)

  16. Removal of organic matter and heavy metals of low concentration from wastewater via micellar-enhanced ultrafiltration: an overview

    NASA Astrophysics Data System (ADS)

    Li, F.; Li, X.; Zhang, J. D.; Peng, L.; Liu, C. Y.

    2017-01-01

    As a new and effective means of wastewater treatment, the micellar-enhanced ultrafiltration (MEUF) has been extensively studied. In this paper, MEUF was introduced from the aspects of theory basis, ultrafiltration membranes, and surfactants. Additionally, the latest research achievements in removing organic matter and heavy ions, its application in actual wastewater, and the characterization parameters of MEUF were introduced and summarized. Then, influences and mechanisms of the primary operation parameters, including surfactant concentration, pH, electrolytes, and transmembrane pressure on the performance of the MEUF process were analyzed. Finally, existing problems in the MEUF process were identified and developmental trends were predicted.

  17. Giant increase in the metal-enhanced fluorescence of organic molecules in nanoporous alumina templates and large molecule-specific red/blue-shift of the fluorescence peak.

    PubMed

    Sarkar, S; Kanchibotla, B; Nelson, J D; Edwards, J D; Anderson, J; Tepper, G C; Bandyopadhyay, S

    2014-10-08

    The fluorescence of organic fluorophore molecules is enhanced when they are placed in contact with certain metals (Al, Ag, Cu, Au, etc.) whose surface plasmon waves couple into the radiative modes of the molecules and increase the radiative efficiency. Here, we report a hitherto unknown size dependence of this metal-enhanced fluorescence (MEF) effect in the nanoscale. When the molecules are deposited in nanoporous anodic alumina films with exposed aluminum at the bottom of the pores, they form organic nanowires standing on aluminum nanoparticles whose plasmon waves have much larger amplitudes. This increases the MEF strongly, resulting in several orders of magnitude increase in the fluorescence intensity of the organic fluorophores. The increase in intensity shows an inverse superlinear dependence on nanowire diameter because the nanowires also act as plasmonic "waveguides" that concentrate the plasmons and increase the coupling of the plasmons with the radiative modes of the molecules. Furthermore, if the nanoporous template housing the nanowires has built-in electric fields due to space charges, a strong molecule-specific red- or blue-shift is induced in the fluorescence peak owing to a renormalization of the dipole moment of the molecule. This can be exploited to detect minute amounts of target molecules in a mixture using their optical signature (fluorescence) despite the presence of confounding background signals. It can result in a unique new technology for biosensing and chemical sensing.

  18. Synthesis of hierarchical porous carbon monoliths with incorporated metal-organic frameworks for enhancing volumetric based CO₂ capture capability.

    PubMed

    Qian, Dan; Lei, Cheng; Hao, Guang-Ping; Li, Wen-Cui; Lu, An-Hui

    2012-11-01

    This work aims to optimize the structural features of hierarchical porous carbon monolith (HCM) by incorporating the advantages of metal-organic frameworks (MOFs) (Cu₃(BTC)₂) to maximize the volumetric based CO₂ capture capability (CO₂ capacity in cm³ per cm³ adsorbent), which is seriously required for the practical application of CO₂ capture. The monolithic HCM was used as a matrix, in which Cu₃(BTC)₂ was in situ synthesized, to form HCM-Cu₃(BTC)₂ composites by a step-by-step impregnation and crystallization method. The resulted HCM-Cu₃(BTC)₂ composites, which retain the monolithic shape and exhibit unique hybrid structure features of both HCM and Cu₃(BTC)₂, show high CO₂ uptake of 22.7 cm³ cm⁻³ on a volumetric basis. This value is nearly as twice as the uptake of original HCM. The dynamic gas separation measurement of HCM-Cu₃(BTC)₂, using 16% (v/v) CO₂ in N₂ as feedstock, illustrates that CO₂ can be easily separated from N₂ under the ambient conditions and achieves a high separation factor for CO₂ over N₂, ranging from 67 to 100, reflecting a strongly competitive CO₂ adsorption by the composite. A facile CO₂ release can be realized by purging an argon flow through the fixed-bed adsorber at 25 °C, indicating the good regeneration ability.

  19. Removal of organic compounds and trace metals from oil sands process-affected water using zero valent iron enhanced by petroleum coke.

    PubMed

    Pourrezaei, Parastoo; Alpatova, Alla; Khosravi, Kambiz; Drzewicz, Przemysław; Chen, Yuan; Chelme-Ayala, Pamela; Gamal El-Din, Mohamed

    2014-06-15

    The oil production generates large volumes of oil sands process-affected water (OSPW), referring to the water that has been in contact with oil sands or released from tailings deposits. There are concerns about the environmental impacts of the release of OSPW because of its toxicity. Zero valent iron alone (ZVI) and in combination with petroleum coke (CZVI) were investigated as environmentally friendly treatment processes for the removal of naphthenic acids (NAs), acid-extractable fraction (AEF), fluorophore organic compounds, and trace metals from OSPW. While the application of 25 g/L ZVI to OSPW resulted in 58.4% removal of NAs in the presence of oxygen, the addition of 25 g petroleum coke (PC) as an electron conductor enhanced the NAs removal up to 90.9%. The increase in ZVI concentration enhanced the removals of NAs, AEF, and fluorophore compounds from OSPW. It was suggested that the electrons generated from the oxidation of ZVI were transferred to oxygen, resulting in the production of hydroxyl radicals and oxidation of NAs. When OSPW was de-oxygenated, the NAs removal decreased to 17.5% and 65.4% during treatment with ZVI and CZVI, respectively. The removal of metals in ZVI samples was similar to that obtained during CZVI treatment. Although an increase in ZVI concentration did not enhance the removal of metals, their concentrations effectively decreased at all ZVI loadings. The Microtox(®) bioassay with Vibrio fischeri showed a decrease in the toxicity of ZVI- and CZVI-treated OSPW. The results obtained in this study showed that the application of ZVI in combination with PC is a promising technology for OSPW treatment.

  20. Nanoscale metal-organic materials.

    PubMed

    Carné, Arnau; Carbonell, Carlos; Imaz, Inhar; Maspoch, Daniel

    2011-01-01

    Metal-organic materials are found to be a fascinating novel class of functional nanomaterials. The limitless combinations between inorganic and organic building blocks enable researchers to synthesize 0- and 1-D metal-organic discrete nanostructures with varied compositions, morphologies and sizes, fabricate 2-D metal-organic thin films and membranes, and even structure them on surfaces at the nanometre length scale. In this tutorial review, the synthetic methodologies for preparing these miniaturized materials as well as their potential properties and future applications are discussed. This review wants to offer a panoramic view of this embryonic class of nanoscale materials that will be of interest to a cross-section of researchers working in chemistry, physics, medicine, nanotechnology, materials chemistry, etc., in the next years.

  1. A simple and powerful co-delivery system based on pH-responsive metal-organic frameworks for enhanced cancer immunotherapy.

    PubMed

    Duan, Fei; Feng, Xiaochen; Yang, Xinjian; Sun, Wentong; Jin, Yi; Liu, Huifang; Ge, Kun; Li, Zhenhua; Zhang, Jinchao

    2017-04-01

    Tumor-associated antigens (TAAs)-loaded nanoparticles are able to be actively internalized by antigen-presenting cells (APCs) and have shown promising potential in cancer immunotherapy. However, current TAAs delivery strategy exhibits limitations of complicated synthesis process, low loading efficiency and inefficient CD8(+) cytotoxic T lymphocyte activation leading to unsatisfactory therapeutic effect. Thus, the construction of novel TAAs-delivery systems for enhanced cancer therapy is highly desirable. In this work, we fabricated a very simple yet powerful antigens-delivery system for cancer immunotherapy based-on pH-responsive metal-organic frameworks (MOFs) with size about 30 nm. TAAs can be loaded into MOFs in the one-pot synthesis process and released with the degradation of MOFs in the acidic environment of endo/lysosome as the result of relatively labile metal-ligand bonds. The endosomolytic nanoparticles would facilitate protein antigens escape from endo/lysosome and optimal for enhancing antigen cross-presentation. Furthermore, the introduction of immunostimulatory unmethylated cytosine-phosphate-guanine oligonucleotide (CpG) through Watson-Crick base pairing would further enhance CD8(+) cytotoxic T lymphocyte responses. We demonstrated that the method to co-delivery antigens and immunostimulatory molecules was very simple, convenient and effective and showed no obvious toxicity both in vitro and in vivo. This method gave a high antigens-loading capacity and the maximal antigen encapsulating efficiency was about 55% (w/w). Additionally, the pH-responsive co-delivery system exerted enhanced antitumor outcome (about 100% survival) in B16-OVA melanoma cancers in vivo. Furthermore, we confirmed that this high rating of therapeutic effect was attributed to the recruitment of tumor-killing immunocyte. This work demonstrates the ability of pH-responsive, endosomolytic MOFs to induce strong cellular immune responses for cancer therapy by co-delivery of CpG ODN

  2. "Clickable" metal-organic framework.

    PubMed

    Goto, Yuta; Sato, Hiroki; Shinkai, Seiji; Sada, Kazuki

    2008-11-05

    We demonstrated the metal-organic framework bearing the azide group in the organic linkers and in situ click reactions with some small alkynes. The XRPD patterns indicated that the click reaction proceeded without any decomposition of the original MOF network. Controlling the organic linkers and incorporation of the azide groups should provide the designer-made MOFs that have controlled molecular cavities with the desired steric dimensions and functionality.

  3. Organic metal neutron detector

    DOEpatents

    Butler, M.A.; Ginley, D.S.

    1984-11-21

    A device for detection of neutrons comprises: as an active neutron sensing element, a conductive organic polymer having an electrical conductivity and a cross-section for said neutrons whereby a detectable change in said conductivity is caused by impingement of said neutrons on the conductive organic polymer which is responsive to a property of said polymer which is altered by impingement of said neutrons on the polymer; and means for associating a change in said alterable property with the presence of neutrons at the location of said device.

  4. Imparting surface hydrophobicity to metal-organic frameworks using a facile solution-immersion process to enhance water stability for CO2 capture.

    PubMed

    Qian, Xukun; Sun, Fuxing; Sun, Jing; Wu, Hongyu; Xiao, Fei; Wu, Xinxin; Zhu, Guangshan

    2017-02-02

    The water sensitivity of metal-organic frameworks (MOFs) poses a critical issue for their large-scale applications. One effective method to solve this is to provide MOFs with a hydrophobic surface. Herein, we develop a facile solution-immersion process to deposit a hydrophobic coating on the MOFs' external surface without blocking their intrinsic pores. The water contact angle of the surface hydrophobic (SH) MOFs is ∼146°. The hydrophobic coating not only greatly enhances MOFs' water stability but also provides durable protection against the attack of water molecules. When exposed to liquid water, the SH samples well retain their crystal structure, morphology, surface area and CO2 uptake capacity. However, the as-synthesized (AS) samples nearly collapse and lose their porosity as well as CO2 uptake capacity after the same exposure. This study opens up a new avenue for the MOFs' application of gas sorption in the presence of water.

  5. Facile in Situ Synthesis of Silver Nanoparticles on the Surface of Metal-Organic Framework for Ultrasensitive Surface-Enhanced Raman Scattering Detection of Dopamine.

    PubMed

    Jiang, Zhongwei; Gao, Pengfei; Yang, Lin; Huang, Chengzhi; Li, Yuanfang

    2015-12-15

    Surface-enhanced Raman scattering (SERS) signals are intensively dominated by the Raman hot spots and distance between analyte molecules and metallic nanostructures. Herein, an efficient SERS substrate was developed by in situ synthesis of silver nanoparticles (AgNPs) on the surface of MIL-101 (Fe), a typical metal-organic framework (MOF). The as-prepared SERS substrate combines the numerous Raman hot spots between the high-density Ag NPs and the excellent adsorption performance of MOFs, making it an excellent SERS substrate for highly sensitive SERS detection by effectively concentrating analytes in close proximity to the Raman hot spots domains between the adjacent AgNPs. The resulting hybrid material was used for ultrasensitive SERS detection of dopamine based on the peroxidase-like activity of MIL-101 (Fe) by utilizing the enzyme-linked immunosorbent assay (ELISA) colorimetric substrate, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS) as a SERS marker. This new developed method showed good linearity in the range from 1.054 pM to 210.8 nM for dopamine with the correlation coefficient of 0.992, detection limit of approximately 0.32 pM [signal-to-noise ratio (S/N) = 3], and acceptable recoveries ranging from 99.8% to 108.0% in human urine. These results predict that the proposed SERS system may open up a new opportunity for chemical and biological assay applications.

  6. Metal-doped organic foam

    DOEpatents

    Rinde, James A.

    1982-01-01

    Organic foams having a low density and very small cell size and method for producing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  7. Near-Infrared- and Visible-Light-Enhanced Metal-Free Catalytic Degradation of Organic Pollutants over Carbon-Dot-Based Carbocatalysts Synthesized from Biomass.

    PubMed

    Wang, Hui; Zhuang, Jianqin; Velado, David; Wei, Zengyan; Matsui, Hiroshi; Zhou, Shuiqin

    2015-12-23

    Cost-efficient nanoparticle carbocatalysts composed of fluorescent carbon dots (CDs) embedded in carbon matrix were synthesized via one-step acid-assisted hydrothermal treatment (200 °C) of glucose. These as-synthesized CD-based carbocatalysts have excellent photoluminescence (PL) properties over a broad range of wavelengths and the external visible or NIR irradiation on the carbocatalysts could produce electrons to form electron-hole (e(-)-h(+)) pairs on the surface of carbocatalysts. These restant electron-hole pairs will react with the adsorbed oxidants/reducers on the surface of the CD-based carbocatalysts to produce active radicals for reduction of 4-nitrophenol and degradation of dye molecules. Moreover, the local temperature increase over CD-based carbocatalyst under NIR irradiation can enhance the electron transfer rate between the organic molecules and CD-based carbocatalysts, thus obviously increase the catalytic activity of the CD-based carbocatalyst for the reduction of 4-nitrophenol and the degradation of dye molecules. Such a type of CD-based carbocatalysts with excellent properties and highly efficient metal-free photocatalytic activities is an ideal candidate as photocatalysts for the reduction of organic pollutants under visible light and NIR radiation.

  8. Organically modified silicas on metal nanowires.

    PubMed

    Dean, Stacey L; Stapleton, Joshua J; Keating, Christine D

    2010-09-21

    Organically modified silica coatings were prepared on metal nanowires using a variety of silicon alkoxides with different functional groups (i.e., carboxyl groups, polyethylene oxide, cyano, dihydroimidazole, and hexyl linkers). Organically modified silicas were deposited onto the surface of 6-μm-long, ∼300-nm-wide, cylindrical metal nanowires in suspension by the hydrolysis and polycondensation of silicon alkoxides. Syntheses were performed at several ratios of tetraethoxysilane to an organically modified silicon alkoxide to incorporate desired functional groups into thin organosilica shells on the nanowires. These coatings were characterized using transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. All of the organically modified silicas prepared here were sufficiently porous to allow the removal of the metal nanowire cores by acid etching to form organically modified silica nanotubes. Additional functionality provided to the modified silicas as compared to unmodified silica prepared using only tetraethoxysilane precursors was demonstrated by chromate adsorption on imidazole-containing silicas and resistance to protein adsorption on polyethyleneoxide-containing silicas. Organically modified silica coatings on nanowires and other nano- and microparticles have potential application in fields such as biosensing or nanoscale therapeutics due to the enhanced properties of the silica coatings, for example, the prevention of biofouling.

  9. Effectiveness of metal-metal and metal-organic compound combinations against Plutella xylostella: implications for plant elemental defense.

    PubMed

    Jhee, Edward M; Boyd, Robert S; Eubanks, Micky D

    2006-02-01

    Plants that contain elevated foliar metal concentrations can be categorized as accumulators or, if the accumulation is extreme, hyperaccumulators. The defense hypothesis suggests that these plants may be defended against folivore attack, and recent research has indicated that metal concentrations at or below the accumulator range may be defensively effective. This experiment explored the toxicity of four metals hyper-accumulated by plants (Cd, Ni, Pb, and Zn) and asked if combinations of metals, or metals and organic chemicals, might broaden the defensive effectiveness of metals. Metals were used alone and in certain metal + metal (Zn plus Ni, Pb, or Cd) and metal + organic defensive chemical (Ni plus tannic acid, atropine, or nicotine) combinations. Artificial diet amended with these treatments was fed to larvae of the crucifer specialist herbivore Plutella xylostella. Combinations of metals and metals + organic chemicals significantly decreased survival and pupation rates, compared to single treatments, for at least some concentrations in every experiment. Effects of combinations were additive rather than synergistic or antagonistic. Because Zn enhanced the toxicity of other metals and Ni enhanced the toxicity of organic defensive chemicals, our findings suggest that the defensive effects of metals are more widespread among plants than previously believed. They also support the hypothesis that herbivore defense may have led to the evolution of metal hyper-accumulation by increasing the preexisting defensive effects of metals at accumulator levels in plants.

  10. Demonstration of InAlN/AlGaN high electron mobility transistors with an enhanced breakdown voltage by pulsed metal organic chemical vapor deposition

    SciTech Connect

    Xue, JunShuai Zhang, JinCheng; Hao, Yue

    2016-01-04

    In this work, InAlN/AlGaN heterostructures employing wider bandgap AlGaN instead of conventional GaN channel were grown on sapphire substrate by pulsed metal organic chemical vapor deposition, where the nominal Al composition in InAlN barrier and AlGaN channel were chosen to be 83% and 5%, respectively, to achieve close lattice-matched condition. An electron mobility of 511 cm{sup 2}/V s along with a sheet carrier density of 1.88 × 10{sup 13 }cm{sup −2} were revealed in the prepared heterostructures, both of which were lower compared with lattice-matched InAlN/GaN due to increased intrinsic alloy disorder scattering resulting from AlGaN channel and compressively piezoelectric polarization in barrier, respectively. While the high electron mobility transistor (HEMT) processed on these structures not only exhibited a sufficiently high drain output current density of 854 mA/mm but also demonstrated a significantly enhanced breakdown voltage of 87 V, which is twice higher than that of reported InAlN/GaN HEMT with the same device dimension, potential characteristics for high-voltage operation of GaN-based electronic devices.

  11. Ruthenium(II) Complex Incorporated UiO-67 Metal-Organic Framework Nanoparticles for Enhanced Two-Photon Fluorescence Imaging and Photodynamic Cancer Therapy.

    PubMed

    Chen, Rui; Zhang, Jinfeng; Chelora, Jipsa; Xiong, Yuan; Kershaw, Stephen V; Li, King Fai; Lo, Pik-Kwan; Cheah, Kok Wai; Rogach, Andrey L; Zapien, Juan Antonio; Lee, Chun-Sing

    2017-02-22

    Ruthenium(II) tris(bipyridyl) cationic complex (Ru(bpy)3(2+)) incorporated UiO-67 (Universitetet i Oslo) nanoscale metal-organic frameworks (NMOFs) with an average diameter of ∼92 nm were developed as theranostic nanoplatform for in vitro two-photon fluorescence imaging and photodynamic therapy. After incorporation into porous UiO-67 nanoparticles, the quantum yield, luminescence lifetime, and two-photon fluorescence intensity of Ru(bpy)3(2+) guest molecules were much improved owing to the steric confinement effect of MOF pores. Benefiting from these merits, the as-synthesized nanoparticles managed to be internalized by A549 cells while providing excellent red fluorescence in cytoplasm upon excitation with 880 nm irradiation. Photodynamic therapeutic application of the Ru(bpy)3(2+)-incorporated UiO-67 NMOFs was investigated in vitro. The Ru(bpy)3(2+)-incorporated UiO-67 NMOFs exhibited good biocompatibility without irradiation while having good cell-killing rates upon irradiation. In view of these facts, the developed Ru(bpy)3(2+)-incorporated NMOFs give a new potential pathway to achieve enhanced two-photon fluorescence imaging and photodynamic therapy.

  12. Method of stripping metals from organic solvents

    DOEpatents

    Todd, Terry A.; Law, Jack D.; Herbst, R. Scott; Romanovskiy, Valeriy N.; Smirnov, Igor V.; Babain, Vasily A.; Esimantovski, Vyatcheslav M.

    2009-02-24

    A new method to strip metals from organic solvents in a manner that allows for the recycle of the stripping agent. The method utilizes carbonate solutions of organic amines with complexants, in low concentrations, to strip metals from organic solvents. The method allows for the distillation and reuse of organic amines. The concentrated metal/complexant fraction from distillation is more amenable to immobilization than solutions resulting from current practice.

  13. Gas adsorption on metal-organic frameworks

    DOEpatents

    Willis, Richard R [Cary, IL; Low, John J. , Faheem, Syed A.; Benin, Annabelle I [Oak Forest, IL; Snurr, Randall Q [Evanston, IL; Yazaydin, Ahmet Ozgur [Evanston, IL

    2012-07-24

    The present invention involves the use of certain metal organic frameworks that have been treated with water or another metal titrant in the storage of carbon dioxide. The capacity of these frameworks is significantly increased through this treatment.

  14. Microporous Metal Organic Materials for Hydrogen Storage

    SciTech Connect

    S. G. Sankar; Jing Li; Karl Johnson

    2008-11-30

    We have examined a number of Metal Organic Framework Materials for their potential in hydrogen storage applications. Results obtained in this study may, in general, be summarized as follows: (1) We have identified a new family of porous metal organic framework materials with the compositions M (bdc) (ted){sub 0.5}, {l_brace}M = Zn or Co, bdc = biphenyl dicarboxylate and ted = triethylene diamine{r_brace} that adsorb large quantities of hydrogen ({approx}4.6 wt%) at 77 K and a hydrogen pressure of 50 atm. The modeling performed on these materials agree reasonably well with the experimental results. (2) In some instances, such as in Y{sub 2}(sdba){sub 3}, even though the modeling predicted the possibility of hydrogen adsorption (although only small quantities, {approx}1.2 wt%, 77 K, 50 atm. hydrogen), our experiments indicate that the sample does not adsorb any hydrogen. This may be related to the fact that the pores are extremely small or may be attributed to the lack of proper activation process. (3) Some samples such as Zn (tbip) (tbip = 5-tert butyl isophthalate) exhibit hysteresis characteristics in hydrogen sorption between adsorption and desorption runs. Modeling studies on this sample show good agreement with the desorption behavior. It is necessary to conduct additional studies to fully understand this behavior. (4) Molecular simulations have demonstrated the need to enhance the solid-fluid potential of interaction in order to achieve much higher adsorption amounts at room temperature. We speculate that this may be accomplished through incorporation of light transition metals, such as titanium and scandium, into the metal organic framework materials.

  15. Investigation of metal hydride nanoparticles templated in metal organic frameworks.

    SciTech Connect

    Jacobs, Benjamin W.; Herberg, Julie L.; Highley, Aaron M.; Grossman, Jeffrey; Wagner, Lucas; Bhakta, Raghu; Peaslee, D.; Allendorf, Mark D.; Liu, X.; Behrens, Richard, Jr.; Majzoub, Eric H.

    2010-11-01

    Hydrogen is proposed as an ideal carrier for storage, transport, and conversion of energy. However, its storage is a key problem in the development of hydrogen economy. Metal hydrides hold promise in effectively storing hydrogen. For this reason, metal hydrides have been the focus of intensive research. The chemical bonds in light metal hydrides are predominantly covalent, polar covalent or ionic. These bonds are often strong, resulting in high thermodynamic stability and low equilibrium hydrogen pressures. In addition, the directionality of the covalent/ionic bonds in these systems leads to large activation barriers for atomic motion, resulting in slow hydrogen sorption kinetics and limited reversibility. One method for enhancing reaction kinetics is to reduce the size of the metal hydrides to nano scale. This method exploits the short diffusion distances and constrained environment that exist in nanoscale hydride materials. In order to reduce the particle size of metal hydrides, mechanical ball milling is widely used. However, microscopic mechanisms responsible for the changes in kinetics resulting from ball milling are still being investigated. The objective of this work is to use metal organic frameworks (MOFs) as templates for the synthesis of nano-scale NaAlH4 particles, to measure the H2 desorption kinetics and thermodynamics, and to determine quantitative differences from corresponding bulk properties. Metal-organic frameworks (MOFs) offer an attractive alternative to traditional scaffolds because their ordered crystalline lattice provides a highly controlled and understandable environment. The present work demonstrates that MOFs are stable hosts for metal hydrides and their reactive precursors and that they can be used as templates to form metal hydride nanoclusters on the scale of their pores (1-2 nm). We find that using the MOF HKUST-1 as template, NaAlH4 nanoclusters as small as 8 formula units can be synthesized inside the pores. A detailed picture of

  16. Identification of a mechanism by which the methylmercury antidotes N-acetylcysteine and dimercaptopropanesulfonate enhance urinary metal excretion: transport by the renal organic anion transporter-1.

    PubMed

    Koh, Albert S; Simmons-Willis, Tracey A; Pritchard, John B; Grassl, Steven M; Ballatori, Nazzareno

    2002-10-01

    N-Acetylcysteine (NAC) and dimercaptopropanesulfonate (DMPS) are sulfhydryl-containing compounds that produce a dramatic acceleration of urinary methylmercury (MeHg) excretion in poisoned animals, but the molecular mechanism for this effect is unknown. NAC and DMPS are themselves excreted in urine in high concentrations. The present study tested the hypothesis that the complexes formed between MeHg and these anionic chelating agents are transported from blood into proximal tubule cells by the basolateral membrane organic anion transporters (Oat) 1 and Oat3. Xenopus laevis oocytes expressing rat Oat1 showed increased uptake of [(14)C]MeHg when complexed with either NAC or DMPS but not when complexed with L-cysteine, glutathione, dimercaptosuccinate, penicillamine, or gamma-glutamylcysteine. In contrast, none of these MeHg complexes were transported by Oat3-expressing oocytes. The apparent K(m) values for Oat1-mediated transport were 31 +/- 2 microM for MeHg-NAC and 9 +/- 2 microM for MeHg-DMPS, indicating that these are relatively high-affinity substrates. Oat1-mediated uptake of [(14)C]MeHg-NAC and [(14)C]MeHg-DMPS was inhibited by prototypical substrates for Oat1, including p-aminohippurate (PAH), and was trans-stimulated when oocytes were preloaded with 2 mM glutarate but not glutamate. Conversely, efflux of [(3)H]PAH from Oat1-expressing oocytes was trans-stimulated by glutarate, PAH, NAC, DMPS, MeHg-NAC, MeHg-DMPS, and a mercapturic acid, indicating that these are transported solutes. [(3)H]PAH uptake was competitively inhibited by NAC (K(i) of 2.0 +/- 0.3 mM) and DMPS (K(i) of 0.10 +/- 0.02 mM), providing further evidence that these chelating agents are substrates for Oat1. These results indicate that the MeHg antidotes NAC and DMPS and their mercaptide complexes are transported by Oat1 but are comparatively poor substrates for Oat3. This is the first molecular identification of a transport mechanism by which these antidotes may enhance urinary excretion of

  17. Metal-enhanced fluorescence of carbon nanotubes.

    PubMed

    Hong, Guosong; Tabakman, Scott M; Welsher, Kevin; Wang, Hailiang; Wang, Xinran; Dai, Hongjie

    2010-11-17

    The photoluminescence (PL) quantum yield of single-walled carbon nanotubes (SWNTs) is relatively low, with various quenching effects by metallic species reported in the literature. Here, we report the first case of metal enhanced fluorescence (MEF) of surfactant-coated carbon nanotubes on nanostructured gold substrates. The photoluminescence quantum yield of SWNTs is observed to be enhanced more than 10-fold. The dependence of fluorescence enhancement on metal-nanotube distance and on the surface plasmon resonance (SPR) of the gold substrate for various SWNT chiralities is measured to reveal the mechanism of enhancement. Surfactant-coated SWNTs in direct contact with metal exhibit strong MEF without quenching, suggesting a small quenching distance for SWNTs on the order of the van der Waals distance, beyond which the intrinsically fast nonradiative decay rate in nanotubes is little enhanced by metal. The metal enhanced fluorescence of SWNTs is attributed to radiative lifetime shortening through resonance coupling of SWNT emission to the reradiating dipolar plasmonic modes in the metal.

  18. Multiaxis sensing using metal organic frameworks

    DOEpatents

    Talin, Albert Alec; Allendorf, Mark D.; Leonard, Francois; Stavila, Vitalie

    2017-01-17

    A sensor device including a sensor substrate; and a thin film comprising a porous metal organic framework (MOF) on the substrate that presents more than one transduction mechanism when exposed to an analyte. A method including exposing a porous metal organic framework (MOF) on a substrate to an analyte; and identifying more than one transduction mechanism in response to the exposure to the analyte.

  19. Minerals with metal-organic framework structures.

    PubMed

    Huskić, Igor; Pekov, Igor V; Krivovichev, Sergey V; Friščić, Tomislav

    2016-08-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals.

  20. Enhanced phytoremediation of mixed heavy metal (mercury)-organic pollutants (trichloroethylene) with transgenic alfalfa co-expressing glutathione S-transferase and human P450 2E1.

    PubMed

    Zhang, Yuanyuan; Liu, Junhong; Zhou, Yuanming; Gong, Tingyun; Wang, Jing; Ge, Yinlin

    2013-09-15

    Soil contamination is a global environmental problem and many efforts have been made to find efficient remediation methods over the last decade. Moreover, remediation of mixed contaminated soils are more difficult. In the present study, transgenic alfalfa plants pKHCG co-expressing glutathione S-transferase (GST) and human P450 2E1 (CYP2E1) genes were used for phytoremediation of mixed mercury (Hg)-trichloroethylene (TCE) contaminants. Simultaneous expression of GST and CYP2E1 may produce a significant synergistic effect, and leads to improved resistance and accumulation to heavy metal-organic complex contaminants. Based on the tolerance and accumulation assays, pKHCG transgenic plants were more resistant to Hg/TCE complex pollutants and many folds higher in Hg/TCE-accumulation than the non-transgenic control plants in mixed contaminated soil. It is confirmed that GST and CYP2E1 co-expression may be a useful strategy to help achieve mixed heavy metal-organic pollutants phytoremediation.

  1. Synthesis of a metal-organic framework confined in periodic mesoporous silica with enhanced hydrostability as a novel fiber coating for solid-phase microextraction.

    PubMed

    Abolghasemi, Mir Mahdi; Yousefi, Vahid; Piryaei, Marzieh

    2015-04-01

    A metal-organic framework/periodic mesoporous silica (MOF-5@SBA-15) hybrid material has been prepared by using SBA-15 as a matrix. The prepared MOF-5@SBA-15 hybrid material was then deposited on a stainless-steel wire to obtain the fiber for the solid-phase microextraction of phenolic compounds. Modifications in the metal-organic framework structure have proven to improve the extraction performance of MOF/SBA-15 hybrid materials, compared to pure MOF-5 and SBA-15. Optimum conditions include an extraction temperature of 75°C, a desorption temperature of 260°C, and a salt concentration of 20% w/v. The dynamic linear range and limit of detection range from 0.1-500 and from 0.01-3.12 ng/mL, respectively. The repeatability for one fiber (n = 3), expressed as relative standard deviation, is between 4.3 and 9.6%. The method offers the advantage of being simple to use, rapid, and low cost, the thermal stability of the fiber, and high relative recovery (compared to conventional methods) represent additional attractive features.

  2. Polarization-diverse light absorption enhancement in organic photovoltaic structures with one-dimensional, long-pitch metallic gratings: Design and experiment

    NASA Astrophysics Data System (ADS)

    Liu, Yifen; Dhakal, Rabin; Dalal, Vikram; Kim, Jaeyoun

    2012-12-01

    We report the design and experimental realization of an organic photovoltaic device structure that can trap incident light in all polarization states without relying on two-dimensional, short-pitch (<400 nm) gratings. Instead, we utilized easily patternable one-dimensional, long-pitch (>1000 nm) gratings and achieved the polarization diversity through balanced allocation of the plasmonic and guided mode-based light trapping routes to different polarization states. The experimental results showed strong enhancements in light absorption in all polarization states that would translate into a 15%-25% increase in the power conversion efficiency.

  3. Metal-loaded organic scintillators for neutrino physics

    NASA Astrophysics Data System (ADS)

    Buck, Christian; Yeh, Minfang

    2016-09-01

    Organic liquid scintillators are used in many neutrino physics experiments of the past and present. In particular for low energy neutrinos when realtime and energy information are required, liquid scintillators have several advantages compared to other technologies. In many cases the organic liquid needs to be loaded with metal to enhance the neutrino signal over background events. Several metal loaded scintillators of the past suffered from chemical and optical instabilities, limiting the performance of these neutrino detectors. Different ways of metal loading are described in the article with a focus on recent techniques providing metal loaded scintillators that can be used under stable conditions for many years even in ton scale experiments. Applications of metal loaded scintillators in neutrino experiments are reviewed and the performance as well as the prospects of different scintillator types are compared.

  4. Metal-loaded organic scintillators for neutrino physics

    DOE PAGES

    Buck, Christian; Yeh, Minfang

    2016-08-03

    Organic liquid scintillators are used in many neutrino physics experiments of the past and present. In particular for low energy neutrinos when realtime and energy information are required, liquid scintillators have several advantages compared to other technologies. In many cases the organic liquid needs to be loaded with metal to enhance the neutrino signal over background events. Several metal loaded scintillators of the past suffered from chemical and optical instabilities, limiting the performance of these neutrino detectors. Different ways of metal loading are described in the article with a focus on recent techniques providing metal loaded scintillators that can bemore » used under stable conditions for many years even in ton scale experiments. Lastly, we review applications of metal loaded scintillators in neutrino experiments and compare the performance as well as the prospects of different scintillator types.« less

  5. Metal-loaded organic scintillators for neutrino physics

    SciTech Connect

    Buck, Christian; Yeh, Minfang

    2016-08-03

    Organic liquid scintillators are used in many neutrino physics experiments of the past and present. In particular for low energy neutrinos when realtime and energy information are required, liquid scintillators have several advantages compared to other technologies. In many cases the organic liquid needs to be loaded with metal to enhance the neutrino signal over background events. Several metal loaded scintillators of the past suffered from chemical and optical instabilities, limiting the performance of these neutrino detectors. Different ways of metal loading are described in the article with a focus on recent techniques providing metal loaded scintillators that can be used under stable conditions for many years even in ton scale experiments. Lastly, we review applications of metal loaded scintillators in neutrino experiments and compare the performance as well as the prospects of different scintillator types.

  6. An amide-containing metal-organic tetrahedron responding to a spin-trapping reaction in a fluorescent enhancement manner for biological imaging of NO in living cells.

    PubMed

    Wang, Jian; He, Cheng; Wu, Pengyan; Wang, Jing; Duan, Chunying

    2011-08-17

    Metal-organic polyhedra represent a unique class of functional molecular containers that display interesting molecular recognition properties and fascinating reactivity reminiscent of the natural enzymes. By incorporating a triphenylamine moiety as a bright blue emitter, a robust cerium-based tetrahedron was developed as a luminescent detector of nitronyl nitroxide (PTIO), a specific spin-labeling nitric oxide (NO) trapper. The tetrahedron encapsulates molecules of NO and PTIO within the cavity to prompt the spin-trapping reaction and transforms the normal EPR responses into a more sensitively luminescent signaling system with the limit of detection improved to 5 nM. Twelve-fold amide groups are also functionalized within the tetrahedron to modify the hydrophilic/lipophilic environment, ensuring the successful application of biological imaging in living cells.

  7. Metal-Organic Framework Templated Synthesis of Ultrasmall Catalyst Loaded ZnO/ZnCo2O4 Hollow Spheres for Enhanced Gas Sensing Properties

    PubMed Central

    Koo, Won-Tae; Choi, Seon-Jin; Jang, Ji-Soo; Kim, Il-Doo

    2017-01-01

    To achieve the rational design of nanostructures for superior gas sensors, the ultrasmall nanoparticles (NPs) loaded on ternary metal oxide (TMO) hollow spheres (HS) were synthesized by using the polystyrene (PS) sphere template and bimetallic metal-organic framework (BM-MOFs) mold. The zinc and cobalt based zeolite imidazole frameworks (BM-ZIFs) encapsulating ultrasmall Pd NPs (2–3 nm) were assembled on PS spheres at room temperature. After calcination at 450 °C, these nanoscale Pd particles were effectively infiltrated on the surface of ZnO/ZnCo2O4 HSs. In addition, the heterojunctions of Pd-ZnO, Pd-ZnCo2O4, and ZnO-ZnCo2O4 were formed on each phase. The synthesized Pd-ZnO/ZnCo2O4 HSs exhibited extremely high selectivity toward acetone gas with notable sensitivity (S = 69% to 5 ppm at 250 °C). The results demonstrate that MOF driven ultrasmall catalyst loaded TMO HSs were highly effective platform for high performance chemical gas sensors. PMID:28327599

  8. Metal-Organic Framework Templated Synthesis of Ultrasmall Catalyst Loaded ZnO/ZnCo2O4 Hollow Spheres for Enhanced Gas Sensing Properties

    NASA Astrophysics Data System (ADS)

    Koo, Won-Tae; Choi, Seon-Jin; Jang, Ji-Soo; Kim, Il-Doo

    2017-03-01

    To achieve the rational design of nanostructures for superior gas sensors, the ultrasmall nanoparticles (NPs) loaded on ternary metal oxide (TMO) hollow spheres (HS) were synthesized by using the polystyrene (PS) sphere template and bimetallic metal-organic framework (BM-MOFs) mold. The zinc and cobalt based zeolite imidazole frameworks (BM-ZIFs) encapsulating ultrasmall Pd NPs (2–3 nm) were assembled on PS spheres at room temperature. After calcination at 450 °C, these nanoscale Pd particles were effectively infiltrated on the surface of ZnO/ZnCo2O4 HSs. In addition, the heterojunctions of Pd-ZnO, Pd-ZnCo2O4, and ZnO-ZnCo2O4 were formed on each phase. The synthesized Pd-ZnO/ZnCo2O4 HSs exhibited extremely high selectivity toward acetone gas with notable sensitivity (S = 69% to 5 ppm at 250 °C). The results demonstrate that MOF driven ultrasmall catalyst loaded TMO HSs were highly effective platform for high performance chemical gas sensors.

  9. Coating to enhance metal-polymer adhesion

    SciTech Connect

    Parthasarathi, A.; Mahulikar, D.

    1996-12-31

    An ultra-thin electroplated coating has been developed to enhance adhesion of metals to polymers. The coating was developed for microelectronic packaging applications where it greatly improves adhesion of metal leadframes to plastic molding compounds. Recent tests show that the coating enhances adhesion of different metals to other types of adhesives as well and may thus have wider applicability. Results of adhesion tests with this coating, as well as its other characteristics such as corrosion resistance, are discussed. The coating is a very thin transparent electroplated coating containing zinc and chromium. It has been found to be effective on a variety of metal surfaces including copper alloys, Fe-Ni alloys, Al alloys, stainless steel, silver, nickel, Pd/Ni and Ni-Sn. Contact resistance measurements show that the coating has little or no effect on electrical resistivity.

  10. Magnetism in metal-organic capsules

    SciTech Connect

    Atwood, Jerry L.; Brechin, Euan K; Dalgarno, Scott J.; Inglis, Ross; Jones, Leigh F.; Mossine, Andrew; Paterson, Martin J.; Power, Nicholas P.; Teat, Simon J.

    2010-01-07

    Nickel and cobalt seamed metal-organic capsules have been isolated and studied using structural, magnetic and computational approaches. Antiferromagnetic exchange in the Ni capsule results from coordination environments enforced by the capsule framework.

  11. Near-infrared emitting ytterbium metal-organic frameworks with tunable excitation properties.

    PubMed

    White, Kiley A; Chengelis, Demetra A; Zeller, Matthias; Geib, Steven J; Szakos, Jessica; Petoud, Stéphane; Rosi, Nathaniel L

    2009-08-14

    The design of metal-organic frameworks (MOFs) incorporating near-infrared emitting ytterbium cations and organic sensitizers allows for the preparation of new materials with tunable and enhanced photophysical properties.

  12. Minerals with metal-organic framework structures

    PubMed Central

    Huskić, Igor; Pekov, Igor V.; Krivovichev, Sergey V.; Friščić, Tomislav

    2016-01-01

    Metal-organic frameworks (MOFs) are an increasingly important family of advanced materials based on open, nanometer-scale metal-organic architectures, whose design and synthesis are based on the directed assembly of carefully designed subunits. We now demonstrate an unexpected link between mineralogy and MOF chemistry by discovering that the rare organic minerals stepanovite and zhemchuzhnikovite exhibit structures found in well-established magnetic and proton-conducting metal oxalate MOFs. Structures of stepanovite and zhemchuzhnikovite, exhibiting almost nanometer-wide and guest-filled apertures and channels, respectively, change the perspective of MOFs as exclusively artificial materials and represent, so far, unique examples of open framework architectures in organic minerals. PMID:27532051

  13. Enhanced selective hydrogen desorption from metals

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1983-04-01

    The thermal desorption of hydrogen isotopes from a metal is usually a second order process the rate for which becomes asymptotically slow. We present a method for enhancing the desorption rate of one particular isotope by maintaining a constant pressure of another molecular species. This results in an effective first order desorption and concommitant exponential decay of the concentration of the selected isotope. Data is presented for the enhanced desorption of deuterium from a Zr--Al getter. The results agree well with a theoretical model, which is discussed. This enhanced desorption method should be particularly useful for tritium operation in the tokamak fusion test reactor.

  14. Enhanced selective hydrogen desorption from metals

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1982-12-01

    The thermal desorption of hydrogen isotopes from a metal is usually a second order process, the rate for which becomes asymptotically slow. We present a method for enhancing the desorption rate of one particular isotope by maintaining a constant pressure of another molecular species. This results in an effective first order desorption and concomitant exponential decay of the concentration of the selected isotope. Data are presented for the enhanced desorption of deuterium from a Zr-Al getter. The results agree well with a theoretical model, which is discussed. This enhanced desorption method should be particularly useful for tritium operation in the Tokamak Fusion Test Reactor.

  15. Self-exfoliated metal organic nanosheets via hydrolytic unfolding of metal organic polyhedra.

    PubMed

    Banerjee, Rahul; Garai, Bikash; Mallick, Arjit; Das, Anuja; Mukherjee, Rabibrata

    2017-04-04

    Few layer thick metal-organic nanosheets have been synthesized using water-assisted solid state transformation through a combined top-down and bottom-up approach. The metal-organic polyhedra (MOPs) convert into metal-organic frameworks (MOFs) which subsequently self-exfoliate into few layered metal-organic nanosheets. These MOP crystals experience a hydrophobicity gradient with the inner surface during contact with water because of the existence of hydrophobic spikes on their outer surface. When the amount of water available for interaction is higher, the resultant layers are not stacked to form bulk materials; instead few layered nanosheets with high uniformity were obtained in high yield. The phenomenon has resulted high yield production of uniformly distributed layered metal-organic nanosheets from three different MOPs, showing its general adaptability.

  16. Emerging Multifunctional Metal-Organic Framework Materials.

    PubMed

    Li, Bin; Wen, Hui-Min; Cui, Yuanjing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2016-10-01

    Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting type of solid crystalline materials that can be straightforwardly self-assembled through the coordination of metal ions/clusters with organic linkers. Owing to the modular nature and mild conditions of MOF synthesis, the porosities of MOF materials can be systematically tuned by judicious selection of molecular building blocks, and a variety of functional sites/groups can be introduced into metal ions/clusters, organic linkers, or pore spaces through pre-designing or post-synthetic approaches. These unique advantages enable MOFs to be used as a highly versatile and tunable platform for exploring multifunctional MOF materials. Here, the bright potential of MOF materials as emerging multifunctional materials is highlighted in some of the most important applications for gas storage and separation, optical, electric and magnetic materials, chemical sensing, catalysis, and biomedicine.

  17. Methane storage in metal-organic frameworks.

    PubMed

    He, Yabing; Zhou, Wei; Qian, Guodong; Chen, Banglin

    2014-08-21

    Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodology and the emerging porous metal-organic frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-organic frameworks for methane storage.

  18. Field Enhancement using Noble Metal Structures

    NASA Astrophysics Data System (ADS)

    Liu, Benliang

    Resonance may be one of the most fundamental rules of nature. Electromagnetic resonance at nanometer scale could produce a giant field enhancement at optical frequency, providing a way to measure and control the process of atoms and molecules at single molecule scale. For example, the giant field enhancement would provide single molecule sensitivity for Raman scattering, which provides unique tools in measuring the quantity in extremely low concentration. In addition, light-emitting diodes could have high brightness but low input power that would be revolutionary in the optoelectronic industry. Although light enhancement is promising in several key technology areas, there are several challenges remain to be tackled. In particular, since the field enhancement is so strongly geometry dependent that slight modification of the geometry can lead to large variations in the outcome, a thorough understanding in how the geometry of the structure affects the field enhancement and creating proper methods to fabricate these structures reproducibly is of most importance. This thesis is devoted to design, fabrication and characterization of field enhancement generated on the surface of noble metals such as silver or gold with 1D structure. The s-polarized field enhancement arising from one-dimensional metal gratings is designed and optimized by using Rigorous Coupling Wave Analysis (RCWA). After optimization, the strongest enhancement factor is found to be 9.7 for 514nm wavelength light. The theoretical results arc confirmed by angle-dependent reflectivity measurements and the experimental results are found to support the theory. A novel single slit structure employing surface plasmon polaritons (SPPs) for enhancing the electric field is studied. SPPs are first generated on a 50 nm thick metal film using attenuated total reflection coupling, and they are subsequently coupled to the cavity mode induced by the single slit. As a result, the field enhancement is found at least 3

  19. Fluorescence enhancement of photoswitchable metal ion sensors

    NASA Astrophysics Data System (ADS)

    Sylvia, Georgina; Heng, Sabrina; Abell, Andrew D.

    2016-12-01

    Spiropyran-based fluorescence sensors are an ideal target for intracellular metal ion sensing, due to their biocompatibility, red emission frequency and photo-controlled reversible analyte binding for continuous signal monitoring. However, increasing the brightness of spiropyran-based sensors would extend their sensing capability for live-cell imaging. In this work we look to enhance the fluorescence of spiropyran-based sensors, by incorporating an additional fluorophore into the sensor design. We report a 5-membered monoazacrown bearing spiropyran with metal ion specificity, modified to incorporate the pyrene fluorophore. The effect of N-indole pyrene modification on the behavior of the spiropyran molecule is explored, with absorbance and fluorescence emission characterization. This first generation sensor provides an insight into fluorescence-enhancement of spiropyran molecules.

  20. Optical absorption enhancement of hybrid-plasmonic-based metal-semiconductor-metal photodetector incorporating metal nanogratings and embedded metal nanoparticles.

    PubMed

    Tan, Chee Leong; Karar, Ayman; Alameh, Kamal; Lee, Yong Tak

    2013-01-28

    We propose and numerically demonstrate a high absorption hybrid-plasmonic-based metal semiconductor metal photodetector (MSM-PD) comprising metal nanogratings, a subwavelength slit and amorphous silicon or germanium embedded metal nanoparticles (NPs). Simulation results show that by optimizing the metal nanograting parameters, the subwavelength slit and the embedded metal NPs, a 1.3 order of magnitude increase in electric field is attained, leading to 28-fold absorption enhancement, in comparison with conventional MSM-PD structures. This is 3.5 times better than the absorption of surface plasmon polariton (SPP) based MSM-PD structures employing metal nanogratings and a subwavelength slit. This absorption enhancement is due to the ability of the embedded metal NPs to enhance their optical absorption and scattering properties through light-stimulated resonance aided by the conduction electrons of the NPs.

  1. Recent Developments of Metal and Metal Oxide Nanocatalysts in Organic Synthesis.

    PubMed

    Makawana, Jigar A; Sangani, Chetan B; Yao, Yong-Fang; Duan, Yong-Tao; Lv, Peng-Cheng; Zhu, Hai-Liang

    2016-01-01

    Recently, various nanomaterials have been used in many organic transformations as efficient catalysts. The development of new catalysts by nanoscale design has emerged as a fertile field for research and innovation. The ability of nanotechnology to enhance catalytic activity opens the potential to replace expensive catalysts with lower amounts of inexpensive nanocatalysts. Besides, development of efficient and environmentally friendly synthetic methodologies for the synthesis of compound libraries of medicinal scaffolds is an attractive area of research in both academic and pharmaceutical industry. According to above reports and needs, this review deals with applications of nanoparticles as catalysts in various organic syntheses. We detail the topic of organic transformations using nanoparticles: Metal Nanoparticles and Metal Oxide Nanoparticles. In the latter part, different Metal Oxide Nanoparticles, such as ZnO Nanoparticle, TiO2 Nanoparticle, and CuO Nanoparticle are discussed.

  2. Enhanced transmittance of metallic film with nanoaperture array

    NASA Astrophysics Data System (ADS)

    Xu, Ming; Ou, Xia-Li; Zhang, Xu-Lin; Liu, Yu-Shan; Gao, Qiang

    2016-09-01

    Metallic film as an indium tin oxide alternative, which shows excellent mechanical flexibility and high conductivity, has the ideal physical properties for flexible organic solar cells (OSCs). However, a bottleneck of metallic film was a lack of transmittance that limits the application in OSCs. We have demonstrated a nanoaperture metallic film fabricated by a template striping method, which can overcome the above-mentioned bottleneck. This metallic film has a random nanoaperture array. The size and shape of the nanoaperture were dependent on master templates. This metallic film with nanoaperture array is not only able to show high conductivity but also possesses tunable localized surface plasmon (LSP) resonance as well. The LSP could be coupled with dipole mode in nanostructure, which can account for the transmission enhancement and efficiently increase the light absorption of active layer in the OSCs. Moreover, this metallic film with nanoaperture array will exhibit particular advantage in flexible OSCs because the backing layer itself is a flexible substrate. The nanoaperture metallic film fabricated by this method as an electrode was a good choice for OSCs.

  3. Superhydrophobic perfluorinated metal-organic frameworks.

    PubMed

    Chen, Teng-Hao; Popov, Ilya; Zenasni, Oussama; Daugulis, Olafs; Miljanić, Ognjen Š

    2013-08-07

    Three perfluorinated Cu-based metal-organic frameworks (MOFs) were prepared starting from extensively fluorinated biphenyl-based ligands accessed via C-H functionalization. These new materials are highly hydrophobic: with water contact angles of up to 151 ± 1°, they are among the most water-repellent MOFs ever reported.

  4. Mechanism of metal cationization in organic SIMS

    NASA Astrophysics Data System (ADS)

    Wojciechowski, I.; Delcorte, A.; Gonze, X.; Bertrand, P.

    2001-09-01

    A mechanism for metal cationization of phenyl group containing hydrocarbons is discussed. Intact molecules and their fragments are emitted from a thin organic layer covering a metal surface bombarded by fast ions. It is shown that the process of associative ionization of a neutral hydrocarbon molecule and a neutral excited metal atom, occurring above the surface, may contribute to the yield of cationized molecules. To demonstrate this we have calculated the potential energy curves for the model system C 6H 6+Me (Me=Ag, Cu, Au) making use of the density functional theory. The initial states of the metal atoms approaching the benzene ring along the C 6 symmetry axis were set as the ground, ionic, and excited in ( n-1)d 9ns 2 electronic configuration.

  5. Multifunctional Metal-Organic Frameworks for Photocatalysis.

    PubMed

    Wang, Sibo; Wang, Xinchen

    2015-07-01

    Metal-organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO2 reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world-wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF-involved solar-to-chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co-catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated.

  6. Adsorption of volatile organic compounds in porous metal-organic frameworks functionalized by polyoxometalates

    NASA Astrophysics Data System (ADS)

    Ma, Feng-Ji; Liu, Shu-Xia; Liang, Da-Dong; Ren, Guo-Jian; Wei, Feng; Chen, Ya-Guang; Su, Zhong-Min

    2011-11-01

    The functionalization of porous metal-organic frameworks (Cu 3( BTC) 2) was achieved by incorporating Keggin-type polyoxometalates (POMs), and further optimized via alkali metal ion-exchange. In addition to thermal gravimetric analysis, IR, single-crystal X-ray diffraction, and powder X-ray diffraction, the adsorption properties were characterized by N 2 and volatile organic compounds (VOCs) adsorption measurements, including short-chain alcohols ( C<4), cyclohexane, benzene, and toluene. The adsorption enthalpies estimated by the modified Clausius-Clapeyron equation provided insight into the impact of POMs and alkali metal cations on the adsorption of VOCs. The introduction of POMs not only improved the stability, but also brought the increase of adsorption capacity by strengthening the interaction with gas molecules. Furthermore, the exchanged alkali metal cations acted as active sites to interact with adsorbates and enhanced the adsorption of VOCs.

  7. Mechanical Alloying of Metal-Organic Frameworks.

    PubMed

    Panda, Tamas; Horike, Satoshi; Hagi, Keisuke; Ogiwara, Naoki; Kadota, Kentaro; Itakura, Tomoya; Tsujimoto, Masahiko; Kitagawa, Susumu

    2017-02-20

    The solvent-free mechanical milling process for two distinct metal-organic framework (MOF) crystals induced the formation of a solid solution, which is not feasible by conventional solution-based syntheses. X-ray and STEM-EDX studies revealed that performing mechanical milling under an Ar atmosphere promotes the high diffusivity of each metal ion in an amorphous solid matrix; the amorphous state turns into the porous crystalline structure by vapor exposure treatment to form a new phase of a MOF solid solution.

  8. Metal interactions in carcinogenesis: enhancement, inhibition

    PubMed Central

    Nordberg, Gunnar F.; Andersen, Ole

    1981-01-01

    Metals constitute a fundamentally important part of the total human environment. Since human exposure often involves complex mixtures of metal compounds and, possibly, organic compounds which may be carcinogenic per se, interactions between these compounds may add significantly to human cancer risk. Our present knowledge about these kinds of interactions is very limited. The best investigated area is benzo(a)pyrene (BP)-metal oxide particle interactions in respiratory carcinogenesis in the hamster. Metal oxide particles were also shown to modify the carcinogenic effect of nitrosamines. Several reports describe experiments in which selenium compounds exerted a generally anticarcinogenic and antimutagenic activity. Inorganic arsenic compounds, which are accepted to be carcinogenic in man, have so far been negative in animal experiments except for one recent suggested report. Several authors have, however, suggested that these compounds may act as cocarcinogens due to their inhibition of DNA repair, although animal experiments to demonstrate a cocarcinogenic effect of arsenic compounds have been negative so far, except for one preliminary report. The concentration of zinc in the diet seemed to influence both transplanted tumor growth and the carcinogenicity of several organic compounds, and the possibility of a correlation between dietary zinc and certain cancer forms in man has been suggested. Protection against development of Leydigiomas usually induced by cadmium injection was afforded by simultaneous injection of zinc salts. Nickel carcinogenesis has been reported to be antagonized by manganese, and synergism between Ni and organic carcinogens, e.g. BP, has been demonstrated. There is no firm evidence that lead may be a cocarcinogen, although some limited experimental evidence is available. Oxidizing agents have been demonstrated to increase, and reducing agents to antagonize, the mutagenic effect of chromium compounds in vitro. The content of carcinogenic and

  9. Silver nanorod structures for metal enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Badshah, Mohsin Ali; Lu, Xun; Ju, Jonghyun; Kim, Seok-min

    2016-09-01

    Fluorescence based detection is a commonly used methodology in biotechnology and medical diagnostics. Metalenhanced fluorescence (MEF) becomes a promising strategy to improve the sensitivity of fluorescence detection, where fluorophores coupling with surface plasmon on metallic structures results fluorescence enhancement. To apply the MEF methodology in real medical diagnostics, especially for protein or DNA microarray detection, a large area (e.g., slide glass, 75 × 25 mm2) with uniform metallic nanostructures is required. In this study, we fabricated a large area MEF substrates using oblique angle deposition (OAD), which is a single step, inexpensive large area fabrication method of nanostructures. To optimize the morphological effect, Ag-nanorods with various lengths were fabricated on the conventional slide glass substrates. Streptavidin-Cy5 dissolved in buffer solution with different concentration (100ng/ml 100μg/ml) were applied to MEF substrates using a pipette, and the fluorescence signals were measured. The enhancement factor increased with the increase in length of Ag-nanorods and maximum enhancement factor 91x was obtained from Ag-nanorods 750nm length compare to bare glass due to higher surface Plasmon effect.

  10. Spectroscopical properties of organic/metal nanohybrids.

    PubMed

    Dellepiane, Giovanna; Cuniberti, Carla; Alloisio, Marina; Demartini, Anna

    2010-03-28

    The aim of our work was to prepare stable nanohybrids of controlled size and shape consisting of a noble metal core decorated with polydiacetylenes (PDAs). Due to the combination of the outstanding linear and nonlinear optical properties of the polydiacetylenic chains with the electromagnetic field-enhancing capability of metal nanostructures, these novel composites can find potential application in different fields. In particular, the different colours exhibited by PDAs in relation to the chemical nature of the monomer and the polymerization procedure, as well as in response to environmental perturbations, make them excellent materials for the fabrication of sensing devices. On the basis of our previous work on PDA self-assembled monolayers on flat metal surfaces, the results of which are briefly reported, we prepared differently-shaped gold and silver nanocores (spheres, cages) coated with various diacetylenic monomers having end-groups able to firmly anchor to the metal surface. These nanohybrids exhibit in aqueous colloidal solution an enhanced photochemical polymerization monitored step by step with UV-Vis and SERS techniques. It is shown that in these stable assemblies an intra-particle polymerization takes place and that the dominant PDA form is conditioned by the core size and geometry. While the nanoparticles are SERS active in the visible, the nanocages should be excellent SERS substrates from the visible to the near infrared regions.

  11. Metal and metal oxide nanoparticle synthesis from metal organic frameworks (MOFs): finding the border of metal and metal oxides.

    PubMed

    Das, Raja; Pachfule, Pradip; Banerjee, Rahul; Poddar, Pankaj

    2012-01-21

    Herein, for the first time, we report a generalized strategy for the successful synthesis of highly crystalline metal and metal oxide nanoparticles embedded in a carbon matrix by the controlled thermolysis of metal organic frameworks (MOFs). The rationalized synthesis strategy of a broad range of metal and metal oxides nanoparticles, such as Cu/CuO, Co/Co(3)O(4), ZnO, Mn(2)O(3), MgO and CdS/CdO, by thermolysis of MOFs demonstrates for the first time that metal ions with a reduction potential of -0.27 volts or higher present in MOFs always form pure metal nanoparticles during thermolysis in N(2), whereas metal ions with a reduction potential lower than -0.27 volts form metal oxide nanoparticles during thermolysis in N(2). Another point of interest is the fact that we have found a unique relationship between the nanoparticle size and the distance between the secondary building units inside the MOF precursors. Interestingly, the crystallinity of the carbon matrix was also found to be greatly influenced by the environment (N(2) and air) during thermolysis. Moreover, these nanoparticles dispersed in a carbon matrix showed promising H(2) and CO(2) adsorption properties depending on the environment used for the thermolysis of MOFs.

  12. Metallization with generic metallo-organic inks

    NASA Technical Reports Server (NTRS)

    Vest, G. M.

    1983-01-01

    The use and fabrication of metallo-organic films are discussed. Metallo-organic compounds are ones in which a metal is linked to a long chain carbon ligand through a hetero atom such as O, S, N, P or As. Films formed by the thermal decomposition of these metallo-organics are called MOD films. In order that the products of decomposition contain only CO2, H2O, and in rare cases nitrogen compounds, and to avoid S containing products, the use of a set of metallo-organic compounds for ink fabrication where the linking hetero atom was oxygen was pioneered. These links were made from commercially available carboxylates, or synthesized from commonly available reagents. The processing is described and the molecular design criteria are given. The particular carboxylates or amine carboxylates selected were the octoates or neodecanoates, and they are described.

  13. Purification of metal-organic framework materials

    SciTech Connect

    Farha, Omar K.; Hupp, Joseph T.

    2012-12-04

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  14. Porosity in metal-organic framework glasses.

    PubMed

    Thornton, A W; Jelfs, K E; Konstas, K; Doherty, C M; Hill, A J; Cheetham, A K; Bennett, T D

    2016-03-07

    The porosity of a glass formed by melt-quenching a metal-organic framework, has been characterized by positron annihilation lifetime spectroscopy. The results reveal porosity intermediate between the related open and dense crystalline frameworks ZIF-4 and ZIF-zni. A structural model for the glass was constructed using an amorphous polymerization algorithm, providing additional insight into the gas-inaccessible nature of porosity and the possible applications of hybrid glasses.

  15. Purification of metal-organic framework materials

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.

    2015-06-30

    A method of purification of a solid mixture of a metal-organic framework (MOF) material and an unwanted second material by disposing the solid mixture in a liquid separation medium having a density that lies between those of the wanted MOF material and the unwanted material, whereby the solid mixture separates by density differences into a fraction of wanted MOF material and another fraction of unwanted material.

  16. Cascade reactions catalyzed by metal organic frameworks.

    PubMed

    Dhakshinamoorthy, Amarajothi; Garcia, Hermenegildo

    2014-09-01

    Cascade or tandem reactions where two or more individual reactions are carried out in one pot constitute a clear example of process intensification, targeting the maximization of spatial and temporal productivity with mobilization of minimum resources. In the case of catalytic reactions, cascade processes require bi-/multifunctional catalysts that contain different classes of active sites. Herein, we show that the features and properties of metal-organic frameworks (MOFs) make these solids very appropriate materials for the development of catalysts for cascade reactions. Due to composition and structure, MOFs can incorporate different types of sites at the metal nodes, organic linkers, or at the empty internal pores, allowing the flexible design and synthesis of multifunctional catalysts. After some introductory sections on the relevance of cascade reactions from the point of view of competitiveness, sustainability, and environmental friendliness, the main part of the text provides a comprehensive review of the literature reporting the use of MOFs as heterogeneous catalysts for cascade reactions including those that combine in different ways acid/base, oxidation/reduction, and metal-organic centers. The final section summarizes the current state of the art, indicating that the development of a first commercial synthesis of a high-added-value fine chemical will be a crucial milestone in this area.

  17. Metal Vinylidenes as Catalytic Species in Organic Reactions

    PubMed Central

    McClory, Andrew

    2008-01-01

    Organic vinylidene species have found limited use in organic synthesis due to their inaccessibility. In contrast, metal vinylidenes are much more stable, and may be readily accessed through transition metal activation of terminal alkynes. These electrophilic species may be trapped by a number of nucleophiles. Additionally, metal vinylidenes can participate in pericyclic reactions and processes involving migration of a metal ligand to the vinylidene species. This review addresses the reactions and applications of metal vinylidenes in organic synthesis. PMID:18172846

  18. Impact of metals on the biodegradation of organic pollutants.

    PubMed Central

    Sandrin, Todd R; Maier, Raina M

    2003-01-01

    Forty percent of hazardous waste sites in the United States are co-contaminated with organic and metal pollutants. Data from both aerobic and anaerobic systems demonstrate that biodegradation of the organic component can be reduced by metal toxicity. Metal bioavailability, determined primarily by medium composition/soil type and pH, governs the extent to which metals affect biodegradation. Failure to consider bioavailability rather than total metal likely accounts for much of the enormous variability among reports of inhibitory concentrations of metals. Metals appear to affect organic biodegradation through impacting both the physiology and ecology of organic degrading microorganisms. Recent approaches to increasing organic biodegradation in the presence of metals involve reduction of metal bioavailability and include the use of metal-resistant bacteria, treatment additives, and clay minerals. The addition of divalent cations and adjustment of pH are additional strategies currently under investigation. PMID:12826480

  19. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    PubMed Central

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy; Schaef, Herbert T.; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-01-01

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model. PMID:27302196

  20. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    NASA Astrophysics Data System (ADS)

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy; Schaef, Herbert T.; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-06-01

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  1. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids.

    PubMed

    Nandasiri, Manjula I; Liu, Jian; McGrail, B Peter; Jenks, Jeromy; Schaef, Herbert T; Shutthanandan, Vaithiyalingam; Nie, Zimin; Martin, Paul F; Nune, Satish K

    2016-06-15

    Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.

  2. Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids

    SciTech Connect

    Nandasiri, Manjula I.; Liu, Jian; McGrail, B. Peter; Jenks, Jeromy WJ; Schaef, Herbert T.; Shutthanandan, V.; Nie, Zimin; Martin, Paul F.; Nune, Satish K.

    2016-06-15

    Metal organic heat carriers (MOHCs) are recently developed nanofluids containing metal organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. MOHCs utilize the MOF properties to improve the thermo-physical properties of base fluids. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC containing MIL-101(Cr)/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nano MIL-101(Cr) and the properties depend on the amount of GO added. Powder X-ray diffraction (PXRD) confirmed the preserved crystallinity of MIL-101(Cr) in all nanocomposites with the absence of any unreacted GO. Scanning electron microscopy images confirmed the presence of near spherical MIL-101(Cr) nanoparticles in the range of 40-80 nm in diameter. MOHC nanofluids containing MIL-101(Cr)/GO in methanol exhibited significant enhancement in the thermal conductivity (by approxi-mately 50%) relative to that of the intrinsic nano MIL-101(Cr) in methanol. The thermal conductivity of base fluid (methanol) was enhanced by about 20 %. The enhancement in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to graphene oxide functionalization is explained using a classical Maxwell model.

  3. Metal-organic frameworks as selectivity regulators for hydrogenation reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Meiting; Yuan, Kuo; Wang, Yun; Li, Guodong; Guo, Jun; Gu, Lin; Hu, Wenping; Zhao, Huijun; Tang, Zhiyong

    2016-11-01

    Owing to the limited availability of natural sources, the widespread demand of the flavouring, perfume and pharmaceutical industries for unsaturated alcohols is met by producing them from α,β-unsaturated aldehydes, through the selective hydrogenation of the carbon-oxygen group (in preference to the carbon-carbon group). However, developing effective catalysts for this transformation is challenging, because hydrogenation of the carbon-carbon group is thermodynamically favoured. This difficulty is particularly relevant for one major category of heterogeneous catalyst: metal nanoparticles supported on metal oxides. These systems are generally incapable of significantly enhancing the selectivity towards thermodynamically unfavoured reactions, because only the edges of nanoparticles that are in direct contact with the metal-oxide support possess selective catalytic properties; most of the exposed nanoparticle surfaces do not. This has inspired the use of metal-organic frameworks (MOFs) to encapsulate metal nanoparticles within their layers or inside their channels, to influence the activity of the entire nanoparticle surface while maintaining efficient reactant and product transport owing to the porous nature of the material. Here we show that MOFs can also serve as effective selectivity regulators for the hydrogenation of α,β-unsaturated aldehydes. Sandwiching platinum nanoparticles between an inner core and an outer shell composed of an MOF with metal nodes of Fe3+, Cr3+ or both (known as MIL-101; refs 19, 20, 21) results in stable catalysts that convert a range of α,β-unsaturated aldehydes with high efficiency and with significantly enhanced selectivity towards unsaturated alcohols. Calculations reveal that preferential interaction of MOF metal sites with the carbon-oxygen rather than the carbon-carbon group renders hydrogenation of the former by the embedded platinum nanoparticles a thermodynamically favoured reaction. We anticipate that our basic design

  4. Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Bloch, Witold M.; Burgun, Alexandre; Coghlan, Campbell J.; Lee, Richmond; Coote, Michelle L.; Doonan, Christian J.; Sumby, Christopher J.

    2014-10-01

    Post-synthetic metallation is employed strategically to imbue metal-organic frameworks (MOFs) with enhanced performance characteristics. However, obtaining precise structural information for metal-centred reactions that take place within the pores of these materials has remained an elusive goal, because of issues with high symmetry in certain MOFs, lower initial crystallinity for some chemically robust MOFs, and the reduction in crystallinity that can result from carrying out post-synthetic reactions on parent crystals. Here, we report a new three-dimensional MOF possessing pore cavities that are lined with vacant di-pyrazole groups poised for post-synthetic metallation. These metallations occur quantitatively without appreciable loss of crystallinity, thereby enabling examination of the products by single-crystal X-ray diffraction. To illustrate the potential of this platform to garner fundamental insight into metal-catalysed reactions in porous solids we use single-crystal X-ray diffraction studies to structurally elucidate the reaction products of consecutive oxidative addition and methyl migration steps that occur within the pores of the Rh-metallated MOF, 1·[Rh(CO)2][Rh(CO)2Cl2].

  5. DEMONSTRATION BULLETIN: METAL-ENHANCED ABIOTIC DEGRADATION TECHNOLOGY - ENVIROMETAL TECHNOLOGIES, INC.

    EPA Science Inventory

    EnviroMetal Technologies, Inc. (ETI), of Guelph, ON, Canada, has developed the metal-enhanced abiotic degradation technology to treat halogenated volatile organic compounds (VOC) in water. A reactive, zero-valent, granular iron medium causes reductive dehalogenation of VOCs yield...

  6. Advanced Organic Ligands for Protecting Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Yu, Jonathan Ka-Wing

    Organic monolayer protected metal nanoparticles have been utilized in many different fields such as catalysis, drug delivery, and sensor chemistry. However, these nanomaterials are prone to increase in size consequently losing its function at the nanoscale. The stability these nanoparticles have been a great interest of research. This thesis focuses on the synthesis of a novel cross-linkable ligand for the protection of metal nanoparticles. Chapter 1 reviews key concepts of nanoparticles, its usefulness in applications, some of the stabilizing strategies employed, and the scope of the thesis project. Chapter 2 describes the synthetic attempts and optimization of the novel cross-linkable ligand. In addition, its characterization data is also included. Section 2.8 also highlights another fully synthesized novel hydrophobic ligand. Chapter 3 contains the summary of the work and closing remarks. Future works is also included to describe the prospects of the synthesis of the novel ligand. Chapter 4 entails the experimental data and supplementary information.

  7. Enhanced proton conductivity of Nafion hybrid membrane under different humidities by incorporating metal-organic frameworks with high phytic acid loading.

    PubMed

    Li, Zhen; He, Guangwei; Zhang, Bei; Cao, Ying; Wu, Hong; Jiang, Zhongyi; Tiantian, Zhou

    2014-06-25

    In this study, phytic acid (myo-inositol hexaphosphonic acid) was first immobilized by MIL101 via vacuum-assisted impregnation method. The obtained phytic@MIL101 was then utilized as a novel filler to incorporate into Nafion to fabricate hybrid proton exchange membrane for application in PEMFC under different relative humidities (RHs), especially under low RHs. High loading and uniform dispersion of phytic acid in MIL 101(Cr) were achieved as demonstrated by ICP, FT-IR, XPS, and EDS-mapping. The phytic@MIL101 was dispersed homogeneously in the Nafion matrix when the filler content was less than 12%. Hybrid membranes were evaluated by proton conductivity, mechanical property, thermal stability, and so forth. Remarkably, the Nafion/phytic@MIL hybrid membranes showed high proton conductivity at different RHs, especially under low RHs, which was up to 0.0608 S cm(-1) and 7.63 × 10(-4) S cm(-1) at 57.4% RH and 10.5% RH (2.8 and 11.0 times higher than that of pristine membrane), respectively. Moreover, the mechanical property of Nafion/phtic@MIL hybrid membranes was substantially enhanced and the thermal stability of membranes was well preserved.

  8. Dependence of metal-enhanced fluorescence on surface roughness

    NASA Astrophysics Data System (ADS)

    François, Alexandre; Sciacca, Beniamino; Zuber, Agnieszka; Klantsataya, Elizaveta; Monro, Tanya M.

    2014-03-01

    Metal Enhanced Fluorescence (MEF) takes advantage of the coupling between surface plasmons, in either a metallic thin film or metallic nanoparticles, and fluorophores located in proximity of the metal, yielding an increase of the fluorophore emission. While MEF has been widely studied on metallic nanoparticles with the emphasis on creating brighter fluorescent labels, planar surfaces have not benefitted from the same attention. Here we investigate the influence of the surface roughness of a thin metallic film on the fluorescence enhancement. 50nm thick silver films were deposited on glass slides using either thermal evaporation with different evaporation currents or an electroless plating method based on the Tollens reaction to vary the surface roughness. Multiple layers of positively and negatively charged polyelectrolytes were deposited on top of the metallic coating to map out the enhancement factor as function of the gap between the metallic coating and fluorophore molecules covalently bound to the last polyelectrolyte layer. We show that fluorescence is enhanced by the presence of the metallic film, and in particular that the enhancement increases by a factor 3 to 40 for roughness ranging from 3 nm to 8 nm. Although these enhancement factors are modest compared to the enhancement produced by complex metallic nanoparticles or nano-patterned metallic thin films, the thin films used here are capable of supporting a plasmonic wave and offer the possibility of combining different techniques, such as surface plasmon resonance (with its higher refractive index sensitivity compared to localized plasmons) and MEF within a single device.

  9. Glycine post-synthetic modification of MIL-53(Fe) metal-organic framework with enhanced and stable peroxidase-like activity for sensitive glucose biosensing.

    PubMed

    Dong, Wenfei; Yang, Liaoyuan; Huang, Yuming

    2017-05-15

    A facile and rapid post-synthetic strategy was proposed to prepare a glycine functionalized MIL-53(Fe), namely glycine-MIL-53(Fe), by a simple mixing of water dispersible MIL-53(Fe) and glycine. The FT-IR, SEM, XRD and zeta potential were used to characterize the glycine-MIL-53(Fe). The result showed that glycine post-synthetic modification of MIL-53(Fe) did not change in the morphology and crystal structure of MIL-53(Fe). Interestingly, compared with MIL-53(Fe), the glycine-MIL-53(Fe) exhibits an enhanced peroxidase-like activity, which could catalyze the oxidation of TMB by H2O2 to produce an intensive color reaction. Kinetic analysis indicated that the Km of glycine-MIL-53(Fe) for TMB was one-tenth of that of MIL-53(Fe). The glycine-MIL-53(Fe) as peroxidase mimetic displays better stability under alkaline or acidic conditions than MIL-53(Fe). The good performance of glycine-MIL-53(Fe) over MIL-53(Fe) may be attributed to the increase of affinity between TMB and the glycine-MIL-53(Fe). With these characteristics, a simple and sensitive method was developed for the detection of H2O2 and glucose. The linear detection range for H2O2 is 0.10-10μM with a detection limit of 49nM, and glucose could be linearly detected in the range from 0.25 to 10μM with a detection limit of 0.13μM. The proposed method was successfully used for glucose detection in human serum samples.

  10. Metal-doped organic gels and method thereof

    DOEpatents

    Satcher, Jr., Joe H.; Baumann, Theodore F.

    2003-09-02

    Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

  11. Metal-doped organic gels and method thereof

    DOEpatents

    Satcher, Jr., Joe H.; Baumann, Theodore F.

    2007-10-23

    Disclosed herein is a sol-gel polymerization process for synthesizing metal-doped organic gels. The process polymerizes metal salts of hydroxylated benzenes or hydroxylated benzene derivatives with alkyl or aryl aldehydes to form metal-doped, wet, organic gels. The gels can then be dried by supercritical solvent extraction to form metal-doped aerogels or by evaporation to form metal-doped xerogels. The aerogels and xerogels can then be pyrolyzed.

  12. Hydrogen storage in metal-organic frameworks.

    PubMed

    Hu, Yun Hang; Zhang, Lei

    2010-05-25

    Metal-organic frameworks (MOFs) are highly attractive materials because of their ultra-high surface areas, simple preparation approaches, designable structures, and potential applications. In the past several years, MOFs have attracted worldwide attention in the area of hydrogen energy, particularly for hydrogen storage. In this review, the recent progress of hydrogen storage in MOFs is presented. The relationships between hydrogen capacities and structures of MOFs are evaluated, with emphasis on the roles of surface area and pore size. The interaction mechanism between H(2) and MOFs is discussed. The challenges to obtain a high hydrogen capacity at ambient temperature are explored.

  13. Biomimicry in metal-organic materials

    SciTech Connect

    Zhang, MW; Gu, ZY; Bosch, M; Perry, Z; Zhou, HC

    2015-06-15

    Nature has evolved a great number of biological molecules which serve as excellent constructional or functional units for metal-organic materials (MOMs). Even though the study of biomimetic MOMs is still at its embryonic stage, considerable progress has been made in the past few years. In this critical review, we will highlight the recent advances in the design, development and application of biomimetic MOMs, and illustrate how the incorporation of biological components into MOMs could further enrich their structural and functional diversity. More importantly, this review will provide a systematic overview of different methods for rational design of MOMs with biomimetic features. Published by Elsevier B.V.

  14. Metal-organic frameworks in chromatography.

    PubMed

    Yusuf, Kareem; Aqel, Ahmad; ALOthman, Zeid

    2014-06-27

    Metal-organic frameworks (MOFs) emerged approximately two decades ago and are the youngest class of porous materials. Despite their short existence, MOFs are finding applications in a variety of fields because of their outstanding chemical and physical properties. This review article focuses on the applications of MOFs in chromatography, including high-performance liquid chromatography (HPLC), gas chromatography (GC), and other chromatographic techniques. The use of MOFs in chromatography has already had a significant impact; however, the utilisation of MOFs in chromatography is still less common than other applications, and the number of MOF materials explored in chromatography applications is limited.

  15. Increasing the Stability of Metal-Organic Frameworks

    DOE PAGES

    Bosch, Mathieu; Zhang, Muwei; Zhou, Hong-Cai

    2014-01-01

    Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapsemore » upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.« less

  16. Metal salt catalysts for enhancing hydrogen spillover

    DOEpatents

    Yang, Ralph T; Wang, Yuhe

    2013-04-23

    A composition for hydrogen storage includes a receptor, a hydrogen dissociating metal doped on the receptor, and a metal salt doped on the receptor. The hydrogen dissociating metal is configured to spill over hydrogen to the receptor, and the metal salt is configured to increase a rate of the spill over of the hydrogen to the receptor.

  17. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, W.M.H.; Tzou, M.S.; Jiang, H.J.

    1987-03-31

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  18. Dispersion enhanced metal/zeolite catalysts

    DOEpatents

    Sachtler, Wolfgang M. H.; Tzou, Ming-Shin; Jiang, Hui-Jong

    1987-01-01

    Dispersion stabilized zeolite supported metal catalysts are provided as bimetallic catalyst combinations. The catalyst metal is in a reduced zero valent form while the dispersion stabilizer metal is in an unreduced ionic form. Representative catalysts are prepared from platinum or nickel as the catalyst metal and iron or chromium dispersion stabilizer.

  19. Enhanced optical properties of InAs/InAlGaAs/InP quantum dots grown by metal-organic chemical vapor deposition using a double-cap technique

    NASA Astrophysics Data System (ADS)

    Shi, Bei; Lau, Kei May

    2016-01-01

    The effects of a double-cap procedure on the optical properties of an InAs/InAlGaAs quantum dots (QDs) system grown by metal-organic chemical vapor deposition (MOCVD) have been investigated by atomic force microscopy (AFM) and room temperature photoluminescence (RT-PL) spectroscopy. An optimized QD growth condition has been achieved, with an areal density of 4.6×1010 cm-2. It was found that the thickness and lattice constant of the high temperature second cap layer (SCL) were crucial for improving the integrated PL intensity and line-width of the 1.55 μm emission from the InAs/InAlGaAs QD system grown on a semi-insulating InP (100) substrate. With fine-tuned SCL thickness and lattice constant, the optical performance of the five-stack QDs was enhanced. The improvements can be attributed to the smooth growth front, observed from the AFM images, and the well-balanced stress engineering.

  20. Thermodynamics of metal-organic frameworks

    SciTech Connect

    Wu, Di; Navrotsky, Alexandra

    2015-03-15

    Although there have been extensive studies over the past decade in the synthesis and application of metal-organic frameworks (MOFs), investigation of their thermodynamic stability and of the energetics of guest–host interactions has been much more limited. This review summarizes recent progress in experimental (calorimetric) determination of the thermodynamics of MOF materials. The enthalpies of MOFs relative to dense phase assemblages suggest only modest metastability, with a general increase of enthalpy with increasing molar volume, which becomes less pronounced at higher porosity. The energy landscape of nanoporous materials (inorganic and hybrid) consists of a pair of parallel patterns within a fairly narrow range of metastability of 5–30 kJ per mole of tetrahedra in zeolites and mesoporous silicas or per mole of metal in MOFs. Thus strong thermodynamic instability does not seem to limit framework formation. There are strong interactions within the chemisorption range for small molecule–MOF interactions with defined chemical binding at the metal centers or other specific locations. Coexistence of surface binding and confinement can lead to much stronger guest–host interactions. - Graphical abstract: Energy landscape of inorganic and hybrid porous materials. - Highlights: • Thermochemical data on various MOF structures were experimentally determined. • MOFs are moderately unstable relative to their dense phase assemblage. • Overall energetic landscape of porous materials was revealed. • Guest–host interactions in MOFs were evaluated directly using calorimetry. • Confinement effect and defined chemical binding lead to strong interactions.

  1. Chelation: Harnessing and Enhancing Heavy Metal Detoxification—A Review

    PubMed Central

    Sears, Margaret E.

    2013-01-01

    Toxic metals such as arsenic, cadmium, lead, and mercury are ubiquitous, have no beneficial role in human homeostasis, and contribute to noncommunicable chronic diseases. While novel drug targets for chronic disease are eagerly sought, potentially helpful agents that aid in detoxification of toxic elements, chelators, have largely been restricted to overt acute poisoning. Chelation, that is multiple coordination bonds between organic molecules and metals, is very common in the body and at the heart of enzymes with a metal cofactor such as copper or zinc. Peptides glutathione and metallothionein chelate both essential and toxic elements as they are sequestered, transported, and excreted. Enhancing natural chelation detoxification pathways, as well as use of pharmaceutical chelators against heavy metals are reviewed. Historical adverse outcomes with chelators, lessons learned in the art of using them, and successes using chelation to ameliorate renal, cardiovascular, and neurological conditions highlight the need for renewed attention to simple, safe, inexpensive interventions that offer potential to stem the tide of debilitating, expensive chronic disease. PMID:23690738

  2. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Omar M. Yaghi

    2012-04-26

    Conventional storage of large amounts of hydrogen in its molecular form is difficult and expensive because it requires employing either extremely high pressure gas or very low temperature liquid. Because of the importance of hydrogen as a fuel, the DOE has set system targets for hydrogen storage of gravimetric (5.5 wt%) and volumetric (40 g L-1) densities to be achieved by 2015. Given that these are system goals, a practical material will need to have higher capacity when the weight of the tank and associated cooling or regeneration system is considered. The size and weight of these components will vary substantially depending on whether the material operates by a chemisorption or physisorption mechanism. In the latter case, metal-organic frameworks (MOFs) have recently been identified as promising adsorbents for hydrogen storage, although little data is available for their sorption behavior. This grant was focused on the study of MOFs with these specific objectives. (1) To examine the effects of functionalization, catenation, and variation of the metal oxide and organic linkers on the low-pressure hydrogen adsorption properties of MOFs. (2) To develop a strategy for producing MOFs with high surface area and porosity to reduce the dead space and increase the hydrogen storage capacity per unit volume. (3) To functionalize MOFs by post synthetic functionalization with metals to improve the adsorption enthalpy of hydrogen for the room temperature hydrogen storage. This effort demonstrated the importance of open metal sites to improve the adsorption enthalpy by the systematic study, and this is also the origin of the new strategy, which termed isoreticular functionalization and metalation. However, a large pore volume is still a prerequisite feature. Based on our principle to design highly porous MOFs, guest-free MOFs with ultrahigh porosity have been experimentally synthesized. MOF-210, whose BET surface area is 6240 m2 g-1 (the highest among porous solids), takes up

  3. Stepwise Synthesis of Metal-Organic Frameworks.

    PubMed

    Bosch, Mathieu; Yuan, Shuai; Rutledge, William; Zhou, Hong-Cai

    2017-03-28

    Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using

  4. Transition metal complexes supported on metal-organic frameworks for heterogeneous catalysts

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Delferro, Massimiliano; Klet, Rachel C.

    2017-02-07

    A robust mesoporous metal-organic framework comprising a hafnium-based metal-organic framework and a single-site zirconium-benzyl species is provided. The hafnium, zirconium-benzyl metal-organic framework is useful as a catalyst for the polymerization of an alkene.

  5. Thermodynamics of Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Hughes, James Thomas

    Metal-Organic Frameworks (MOF) are crystalline nanoporous lattices constructed from the combination of cation and multi-dentate organic molecules. MOFs can display both chemical and thermal robustness while having large surface areas and pore volumes. In addition the modular composition of MOFs allows a degree of design and control of MOF structures. These unique physical properties have attracted wide interest and position MOFs to make meaningful contributions towards many applications, such as adsorption, catalysis, separation, and sensing. Despite the extensive investigative work over the last decade on MOF materials, the initial synthesis is still done by trial and error. Of the identified structures some MOFs are robust while others are fragile. It is unclear what role thermodynamics plays in the formation energies of MOFs and guest molecules interactions within the pores. Better understanding of thermochemical properties of MOFs is critical if MOF synthesis is to obtain true predictive design. To address these questions aqueous solution calorimetry was performed on ten different frameworks in both the as-synthesized and activated state. To understand the structural energetics of MOFs, the heat of formation from dense states (metal oxide and protonated organic linkers) to the open MOF framework was measured. Chapter 2 discusses the new aqueous calorimetry methodology developed to measure the enthalpy of solution for hybrid materials. Chapters 3, 4 and 5 detail the enthalpies of formation from their dense states of the frameworks: (MOF-5, ZIF-zni, ZIF-1, ZIF-3, ZIF-4, ZIF-7, ZIF-8, ZIF-9 and Cu-HKUST-1). These chapters also compare the MOF heat of formation energetics to those of zeolites, zeotypes and mesoporous silica materials. Finding that MOFs are metastable with respect to their dense states (metal oxide and protonated organic), following the current destabilization trend of the main group porous materials. The thermochemical effect of solvent on the MOF

  6. Plasmonic enhancement of light trapping into organic solar cells

    NASA Astrophysics Data System (ADS)

    Nguyen, Bich Ha; Hieu Nguyen, Van; Vu, Dinh Lam

    2015-12-01

    The present work is devoted to the review of the methods to improve light trapping into polymer solar cells. After a discussion on the important role of the improvement of the light-trapping technique in the fabrication of solar cells by applying the plasmonic enhancement effect, we review the results of the study on this topic, which were obtained mainly during recent years. The light-trapping nanostructures usually comprised the following basic elements: antireflection coating, randomly distributed or symmetric-periodic monolayers of metallic spherical nanoparticles (NPs), metallic NPs with different shapes, spherical NPs with core-shell structure, nanovoids, plasmonic metallic grating, grating organic active layer, grating indium tin oxide (ITO) layer, dielectric grating, photonic structure, and plasmonic cavity with subwavelength hole array. Each light-trapping nanostructure may use either one or two of the above-mentioned basic elements.

  7. Metal-organic framework materials with ultrahigh surface areas

    DOEpatents

    Farha, Omar K.; Hupp, Joseph T.; Wilmer, Christopher E.; Eryazici, Ibrahim; Snurr, Randall Q.; Gomez-Gualdron, Diego A.; Borah, Bhaskarjyoti

    2015-12-22

    A metal organic framework (MOF) material including a Brunauer-Emmett-Teller (BET) surface area greater than 7,010 m.sup.2/g. Also a metal organic framework (MOF) material including hexa-carboxylated linkers including alkyne bond. Also a metal organic framework (MOF) material including three types of cuboctahedron cages fused to provide continuous channels. Also a method of making a metal organic framework (MOF) material including saponifying hexaester precursors having alkyne bonds to form a plurality of hexa-carboxylated linkers including alkyne bonds and performing a solvothermal reaction with the plurality of hexa-carboxylated linkers and one or more metal containing compounds to form the MOF material.

  8. Heavy metals and arsenic fixation into freshwater organic matter under Gammarus pulex L. influence.

    PubMed

    Schaller, Joerg; Mkandawire, Martin; Gert Dudel, E

    2010-07-01

    Organic sediments are a main sink for metal pollutants in aquatic systems. However, factors that make sediments a sink of metals and metalloids are still not clear. Consequently, we investigate the role of invertebrate shredders (Gammarus pulex L.) on quality of metal and arsenic fixation into organic partitions of sediment in the course of litter decay with laboratory microcosm experiments. During the decomposition of leaf litter, G. pulex significantly facilitated the development of small particles of organic matter. The capacity of metal fixation was significantly higher in smaller particles than leaf litter and litter residuals. Thus, G. pulex enhanced metal fixation into the organic partition of sediments by virtue of increasing the amount smaller particles in the aquatic system. Furthermore, invertebrates have a significant effect on formation of dissolved organic matter and remobilization of cobalt, molybdenum and cesium, but no significant effect on remobilization of all other measured elements.

  9. Homochiral helical metal-organic frameworks of group 1 metals.

    PubMed

    Reger, Daniel L; Leitner, Andrew; Smith, Mark D; Tran, T Thao; Halasyamani, P Shiv

    2013-09-03

    The reactions of (S)-2-(1,8-naphthalimido)propanoic acid (HL(ala)) and (S)-2-(1,8-naphthalimido)-3-hydroxypropanoic acid (HL(ser)), protonated forms of ligands that contain a carboxylate donor group, an enantiopure chiral center, and a 1,8-naphthalimide π···π stacking supramolecular tecton and in the case of HL(ser) an alcohol functional group, with the appropriate alkali metal hydroxide followed by a variety of crystallization methods leads to the formation of crystalline K(L(ala))(MeOH) (1), K(L(ala))(H2O) (2), Na(L(ala))(H2O) (3), KL(ser) (4), CsL(ser) (5), and CsL(ala) (6). Each of these new complexes has a solid state structure based on six-coordinate metals linked into homochiral helical rod secondary building unit (SBU) central cores. In addition to the bonding of the carboxylate and solvent (in the case of L(ser) the ligand alcohol) to the metals, both oxygens on the 1,8-naphthalimide act as donor groups. One naphthalimide oxygen bonds to the same helical rod SBU as the carboxylate group of that ligand forming a chelate ring. The other naphthalimide oxygen bonds to adjacent SBUs. In complexes 1-3, this inter-rod link has a square arrangement bonding four other rods forming a three-dimensional enantiopure metal-organic framework (MOF) structure, whereas in 4-6 this link has a linear arrangement bonding two other rods forming a two-dimensional, sheet structure. In the latter case, the third dimension is supported exclusively by interdigitated π···π stacking interactions of the naphthalimide supramolecular tecton, forming enantiopure supramolecular MOF solids. Compounds 1-3 lose the coordinated solvent when heating above 100 °C. For 1, the polycrystalline powder reverts to 1 only by recrystallization from methanol, whereas compounds 2 and 3 undergo gas/solid, single-crystal to single-crystal transformations to form dehydrated compounds 2* and 3*, and rehydration occurs when crystals of these new complexes are left out in air. The reversible single

  10. Hydrogen Storage in Metal-Organic Frameworks

    SciTech Connect

    Long, Jeffrey R.

    2016-04-28

    The design and characterization of new materials for hydrogen storage is an important area of research, as the ability to store hydrogen at lower pressures and higher temperatures than currently feasible would lower operating costs for small hydrogen fuel cell vehicles. In particular, metal-organic frameworks (MOFs) represent promising materials for use in storing hydrogen in this capacity. MOFs are highly porous, three-dimensional crystalline solids that are formed via linkages between metal ions (e.g., iron, nickel, and zinc) and organic molecules. MOFs can store hydrogen via strong adsorptive interactions between the gas molecules and the pores of the framework, providing a high surface area for gas adsorption and thus the opportunity to store hydrogen at significantly lower pressures than with current technologies. By lowering the energy required for hydrogen storage, these materials hold promise in rendering hydrogen a more viable fuel for motor vehicles, which is a highly desirable outcome given the clean nature of hydrogen fuel cells (water is the only byproduct of combustion) and the current state of global climate change resulting from the combustion of fossil fuels. The work presented in this report is the result of collaborative efforts between researchers at Lawrence Berkeley National Lab (LBNL), the National Institute of Standards and Technology (NIST), and General Motors Corporation (GM) to discover novel MOFs promising for H2 storage and characterize their properties. Described herein are several new framework systems with improved gravimetric and volumetric capacity to strongly bind H2 at temperatures relevant for vehicle storage. These materials were rigorously characterized using neutron diffraction, to determine the precise binding locations of hydrogen within the frameworks, and high-pressure H2 adsorption measurements, to provide a comprehensive picture of H2 adsorption at all relevant pressures. A

  11. Method of enhancing selective isotope desorption from metals

    DOEpatents

    Knize, R.J.; Cecchi, J.L.

    1983-07-26

    This invention relates generally to the field of gas desorption from metals; and, more particularly, to a method of enhancing the selective desorption of a particular isotope of a gas from metals. Enhanced selective desorption is especially useful in the operation of fusion devices.

  12. Stimulus-responsive metal-organic frameworks.

    PubMed

    Nagarkar, Sanjog S; Desai, Aamod V; Ghosh, Sujit K

    2014-09-01

    Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future "smart" technology materials. Metal-organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host-guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus-responsive MOFs or so-called smart MOFs. In particular, the various stimuli used and the utility of stimulus-responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus-responsive smart MOFs and their applications are proposed from a personal perspective.

  13. Proton-Conducting Metal-Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Ford, Jamie; Simmons, Jason; Yildirim, Taner

    2010-03-01

    Vehicles powered by polymer electrolyte membrane (PEM) fuel cells are an exciting alternative to current fossil fuel technology. The membranes in these cells serve as both charge transporter, ferrying protons from the anode to the cathode, and gas diffusion barrier, preventing the backflow of oxygen to the anode. Currently, hydrated sulfonated polymers are the preferred material for these membranes. The presence of water, however, limits the operating temperature to 100 C, reducing the electrode kinetics and CO tolerance of the entire system. In an effort to increase the efficiency and operating temperature of these fuel cells, we are investigating the proton conductivity of new host/guest materials based on metal-organic frameworks (MOFs) loaded with imidazole. These thermally stable frameworks provide well-defined pores that accommodate imidazole networks and form proton-conducting pathways. Here, we will present the structure and proton dynamics of these materials as elucidated by elastic and inelastic neutron scattering measurements.

  14. An Electrically Switchable Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  15. An Electrically Switchable Metal-Organic Framework

    SciTech Connect

    Fernandez, Carlos A.; Martin, Paul F.; Schaef, Herbert T.; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem X.; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ 5 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  16. An Electrically Switchable Metal-Organic Framework

    SciTech Connect

    Fernandez, CA; Martin, PC; Schaef, T; Bowden, ME; Thallapally, PK; Dang, L; Xu, W; Chen, XL; McGrail, BP

    2014-08-19

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication.

  17. An Electrically Switchable Metal-Organic Framework

    PubMed Central

    Fernandez, Carlos A.; Martin, Paul C.; Schaef, Todd; Bowden, Mark E.; Thallapally, Praveen K.; Dang, Liem; Xu, Wu; Chen, Xilin; McGrail, B. Peter

    2014-01-01

    Crystalline metal organic framework (MOF) materials containing interconnected porosity can be chemically modified to promote stimulus-driven (light, magnetic or electric fields) structural transformations that can be used in a number of devices. Innovative research strategies are now focused on understanding the role of chemical bond manipulation to reversibly alter the free volume in such structures of critical importance for electro-catalysis, molecular electronics, energy storage technologies, sensor devices and smart membranes. In this letter, we study the mechanism for which an electrically switchable MOF composed of Cu(TCNQ) (TCNQ = 7,7,8,8-tetracyanoquinodimethane) transitions from a high-resistance state to a conducting state in a reversible fashion by an applied potential. The actual mechanism for this reversible electrical switching is still not understood even though a number of reports are available describing the application of electric-field-induced switching of Cu(TCNQ) in device fabrication. PMID:25135307

  18. Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework.

    PubMed

    An, Jihyun; Farha, Omar K; Hupp, Joseph T; Pohl, Ehmke; Yeh, Joanne I; Rosi, Nathaniel L

    2012-01-03

    Metal-organic frameworks comprising metal-carboxylate cluster vertices and long, branched organic linkers are the most porous materials known, and therefore have attracted tremendous attention for many applications, including gas storage, separations, catalysis and drug delivery. To increase metal-organic framework porosity, the size and complexity of linkers has increased. Here we present a promising alternative strategy for constructing mesoporous metal-organic frameworks that addresses the size of the vertex rather than the length of the organic linker. This approach uses large metal-biomolecule clusters, in particular zinc-adeninate building units, as vertices to construct bio-MOF-100, an exclusively mesoporous metal-organic framework. Bio-MOF-100 exhibits a high surface area (4,300 m(2) g(-1)), one of the lowest crystal densities (0.302 g cm(-3)) and the largest metal-organic framework pore volume reported to date (4.3 cm(3) g(-1)).

  19. Enhancing metal-insulator-insulator-metal tunnel diodes via defect enhanced direct tunneling

    SciTech Connect

    Alimardani, Nasir; Conley, John F.

    2014-08-25

    Metal-insulator-insulator-metal tunnel diodes with dissimilar work function electrodes and nanolaminate Al{sub 2}O{sub 3}-Ta{sub 2}O{sub 5} bilayer tunnel barriers deposited by atomic layer deposition are investigated. This combination of high and low electron affinity insulators, each with different dominant conduction mechanisms (tunneling and Frenkel-Poole emission), results in improved low voltage asymmetry and non-linearity of current versus voltage behavior. These improvements are due to defect enhanced direct tunneling in which electrons transport across the Ta{sub 2}O{sub 5} via defect based conduction before tunneling directly through the Al{sub 2}O{sub 3}, effectively narrowing the tunnel barrier. Conduction through the device is dominated by tunneling, and operation is relatively insensitive to temperature.

  20. Induced metal redistribution and bioavailability enhancement in contaminated river sediment during in situ biogeochemical remediation.

    PubMed

    Liu, Tongzhou; Zhang, Zhen; Mao, Yanqing; Yan, Dickson Y S

    2016-04-01

    In situ sediment remediation using Ca(NO3)2 or CaO2 for odor mitigation and acid volatile sulfide (AVS) and organic pollutant (such as TPH and PAHs) removal was reported in many studies and fieldwork. Yet, the associated effects on metal mobilization and potential distortion in bioavailability were not well documented. In this study, contaminated river sediment was treated by Ca(NO3)2 and CaO2 in bench studies. Through the investigation of AVS removal, organic matter removal, the changes in sediment oxidation-reduction potential (ORP), microbial activity, and other indigenous parameters, the effects on metal bioavailability, bioaccessibility, and fraction redistribution in sediment were evaluated. The major mechanisms for sediment treated by Ca(NO3)2 and CaO2 are biostimulation with indigenous denitrifying bacteria and chemical oxidation, respectively. After applying Ca(NO3)2 and CaO2, the decreases of metal concentrations in the treated sediment were insignificant within a 35-day incubation period. However, the [SEMtot-AVS]/f OC increased near to the effective boundary of toxicity (100 μmol g(-1) organic carbon (OC)), indicating that both bioavailability and bioaccessibility of metals (Cu, Zn, and Ni) to benthic organisms are enhanced after remediation. Metals were found redistributed from relatively stable fractions (oxidizable and residual fractions) to weakly bound fractions (exchangeable and reducible fractions), and the results are in line with the enhanced metal bioavailability. Compared with Ca(NO3)2, CaO2 led to higher enhancement in metal bioavailability and bioaccessibility, and more significant metal redistribution, probably due to its stronger chemical reactive capacity to AVS and sediment organic matter. The reactions in CaO2-treated sediment would probably shift from physicochemical to biochemical heterotrophic oxidation for sediment organic matter degradation. Therefore, further investigation on the long-term metal redistribution and associated

  1. Broadband light absorption enhancement in polymer photovoltaics using metal nanowall gratings as transparent electrodes

    SciTech Connect

    Ye, Zhuo; Chaudhary, Sumit; Kuang, Ping; Ho, Kai-Ming

    2012-05-15

    The authors investigate light absorption in organic solar cells in which indium tin oxide (ITO) is replaced by a new metallic architecture (grating) as a transparent electrode. Different from typical metal nanowire gratings, our gratings consist of metal nanowalls with nanoscale footprint and (sub)microscale height [Adv. Mater. 23, 2469 (2011)], thus ensuring high optical transmittance and electrical conductivity. Simulations reveal that a broadband and polarization-insensitive light absorption enhancement is achieved via two mechanisms, when such silver nanowall gratings are employed in P3HT:PCBM based solar cells. Overall absorption enhanced by ~23% compared to a reference cell with ITO electrode.

  2. Method of enhancing selective isotope desorption from metals

    DOEpatents

    Knize, Randall J.; Cecchi, Joseph L.

    1984-01-01

    A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

  3. Modeling plasmonic efficiency enhancement in organic photovoltaics.

    PubMed

    Taff, Y; Apter, B; Katz, E A; Efron, U

    2015-09-10

    Efficiency enhancement of bulk heterojunction (BHJ) organic solar cells by means of the plasmonic effect is investigated by using finite-difference time-domain (FDTD) optical simulations combined with analytical modeling of exciton dissociation and charge transport efficiencies. The proposed method provides an improved analysis of the cell performance compared to previous FDTD studies. The results of the simulations predict an 11.8% increase in the cell's short circuit current with the use of Ag nano-hexagons.

  4. The origin of the enhanced metallicity of satellite galaxies

    NASA Astrophysics Data System (ADS)

    Bahé, Yannick M.; Schaye, Joop; Crain, Robert A.; McCarthy, Ian G.; Bower, Richard G.; Theuns, Tom; McGee, Sean L.; Trayford, James W.

    2017-01-01

    Observations of galaxies in the local Universe have shown that both the ionized gas and the stars of satellites are more metal-rich than of equally massive centrals. To gain insight into the connection between this metallicity enhancement and other differences between centrals and satellites, such as their star formation rates, gas content, and growth history, we study the metallicities of >3600 galaxies with Mstar > 1010 M⊙ in the cosmological hydrodynamical EAGLE 100 Mpc `Reference' simulation, including ˜1500 in the vicinity of galaxy groups and clusters (M200 ≥ 1013 M⊙). The simulation predicts excess gas and stellar metallicities in satellites consistent with observations, except for stellar metallicities at Mstar ≲ 1010.2 M⊙ where the predicted excess is smaller than observed. The exact magnitude of the effect depends on galaxy selection, aperture, and on whether the metallicity is weighted by stellar mass or luminosity. The stellar metallicity excess in clusters is also sensitive to the efficiency scaling of star formation feedback. We identify stripping of low-metallicity gas from the galaxy outskirts, as well as suppression of metal-poor inflows towards the galaxy centre, as key drivers of the enhancement of gas metallicity. Stellar metallicities in satellites are higher than in the field as a direct consequence of the more metal-rich star-forming gas, whereas stripping of stars and suppressed stellar mass growth, as well as differences in accreted versus in situ star formation between satellites and the field, are of secondary importance.

  5. Modulate Organic-Metal Oxide Heterojunction via [1,6] Azafulleroid for Highly Efficient Organic Solar Cells.

    PubMed

    Li, Chang-Zhi; Huang, Jiang; Ju, Huanxin; Zang, Yue; Zhang, Jianyuan; Zhu, Junfa; Chen, Hongzheng; Jen, Alex K-Y

    2016-09-01

    By creating an effective π-orbital hybridization between the fullerene cage and the aromatic anchor (addend), the azafulleroid interfacial modifiers exhibit enhanced electronic coupling to the underneath metal oxides. High power conversion efficiency of 10.3% can be achieved in organic solar cells using open-cage phenyl C61 butyric acid methyl ester (PCBM)-modified zinc oxide layer.

  6. Quantum Efficiency Enhancement in CsI/Metal Photocathodes

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Hess, Wayne P.

    2015-02-01

    High quantum efficiency enhancement is found for hybrid metal-insulator photocathodes consisting of thin films of CsI deposited on Cu(100), Ag(100), Au(111) and Au films irradiated by 266 nm laser pulses. Low work functions (near or below 2 eV) are observed following ultraviolet laser activation. Work functions are reduced by roughly 3 eV from that of clean metal surfaces. We discuss various mechanisms of quantum efficiency enhancement for alkali halide/metal photocathode systems and conclude that the large change in work function, due to Cs accumulation of Cs metal at the metal-alkali halide interface, is the dominant mechanism for quantum efficiency enhancement

  7. Metal-graphene-metal sandwich contacts for enhanced interface bonding and work function control.

    PubMed

    Gong, Cheng; Hinojos, David; Wang, Weichao; Nijem, Nour; Shan, Bin; Wallace, Robert M; Cho, Kyeongjae; Chabal, Yves J

    2012-06-26

    Only a small fraction of all available metals has been used as electrode materials for carbon-based devices due to metal-graphene interface debonding problems. We report an enhancement of the bonding energy of weakly interacting metals by using a metal-graphene-metal sandwich geometry, without sacrificing the intrinsic π-electron dispersions of graphene that is usually undermined by strong metal-graphene interface hybridization. This sandwich structure further makes it possible to effectively tune the doping of graphene with an appropriate selection of metals. Density functional theory calculations reveal that the strengthening of the interface interaction is ascribed to an enhancement of interface dipole-dipole interactions. Raman scattering studies of metal-graphene-copper sandwiches are used to validate the theoretically predicted tuning of graphene doping through sandwich structures.

  8. Metal-enhanced chemiluminescence from chromium, copper, nickel, and zinc nanodeposits: Evidence for a second enhancement mechanism in metal-enhanced fluorescence

    SciTech Connect

    Weisenberg, Micah; Zhang Yongxia; Geddes, Chris D.

    2010-09-27

    Over the past decade metal-fluorophore interactions, metal-enhanced fluorescence, have attracted significant research attention, with the technology now becoming common place in life science applications. In this paper, we address the underlying mechanisms of metal-enhanced fluorescence (MEF) and experimentally show using chemiluminescence solutions that MEF is indeed underpinned by two complimentary mechanisms, consistent with the recent reports by Geddes and co-workers [Zhang et al., J. Phys. Chem. C 113, 12095 (2009)] and their enhanced fluorescence hypothesis.

  9. Metal-enhanced chemiluminescence from chromium, copper, nickel, and zinc nanodeposits: Evidence for a second enhancement mechanism in metal-enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Weisenberg, Micah; Zhang, Yongxia; Geddes, Chris D.

    2010-09-01

    Over the past decade metal-fluorophore interactions, metal-enhanced fluorescence, have attracted significant research attention, with the technology now becoming common place in life science applications. In this paper, we address the underlying mechanisms of metal-enhanced fluorescence (MEF) and experimentally show using chemiluminescence solutions that MEF is indeed underpinned by two complimentary mechanisms, consistent with the recent reports by Geddes and co-workers [Zhang et al., J. Phys. Chem. C 113, 12095 (2009)] and their enhanced fluorescence hypothesis.

  10. Photodeposition of Silver Can Result in Metal-Enhanced Fluorescence

    PubMed Central

    GEDDES, CHRIS D.; PARFENOV, ALEXANDR

    2009-01-01

    Chemically deposited silver particles are widely used for surface-enhanced Raman scattering (SERS) and more recently for surface-enhanced fluorescence (SEF), also known as metal-enhanced fluorescence (MEF). We now show that metallic silver deposited by laser illumination results in an ~7-fold increased intensity of locally bound indocyanine green. The increased intensity is accompanied by a decreased lifetime and increased photostability. These results demonstrate the possibility of photolithographic preparation of surfaces for enhanced fluorescence in microfluidics, medical diagnostics, and other applications. PMID:14658678

  11. Metal oxide charge transport material doped with organic molecules

    DOEpatents

    Forrest, Stephen R.; Lassiter, Brian E.

    2016-08-30

    Doping metal oxide charge transport material with an organic molecule lowers electrical resistance while maintaining transparency and thus is optimal for use as charge transport materials in various organic optoelectronic devices such as organic photovoltaic devices and organic light emitting devices.

  12. Dissolved organic matter enhances microbial mercury methylation under sulfidic conditions

    USGS Publications Warehouse

    Graham, Andrew M.; Aiken, George R.; Gilmour, Cynthia

    2012-01-01

    Dissolved organic matter (DOM) is generally thought to lower metal bioavailability in aquatic systems due to the formation of metal–DOM complexes that reduce free metal ion concentrations. However, this model may not be pertinent for metal nanoparticles, which are now understood to be ubiquitous, sometimes dominant, metal species in the environment. The influence of DOM on Hg bioavailability to microorganisms was examined under conditions (0.5–5.0 nM Hg and 2–10 μM sulfide) that favor the formation of β-HgS(s) (metacinnabar) nanoparticles. We used the methylation of stable-isotope enriched 201HgCl2 by Desulfovibrio desulfuricans ND132 in short-term washed cell assays as a sensitive, environmentally significant proxy for Hg uptake. Suwannee River humic acid (SRHA) and Williams Lake hydrophobic acid (WLHPoA) substantially enhanced (2- to 38-fold) the bioavailability of Hg to ND132 over a wide range of Hg/DOM ratios (9.4 pmol/mg DOM to 9.4 nmol/mg DOM), including environmentally relevant ratios. Methylmercury (MeHg) production by ND132 increased linearly with either SRHA or WLHPoA concentration, but SRHA, a terrestrially derived DOM, was far more effective at enhancing Hg-methylation than WLHPoA, an aquatic DOM dominated by autochthonous sources. No DOM-dependent enhancement in Hg methylation was observed in Hg–DOM–sulfide solutions amended with sufficient l-cysteine to prevent β-HgS(s) formation. We hypothesize that small HgS particles, stabilized against aggregation by DOM, are bioavailable to Hg-methylating bacteria. Our laboratory experiments provide a mechanism for the positive correlations between DOC and MeHg production observed in many aquatic sediments and wetland soils.

  13. Recent Advances in Carbon Capture with Metal-Organic Frameworks.

    PubMed

    Stylianou, Kyriakos C; Queen, Wendy L

    2015-01-01

    The escalating level of CO(2) in the atmosphere is one of the most critical environmental issues of our age. The carbon capture and storage from pilot test plants represents an option for reducing CO(2) emissions, however, the energy cost associated with post-combustion carbon capture process alone is ∼30% of the total energy generated by the power plant. Thus, the generation of carbon capture adsorbents with high uptake capacities, great separation performance and low cost is of paramount importance. Metal-organic frameworks are infinite networks of metal-containing nodes bridged by organic ligands through coordination bonds into porous extended structures and several reports have revealed that they are ideal candidates for the selective capture of CO(2). In this review we summarize recent advances related to the synthesis of porous MOFs and the latest strategies to enhance the CO(2) adsorption enthalpies and capacities at low-pressures, increase hydrolytic and mechanical stabilities, and improve the ease of regeneration. Although they show great promise for post-combustion carbon capture, there are still major challenges that must be overcome before they can be used for such a large-scale application.

  14. Metal-organic framework composites: from fundamentals to applications

    NASA Astrophysics Data System (ADS)

    Li, Shaozhou; Huo, Fengwei

    2015-04-01

    Metal-organic frameworks (MOFs) are a class of crystallized porous polymeric materials consisting of metal ions or clusters linked together by organic bridging ligands. Due to their permanent porosity, rich surface chemistry and tuneable pore sizes, MOFs have emerged as one type of important porous solid and have attracted intensive interests in catalysis, gas adsorption, separation and storage over the past two decades. When compared with pure MOFs, the combination of MOFs with functional species or matrix materials not only shows enhanced properties, but also broadens the applications of MOFs in new fields, such as bio-imaging, drug delivery and electrical catalysis, owing to the interactions of the functional species/matrix with the MOF structures. Although the synthesis, chemical modification and potential applications of MOFs have been reviewed previously, there is an increasing awareness on the synthesis and applications of their composites, which have rarely been reviewed. This review aims to fill this gap and discuss the fabrication, properties, and applications of MOF composites. The remaining challenges and future opportunities in this field, in terms of processing techniques, maximizing composite properties, and prospects for applications, have also been indicated.

  15. Graphene-ribbon-coupled tunable enhanced transmission through metallic grating

    NASA Astrophysics Data System (ADS)

    Peng, Yu-Xiang; He, Meng-Dong; Li, Ze-Jun; Wang, Kai-Jun; Li, Shui; Li, Jian-Bo; Liu, Jian-Qiang; Long, Mengqiu; Hu, Wei-Da; Chen, Xiaoshuang

    2017-01-01

    We report the tunable enhanced transmission of light through a hybrid metal-graphene structure, in which a graphene ribbon array is situated over a metallic grating. The graphene ribbon is employed to make the graphene-insulator-metal waveguide of finite length as a Fabry-Perot (F-P) cavity. When the slit of metallic grating is opened at the position with a maximal magnetic field in F-P resonant cavity, the transmission of light through metallic grating is greatly enhanced since the strongly localized magnetic field is effectively coupled to the slit. The transmission spectrum and the enhancement factor can be adjusted by changing geometrical parameters including the width and the length of slit, the width of graphene ribbon and the period of metallic grating. The transmission peaks exhibit a broad tuning range with a small change in the Fermi energy level of graphene. Moreover, the enhancement factor of transmission peak can be manipulated by the Fermi energy level and the carrier mobility of graphene, and an enhancement factor of 154 is obtained. The findings expand our understanding of hybrid metal-graphene plasmons and have potential applications in building active plasmonic devices.

  16. Integration of metal-organic frameworks into an electrochemical dielectric thin film for electronic applications

    PubMed Central

    Li, Wei-Jin; Liu, Juan; Sun, Zhi-Hua; Liu, Tian-Fu; Lü, Jian; Gao, Shui-Ying; He, Chao; Cao, Rong; Luo, Jun-Hua

    2016-01-01

    The integration of porous metal-organic frameworks onto the surface of materials, for use as functional devices, is currently emerging as a promising approach for gas sensing and flexible displays. However, research focused on potential applications in electronic devices is in its infancy. Here we present a facile strategy by which interpenetrated, crystalline metal-organic framework films are deposited onto conductive metal-plate anodes via in situ temperature-controlled electrochemical assembly. The nanostructure of the surface as well as the thickness and uniformity of the film are well controlled. More importantly, the resulting films exhibit enhanced dielectric properties compared to traditional inorganic or organic gate dielectrics. This study demonstrates the successful implementation of the rational design of metal-organic framework thin films on conductive supports with high-performance dielectric properties. PMID:27282348

  17. Integration of metal-organic frameworks into an electrochemical dielectric thin film for electronic applications

    NASA Astrophysics Data System (ADS)

    Li, Wei-Jin; Liu, Juan; Sun, Zhi-Hua; Liu, Tian-Fu; Lü, Jian; Gao, Shui-Ying; He, Chao; Cao, Rong; Luo, Jun-Hua

    2016-06-01

    The integration of porous metal-organic frameworks onto the surface of materials, for use as functional devices, is currently emerging as a promising approach for gas sensing and flexible displays. However, research focused on potential applications in electronic devices is in its infancy. Here we present a facile strategy by which interpenetrated, crystalline metal-organic framework films are deposited onto conductive metal-plate anodes via in situ temperature-controlled electrochemical assembly. The nanostructure of the surface as well as the thickness and uniformity of the film are well controlled. More importantly, the resulting films exhibit enhanced dielectric properties compared to traditional inorganic or organic gate dielectrics. This study demonstrates the successful implementation of the rational design of metal-organic framework thin films on conductive supports with high-performance dielectric properties.

  18. Plasmonic-enhanced organic photovoltaics: breaking the 10% efficiency barrier.

    PubMed

    Gan, Qiaoqiang; Bartoli, Filbert J; Kafafi, Zakya H

    2013-05-07

    Recent advances in molecular organic photovoltaics (OPVs) have shown 10% power conversion efficiency (PCE) for single-junction cells, which put them in direct competition with PVs based on amorphous silicon. Incorporation of plasmonic nanostructures for light trapping in these thin-film devices offers an attractive solution to realize higher-efficiency OPVs with PCE>10%. This article reviews recent progress on plasmonic-enhanced OPV devices using metallic nanoparticles, and one-dimensional (1D) and two-dimensional (2D) patterned periodic nanostructures. We discuss the benefits of using various plasmonic nanostructures for broad-band, polarization-insensitive and angle-independent absorption enhancement, and their integration with one or two electrode(s) of an OPV device.

  19. Single crystalline hollow metal-organic frameworks: a metal-organic polyhedron single crystal as a sacrificial template.

    PubMed

    Kim, Hyehyun; Oh, Minhak; Kim, Dongwook; Park, Jeongin; Seong, Junmo; Kwak, Sang Kyu; Lah, Myoung Soo

    2015-02-28

    Single crystalline hollow metal-organic frameworks (MOFs) with cavity dimensions on the order of several micrometers and hundreds of micrometers were prepared using a metal-organic polyhedron single crystal as a sacrificial hard template. The hollow nature of the MOF crystal was confirmed by scanning electron microscopy of the crystal sliced using a focused ion beam.

  20. Electroluminescence Efficiency Enhancement using Metal Nanoparticles

    DTIC Science & Technology

    2008-06-22

    the vicinity of isolated metal nanoparticles and their arrays. Using the example of an InGaN /GaN quantum-well active region positioned in close...emitters placed in the vicinity of isolated metal nanoparticles and their arrays. Using the example of an InGaN /GaN quantum-well active region...electron-hole pair states are localized on the scale of the coherent length on the order of a few nanometers at room temperature, the spontaneous

  1. Nanocomposites for enhancing current collection in organic solar cells

    NASA Astrophysics Data System (ADS)

    Peterson, Eric David

    The enhancement of charge collection in organic photovoltaics by using nanocomposite materials is investigated. Two such approaches are detailed in this thesis. Chapter 1 addresses the addition of metal nanorods to the PEDOT layer of an organic solar cell in an attempt to focus incident light for better absorption by the polymer layer. Composites designed to facilitate charge transfer from nanoparticles to the polymer/fullerene system are the focus of the second chapter. Chapter 3 details a refinement to the research presented in chapter 2, adding fullerenes to the mix and creating ternary systems and providing an analytical framework for evaluating these systems. The material choices are expanded in chapter 4; we investigate a new, lower band gap conjugated polymer (PCPDTBT) as well as core-shell nanoparticles and how they interact in the system. Results are reported and further avenues of research are suggested.

  2. On nutrients and trace metals: Effects from Enhanced Weathering

    NASA Astrophysics Data System (ADS)

    Amann, T.; Hartmann, J.

    2015-12-01

    The application of rock flour on suitable land ("Enhanced Weathering") is one proposed strategy to reduce the increase of atmospheric CO2 concentrations. At the same time it is an old and established method to add fertiliser and influence soil properties. Investigations of this method focused on the impact on the carbonate system, as well as on engineering aspects of a large-scale application, but potential side effects were never discussed quantitatively. We analysed about 120,000 geochemically characterised volcanic rock samples from the literature. Applying basic statistics, theoretical release rates of nutrients and potential contaminants by Enhanced Weathering were evaluated for typical rock types. Applied rock material can contain significant amounts of essential or beneficial nutrients (potassium, phosphorus, micronutrients). Their release can partly cover the demand of major crops like wheat, rice or corn, thereby increasing crop yield on degraded soils. However, the concentrations of considered elements are variable within a specific rock type, depending on the geological setting. High heavy metal concentrations are found in (ultra-) basic rocks, the class with the highest CO2 drawdown potential. More acidic rocks contain less or no critical amounts, but sequester less CO2. Findings show that the rock selection determines the capability to supply significant amounts of nutrients, which could partly substitute industrial mineral fertiliser usage. At the same time, the release of harmful trace element has to be considered. Through careful selection of regionally available rocks, benefits could be maximised and drawbacks reduced. The deployment of Enhanced Weathering to sequester CO2 and to ameliorate soils necessitates an ecosystem management, considering the release and fate of weathered elements in plants, soils and water. Cropland with degraded soils would benefit while having a net negative CO2 effect, while other carbon dioxide removal strategies, like

  3. Surface Plasmon Enhanced Phosphorescent Organic Light Emitting Diodes

    SciTech Connect

    Guillermo Bazan; Alexander Mikhailovsky

    2008-08-01

    The objective of the proposed work was to develop the fundamental understanding and practical techniques for enhancement of Phosphorescent Organic Light Emitting Diodes (PhOLEDs) performance by utilizing radiative decay control technology. Briefly, the main technical goal is the acceleration of radiative recombination rate in organometallic triplet emitters by using the interaction with surface plasmon resonances in noble metal nanostructures. Increased photonic output will enable one to eliminate constraints imposed on PhOLED efficiency by triplet-triplet annihilation, triplet-polaron annihilation, and saturation of chromophores with long radiative decay times. Surface plasmon enhanced (SPE) PhOLEDs will operate more efficiently at high injection current densities and will be less prone to degradation mechanisms. Additionally, introduction of metal nanostructures into PhOLEDs may improve their performance due to the improvement of the charge transport through organic layers via multiple possible mechanisms ('electrical bridging' effects, doping-like phenomena, etc.). SPE PhOLED technology is particularly beneficial for solution-fabricated electrophosphorescent devices. Small transition moment of triplet emitters allows achieving a significant enhancement of the emission rate while keeping undesirable quenching processes introduced by the metal nanostructures at a reasonably low level. Plasmonic structures can be introduced easily into solution-fabricated PhOLEDs by blending and spin coating techniques and can be used for enhancement of performance in existing device architectures. This constitutes a significant benefit for a large scale fabrication of PhOLEDs, e.g. by roll-to-roll fabrication techniques. Besides multieexciton annihilation, the power efficacy of PhOLEDs is often limited by high operational bias voltages required for overcoming built-in potential barriers to injection and transport of electrical charges through a device. This problem is especially

  4. Metal Nanostructures for Detection and Imaging Enhancements

    DTIC Science & Technology

    2011-01-03

    source spectrum, is delivered into a pig adipose sample. OCT is a widely used optical imaging technique for the diagnoses of many diseases [27-29... Fahr , C. Rockstuhl, and F. Lederer, “Engineering the randomness for enhanced absorption in solar cells,” Appl. Phys. Lett. 92, 171114 (2008). 7. T...Rockstuhl, S. Fahr , and F. Lederer, “Absorption enhancement in solar cells by localized plasmon polaritons,” J. Appl. Phys. 104, 123102 (2008). 31. A

  5. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes

    NASA Astrophysics Data System (ADS)

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-08-01

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  6. Chemoselective single-site Earth-abundant metal catalysts at metal-organic framework nodes.

    PubMed

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X; Urban, Ania; Thacker, Nathan C; Lin, Wenbin

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C-H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  7. Combinatorial Approach to Studying Metal Enhanced Fluorescence from Quantum Dots

    NASA Astrophysics Data System (ADS)

    Le, Nguyet; Corrigan, Timothy; Norton, Michael; Neff, David

    2013-03-01

    Fluorescence is extensively used in biochemistry for determining the concentration or purity of molecules in a biological environment. In metal-enhanced fluorescence (MEF), the fluorescence molecules separated from a metal surface by several nanometers can be enhanced. The fluorescent enhancement is dependent on the size and spacing of the nanoparticles, as has been shown previously for a number of fluorophore molecules. Fluorescence from quantum dots is of particular interest because the quantum dots do not lose fluorescence ability when exposed to light and they have higher intensity of fluorescence. The purpose of this study is to determine the effect of size and spacing on fluorescence intensity when coupling gold nano-particles with quantum dots. We employ a combinatorial approach, depositing gold particles ranging in diameter from 30 nm to 130 nm with varied spacings onto the substrate, followed by a protein spacer-layer and quantum dots. The fluorescence signal from the metal enhanced quantum dots were determined by confocal microscopy.

  8. Biomimetic mineralization of metal-organic frameworks as protective coatings for biomacromolecules

    PubMed Central

    Liang, Kang; Ricco, Raffaele; Doherty, Cara M.; Styles, Mark J.; Bell, Stephen; Kirby, Nigel; Mudie, Stephen; Haylock, David; Hill, Anita J.; Doonan, Christian J.; Falcaro, Paolo

    2015-01-01

    Enhancing the robustness of functional biomacromolecules is a critical challenge in biotechnology, which if addressed would enhance their use in pharmaceuticals, chemical processing and biostorage. Here we report a novel method, inspired by natural biomineralization processes, which provides unprecedented protection of biomacromolecules by encapsulating them within a class of porous materials termed metal-organic frameworks. We show that proteins, enzymes and DNA rapidly induce the formation of protective metal-organic framework coatings under physiological conditions by concentrating the framework building blocks and facilitating crystallization around the biomacromolecules. The resulting biocomposite is stable under conditions that would normally decompose many biological macromolecules. For example, urease and horseradish peroxidase protected within a metal-organic framework shell are found to retain bioactivity after being treated at 80 °C and boiled in dimethylformamide (153 °C), respectively. This rapid, low-cost biomimetic mineralization process gives rise to new possibilities for the exploitation of biomacromolecules. PMID:26041070

  9. Metal solubility enhancing peptides derived from barley protein.

    PubMed

    Eckert, Ewelina; Bamdad, Fatemeh; Chen, Lingyun

    2014-09-15

    Mineral supplements are required to be soluble as their bioavailability is highly correlated to their solubility in body fluids. In this study, metal binding capacity of barley protein hydrolysates and their purified fractions was investigated and expressed as increase in solubility of metal ions. Metal ions in the presence of hydrolysates exhibited a remarkable increase in solubility: 118, 32, 10, 29 and 35-fold for Fe(2+), Fe(3+), Ca(2+), Cu(2+) and Zn(2+), respectively. A mixture of low molecular weight peptides possesses a synergistic combination of both charged and hydrophobic residues and achieves the best binding metal ions. Electrostatic interactions via charged side chains and coordination binding with His and Cys, initially attract the metal ions and, afterward, hydrophobic interactions and aromatic ring stacking stabilize the positioning of metal ions in the structure of the peptide. Barley hordein hydrolysates show potential as dietary supplements that enhance both mineral solubility and bioavailability.

  10. Water-enhanced solvation of organics

    SciTech Connect

    Lee, Jane H.

    1993-07-01

    Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log γs vs xw/xs curve. From graph shape Δ(log γs) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement Δ(log γacid)/Δ(xw/xacid) = -0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was -0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

  11. Organic matter in hydrothermal metal ores and hydrothermal fluids

    USGS Publications Warehouse

    Orem, W.H.; Spiker, E. C.; Kotra, R.K.

    1990-01-01

    Massive polymetallic sulfides are currently being deposited around active submarine hydrothermal vents associated with spreading centers. Chemoautolithotrophic bacteria are responsible for the high production of organic matter also associated with modern submarine hydrothermal activity. Thus, there is a significant potential for organic matter/metal interactions in these systems. We have studied modern and ancient hydrothermal metal ores and modern hydrothermal fluids in order to establish the amounts and origin of the organic matter associated with the metal ores. Twenty-six samples from modern and ancient hydrothermal systems were surveyed for their total organic C contents. Organic C values ranged from 0.01% to nearly 4.0% in these samples. Metal ores from modern and ancient sediment-covered hydrothermal systems had higher organic C values than those from modern and ancient hydrothermal systems lacking appreciable sedimentary cover. One massive pyrite sample from the Galapagos spreading center (3% organic C) had stable isotope values of -27.4% (??13C) and 2.1% (??15N), similar to those in benthic siphonophors from active vents and distinct from seep sea sedimentary organic matter. This result coupled with other analyses (e.g. 13C NMR, pyrolysis/GC, SEM) of this and other samples suggests that much of the organic matter may originate from chemoautolithotrophic bacteria at the vents. However, the organic matter in hydrothermal metal ores from sediment covered vents probably arises from complex sedimentary organic matter by hydrothermal pyrolysis. The dissolved organic C concentrations of hydrothermal fluids from one site (Juan de Fuca Ridge) were found to be the same as that of background seawater. This result may indicate that dissolved organic C is effectively scavenged from hydrothermal fluids by biological activity or by co-precipitation with metal ores. ?? 1990.

  12. Quantification of Stereochemical Communication in Metal-Organic Assemblies.

    PubMed

    Castilla, Ana M; Miller, Mark A; Nitschke, Jonathan R; Smulders, Maarten M J

    2016-08-26

    The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal-organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per "incorrect" amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra- and inter-vertex coupling constants are used to track the degree of stereochemical communication across a range of metal-organic assemblies (employing different ligands, peripheral amines, and metals); temperature-dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal-organic container molecules.

  13. On the performance of Cu-BTC metal organic framework for carbon tetrachloride gas removal.

    PubMed

    Calero, Sofía; Martín-Calvo, Ana; Hamad, Said; García-Pérez, Elena

    2011-01-07

    The performance of Cu-BTC metal organic framework for carbon tetrachloride removal from air has been studied using molecular simulations. According to our results, this material shows extremely high adsorption selectivity in favour of carbon tetrachloride. We demonstrate that this selectivity can be further enhanced by selective blockage of the framework.

  14. USING ZERO-VALENT METAL NANOPARTICLES TO REMEDIATE ORGANIC CONTAMINANTS

    EPA Science Inventory

    The transport of organic contaminants down the soil profile constitutes a serious threat to the quality of ground water. Zero-valent metals are considered innocuous abiotic agents capable of mediating decontamination processes in terrestrial systems. In this investigation, ze...

  15. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis.

    PubMed

    Liu, Jiewei; Chen, Lianfen; Cui, Hao; Zhang, Jianyong; Zhang, Li; Su, Cheng-Yong

    2014-08-21

    This review summarizes the use of metal-organic frameworks (MOFs) as a versatile supramolecular platform to develop heterogeneous catalysts for a variety of organic reactions, especially for liquid-phase reactions. Following a background introduction about catalytic relevance to various metal-organic materials, crystal engineering of MOFs, characterization and evaluation methods of MOF catalysis, we categorize catalytic MOFs based on the types of active sites, including coordinatively unsaturated metal sites (CUMs), metalloligands, functional organic sites (FOS), as well as metal nanoparticles (MNPs) embedded in the cavities. Throughout the review, we emphasize the incidental or deliberate formation of active sites, the stability, heterogeneity and shape/size selectivity for MOF catalysis. Finally, we briefly introduce their relevance into photo- and biomimetic catalysis, and compare MOFs with other typical porous solids such as zeolites and mesoporous silica with regard to their different attributes, and provide our view on future trends and developments in MOF-based catalysis.

  16. Porous materials: Lining up metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Champness, Neil R.

    2017-02-01

    A new report demonstrates an innovative approach to aligning crystallites of metal-organic frameworks such that thin films are created with oriented channels -- potentially overcoming one of the major barriers to application of these highly topical materials.

  17. From metal-organic framework to intrinsically fluorescent carbon nanodots.

    PubMed

    Amali, Arlin Jose; Hoshino, Hideto; Wu, Chun; Ando, Masanori; Xu, Qiang

    2014-07-01

    Highly photoluminescent carbon nanodots (CNDs) were synthesized for the first time from metal-organic framework (MOF, ZIF-8) nanoparticles. Coupled with fluorescence and non-toxic characteristics, these carbon nanodots could potentially be used in biosafe color patterning.

  18. Toward "metalloMOFzymes": Metal-Organic Frameworks with Single-Site Metal Catalysts for Small-Molecule Transformations.

    PubMed

    Cohen, Seth M; Zhang, Zhenjie; Boissonnault, Jake A

    2016-08-01

    Metal-organic frameworks (MOFs) are being increasingly studied as scaffolds and supports for catalysis. The solid-state structures of MOFs, combined with their high porosity, suggest that MOFs may possess advantages shared by both heterogeneous and homogeneous catalysts, with few of the shortcomings of either. Herein, efforts to create single-site catalytic metal centers appended to the organic ligand struts of MOFs will be discussed. Reactions important for advanced energy applications, such as H2 production and CO2 reduction, will be highlighted. Examining how these active sites can be introduced, their performance, and their existing limitations should provide direction for design of the next generation of MOF-based catalysts for energy-relevant, small-molecule transformations. Finally, the introduction of second-sphere interactions (e.g., hydrogen bonding via squaramide groups) as a possible route to enhancing the activity of these metal centers is reported.

  19. Metal-organic framework for the separation of alkane isomers

    DOEpatents

    Long, Jeffrey R.; Herm, Zoey R.; Wiers, Brian M.; Krishna, Rajamani

    2017-01-10

    A metal organic framework Fe.sub.2(bdp).sub.3 (BDP.sup.2-=1,4-benzenedipyrazolate) with triangular channels is particularly suited for C5-C7 separations of alkanes according to the number of branches in the molecule rather than by carbon number. The metal-organic framework can offer pore geometries that is unavailable in zeolites or other porous media, facilitating distinct types of shape-based molecular separations.

  20. [Effects of Tillage on Distribution of Heavy Metals and Organic Matter Within Purple Paddy Soil Aggregates].

    PubMed

    Shi, Qiong-bin; Zhao, Xiu-lan; Chang, Tong-ju; Lu, Ji-wen

    2016-05-15

    A long-term experiment was utilized to study the effects of tillage methods on the contents and distribution characteristics of organic matter and heavy metals (Cu, Zn, Pb, Cd, Fe and Mn) in aggregates with different sizes (including 1-2, 0.25-1, 0.05-0.25 mm and < 0.05 mm) in a purple paddy soil under two tillage methods including flooded paddy field (FPF) and paddy-upland rotation (PR). The relationship between heavy metals and organic matter in soil aggregates was also analyzed. The results showed that the aggregates of two tillage methods were dominated by 0.05-0.25 mm and < 0.05 mm particle size, respectively. The contents of organic matter in each aggregate decreased with the decrease of aggregate sizes, however, compared to PR, FPF could significantly increase the contents of organic matter in soils and aggregates. The tillage methods did not significantly affect the contents of heavy metals in soils, but FPF could enhance the accumulation and distribution of aggregate, organic matter and heavy metals in aggregates with diameters of 1-2 mm and 0.25-1 mm. Correlation analysis found that there was a negative correlation between the contents of heavy metals and organic matter in soil aggregates, but a positive correlation between the amounts of heavy metal and organic matter accumulated in soil aggregates. From the slope of the correlation analysis equations, we could found that the sensitivities of heavy metals to the changes of soil organic matters followed the order of Mn > Zn > Pb > Cu > Fe > Cd under the same tillage. When it came to the same heavy metal, it was more sensitive in PR than in FPF.

  1. Solution processed metal oxide thin film hole transport layers for high performance organic solar cells

    DOEpatents

    Steirer, K. Xerxes; Berry, Joseph J.; Chesin, Jordan P.; Lloyd, Matthew T.; Widjonarko, Nicodemus Edwin; Miedaner, Alexander; Curtis, Calvin J.; Ginley, David S.; Olson, Dana C.

    2017-01-10

    A method for the application of solution processed metal oxide hole transport layers in organic photovoltaic devices and related organic electronics devices is disclosed. The metal oxide may be derived from a metal-organic precursor enabling solution processing of an amorphous, p-type metal oxide. An organic photovoltaic device having solution processed, metal oxide, thin-film hole transport layer.

  2. Plasmonic effects for light concentration in organic photovoltaic thin films induced by hexagonal periodic metallic nanospheres

    NASA Astrophysics Data System (ADS)

    Zhu, Jinfeng; Xue, Mei; Shen, Huajun; Wu, Zhe; Kim, Seongku; Ho, Jyh-Jier; Hassani-Afshar, Aram; Zeng, Baoqing; Wang, Kang L.

    2011-04-01

    We present a plasmonic nanostructure design by embedding a layer of hexagonal periodic metallic nanospheres between the active layer and transparent anode for bulk heterojunction organic solar cells. The hybrid structure shows broadband optical absorption enhancement from localized surface plasmon resonance with a weak dependence on polarization of incident light. We also theoretically study the optimization of the design to enhance the absorption up to 1.90 times for a typical hybrid active layer based on a low band gap material.

  3. Enhancement of Raman scattering from molecules placed near metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Barbiellini, B.

    2017-01-01

    Large Raman scattering cross sections from molecules on surfaces of metallic nanoparticles are described within a renormalization-group theory. In this approach the valence electrons of the molecules are embedded in an effective medium described by a dielectric function, which integrates out the effect of the plasmonic excitations of the metallic nanoparticles. The source of the enhanced photon inelastic scattering is produced by the resonant excitation of surface plasmons at the metallic nanoparticles. A similar theory has been successfully used to explain the resonant x-ray inelastic scattering and the behavior of nonlinear susceptibilities at the x-ray edges.

  4. Surface-plasmon-enhanced photoconversion in organic photovoltaics

    NASA Astrophysics Data System (ADS)

    Morfa, Anthony John

    In this thesis, the benefits of including surface-plasmon-active materials into organic photovoltaics are investigated. First, the effect of discontinuous silver thin-films formed by physical vapor deposition at the transparent front electrode of the device is explored. A reproducible near doubling in efficiency is seen in these devices which arises from a near doubling of the short-circuit current. Analysis of the wavelength-dependence of the increase in current shows that the increase in current is due to surface-plasmon-enhanced optical absorption in the active layer of the devices. Additionally, these results are shown to be reproducible over several trials when using a fabrication routine that employs a low-temperature annealing step that retains the surface-plasmon activity of the substrate and prevents delamination of the active layers. The relative dielectric function of the active-layer material was determined at optical frequencies using variable-angle spectroscopic ellipsometry. A Huang-Rhys vibronic progression is used to model the peak energies of excitonic transitions in the film and the resulting parameters are found to be in excellent agreement with previously reported values. Theoretical calculations of the surface-plasmon enhancement are performed using the aforementioned dielectric function. The theoretical calculation of the skin depth of the surface plasmon is shown to be consistent with the observed wavelength dependence of the plasmonically enhanced current in organic photodiodes. In order to better understand the enhancement process and the fate of photogenerated holes and electrons, additional work was done to explore the electronic structure of the organic films using impedance spectroscopy. The results of this work indicate the presence of a Schottky diode at the metal/organic interface in standard device geometries. This result has several implications on charge extraction for standard devices and those including silver thin-films. It is

  5. A metal-organic framework-derived bifunctional oxygen electrocatalyst

    NASA Astrophysics Data System (ADS)

    Xia, Bao Yu; Yan, Ya; Li, Nan; Wu, Hao Bin; Lou, Xiong Wen (David); Wang, Xin

    2016-01-01

    Oxygen electrocatalysis is of great importance for many energy storage and conversion technologies, including fuel cells, metal-air batteries and water electrolysis. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive non-noble metal-based oxygen electrocatalysts is critical for the practical applications of these technologies. Here we report a general approach for the synthesis of hollow frameworks of nitrogen-doped carbon nanotubes derived from metal-organic frameworks, which exhibit higher electrocatalytic activity and stability for oxygen reduction and evolution than commercial Pt/C electrocatalysts. The remarkable electrochemical properties are mainly attributed to the synergistic effect from chemical compositions and the robust hollow structure composed of interconnected crystalline nitrogen-doped carbon nanotubes. The presented strategy for controlled design and synthesis of metal-organic framework-derived functional nanomaterials offers prospects in developing highly active electrocatalysts in electrochemical energy devices.

  6. Separating of organic and inorganic forms of metals in sediments

    SciTech Connect

    Hsieh, Yuch Ping

    1995-12-31

    Separating organic forms of trace metals from their pyritic forms is a difficult problem one constantly faced when studying trace metals in a reduced soil. It is known that pyritic forms and organic forms of metals can be separated by solubilizing pyritic forms in a reducing agent while leaving the organic forms intact. The problem is that the reducing agents used in those procedures are also metals such as Cr or Sn that makes the study of trace metals impossible. If oxidation procedure is used, both pyritic anorganic forms oxidize almost at the same rate which resulted in hardly any separation. Reported here is a new procedure that oxidizes > 95% of pyritic forms and < 5% of organic forms of heavy metal using a modified hydrogen peroxide solution. The procedure is examined using mixtures of standards and salt marsh sediments. Using this procedure, we prove that rarely any added Cu retained in salt marshes is in organic form, a result has been repeatedly mistakenly reported.

  7. Alkylamine-tethered stable metal-organic framework for CO(2) capture from flue gas.

    PubMed

    Hu, Yingli; Verdegaal, Wolfgang M; Yu, Shu-Hong; Jiang, Hai-Long

    2014-03-01

    Different alkylamine molecules were post-synthetically tethered to the unsaturated Cr(III) centers in the metal-organic framework MIL-101. The resultant metal-organic frameworks show almost no N2 adsorption with significantly enhanced CO2 capture under ambient conditions as a result of the interaction between amine groups and CO2 molecules. Given the extraordinary stability, high CO2 uptake, ultrahigh CO2 /N2 selectivity, and mild regeneration energy, MIL-101-diethylenetriamine holds exceptional promise for post-combustion CO2 capture and CO2 /N2 separation.

  8. Surface modification of hollow magnetic Fe3O4@NH2-MIL-101(Fe) derived from metal-organic frameworks for enhanced selective removal of phosphates from aqueous solution

    PubMed Central

    Li, Yan; Xie, Qiying; Hu, Qian; Li, Chengping; Huang, Zhangjie; Yang, Xiangjun; Guo, Hong

    2016-01-01

    Hollow magnetic Fe3O4@NH2-MIL-101(Fe) derived from metal-organic frameworks are fabricated through a general facile strategy. The synthetic parameters are regulated to control the shape of the as-prepared samples. The concentration of phosphates decreased sharply from the initial 0.60 to 0.045 mg.L−1 with the exposure time in 50 minutes. The correlation between the most significant parameters such as contact time, adsorbent dose, pH, as well as adsorption capacities was optimized, and the effects of these parameters on the removal efficiency of phosphates were investigated. Surface functionalization of magnetic hollow materials is a well-designed way to bridge the gap between high adsorption activity, excellent separation and recovery of phosphates from the water treatment system. Therefore, it exhibits a remarkable selective removal of phosphates from aqueous solution. PMID:27470443

  9. Surface modification of hollow magnetic Fe3O4@NH2-MIL-101(Fe) derived from metal-organic frameworks for enhanced selective removal of phosphates from aqueous solution

    NASA Astrophysics Data System (ADS)

    Li, Yan; Xie, Qiying; Hu, Qian; Li, Chengping; Huang, Zhangjie; Yang, Xiangjun; Guo, Hong

    2016-07-01

    Hollow magnetic Fe3O4@NH2-MIL-101(Fe) derived from metal-organic frameworks are fabricated through a general facile strategy. The synthetic parameters are regulated to control the shape of the as-prepared samples. The concentration of phosphates decreased sharply from the initial 0.60 to 0.045 mg.L‑1 with the exposure time in 50 minutes. The correlation between the most significant parameters such as contact time, adsorbent dose, pH, as well as adsorption capacities was optimized, and the effects of these parameters on the removal efficiency of phosphates were investigated. Surface functionalization of magnetic hollow materials is a well-designed way to bridge the gap between high adsorption activity, excellent separation and recovery of phosphates from the water treatment system. Therefore, it exhibits a remarkable selective removal of phosphates from aqueous solution.

  10. A new metalation complex for organic synthesis and polymerization reactions

    NASA Technical Reports Server (NTRS)

    Hirshfield, S. M.

    1971-01-01

    Organometallic complex of N,N,N',N' tetramethyl ethylene diamine /TMEDA/ and lithium acts as metalation intermediate for controlled systhesis of aromatic organic compounds and polymer formation. Complex of TMEDA and lithium aids in preparation of various organic lithium compounds.

  11. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications

    NASA Astrophysics Data System (ADS)

    He, Jie; Liu, Yijing; Hood, Taylor C.; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-05-01

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  12. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications.

    PubMed

    He, Jie; Liu, Yijing; Hood, Taylor C; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-06-21

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  13. Metal-Organic Frameworks for Highly Selective Separations

    SciTech Connect

    Omar M. Yaghi

    2009-09-28

    This grant was focused on the study of metal-organic frameworks with these specific objectives. (1) To examine the use of MOFs with well-defined open metal sites for binding of gases and small organics. (2) To develop a strategy for producing MOFs that combine large pore size with high surface area for their use in gas adsorption and separation of polycyclic organic compounds. (3) To functionalize MOFs for the storage of inert gases such as methane. A brief outline of our progress towards these objectives is presented here as it forms part of the basis for the ideas to be developed under the present proposal.

  14. Plasmonic-enhanced organic solar cells

    NASA Astrophysics Data System (ADS)

    Shahin, Shiva; Gangopadhyay, Palash; Norwood, Robert

    2012-10-01

    Organic bulk-heterojunction solar cells have several good characteristics, such as ease of fabrication, and low-cost materials. However, the bottleneck in their adoption is their much lower efficiency as compared with their silicon counterparts. In our previous work, we demonstrated that by appropriately inserting AuNPs in the OPV device, the efficiency can be increased by 30% and that silanization of ITO positively impacts device performance, where we identified the field enhancement due to AuNPs as the main reason for the increase in the efficiency of the device. In this work, we further investigate the impact of self-assembly of the gold nanoparticles on the efficiency by also considering two other factors which can possibly contribute to the improvement of our structure's performance. One is the change in the substrate's workfunction after silanization, and the other factor is the variations in PEDOT: PSS characteristics due to the AuNPs' plasmonic resonance. We conclude that the AuNPs not only increase the photon absorption efficiency but also increase the conductivity of the surrounding medium (PEDOT: PSS) thereby facilitating charge transport through PEDOT: PSS.

  15. Broadband enhanced transmission of acoustic waves through serrated metal gratings

    NASA Astrophysics Data System (ADS)

    Qi, Dong-Xiang; Deng, Yu-Qiang; Xu, Di-Hu; Fan, Ren-Hao; Peng, Ru-Wen; Chen, Ze-Guo; Lu, Ming-Hui; Huang, X. R.; Wang, Mu

    2015-01-01

    In this letter, we have demonstrated that serrated metal gratings, which introduce gradient coatings, can give rise to broadband transmission enhancement of acoustic waves. Here, we have experimentally and theoretically studied the acoustic transmission properties of metal gratings with or without serrated boundaries. The average transmission is obviously enhanced for serrated metal gratings within a wide frequency range, while the Fabry-Perot resonance is significantly suppressed. An effective medium hypothesis with varying acoustic impedance is proposed to analyze the mechanism, which was verified through comparison with finite-element simulation. The serrated boundary supplies gradient mass distribution and gradient normal acoustic impedance, which could efficiently reduce the boundary reflection. Further, by increasing the region of the serrated boundary, we present a broadband high-transmission grating for wide range of incident angle. Our results may have potential applications to broadband acoustic imaging, acoustic sensing, and acoustic devices.

  16. Multiphoton absorption in graphene and metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Weiqiang, Chen

    Materials possessing large multiphoton absorption are of direct relevance to both photonics applications and materials physics. In this dissertation, we present our investigations into two novel materials: namely, (1) graphene and (2) metal-organic frameworks (MOFs). The dissertation divides into two parts. The first part of the dissertation reports our systematical Z-scan measurements onto two-photon absorption (2PA) in graphene in the spectral range of 435-1100 nm with femtosecond laser pulses. We report that the measured 2PA coefficients of graphene in the near-infrared (NIR) range of 800-1100 nm can be explained by a theoretical model based on the optical transitions near the Dirac point (K point). We also determine the 2PA coefficients of graphene in the visible spectrum (435-700 nm) and observe an enhancement induced by the excitonic Fano resonance at the saddle point (M point). By applying the second-order, time-dependent perturbation theory on interband transitions among three states near the saddle point, we develop a semi-empirical model to take excitons in graphene into consideration. And the model is in agreement with the photon-energy dependence of the observed 2PA spectrum with a scaling factor of B = (1 5) x 102 cm/MW/eV5. Our results verify, for the first time, that the excitonic Fano resonance plays an important role for the 2PA of graphene in the visible spectrum. Besides, we also detail our measurements on the spectral dependence of one-photon absorption (1PA) saturation in graphene over the visible-NIR range. A quadratic photon energy dependence of the measured saturation intensity/fluence is observed over the investigated spectral range. The underlying photo-dynamics is discussed. In the second part of the dissertation, we investigate multiphoton excited photoluminescence (MEPL) from three solid-state crystals of metal-organic frameworks (MOFs): (1) [Zn2(trans,trans-4,4 stilbenedicarboxylic acid (SDC))2(trans, trans-9, 10-bis (4-pyridylethenyl

  17. Multicolor microwave-triggered metal-enhanced chemiluminescence.

    PubMed

    Aslan, Kadir; Malyn, Stuart N; Geddes, Chris D

    2006-10-18

    We describe a novel platform technology for both significantly enhancing and obtaining chemiluminescence signatures "on-demand", subsequently named Microwave-Triggered Metal-Enhanced Chemiluminescence. By combining the use of silver nanoparticles to plasmon enhance chemiluminescence with the use of low power microwaves to localize heating around the nanostructures, we can both optically amplify and trigger chemiluminescence reactions. This approach is a significant advantage over traditional chemiluminescence techniques and methodologies, such as those used for Western Blots, which typically require long periods of time to collect chemiluminescence and offer few possibilities of optically amplifying the signatures.

  18. Enhanced-electrokinetic extraction of heavy metals from dredged harbor sediment.

    PubMed

    Yoo, Jong-Chan; Yang, Jung-Seok; Jeon, Eun-Ki; Baek, Kitae

    2015-07-01

    In this study, the feasibility of an ex situ electrokinetic (EK) process combined with pre-oxidation using hydrogen peroxide (H2O2) and pre-washing using ethylenediaminetetraacetic acid (EDTA) was investigated in enhancing the extraction of Cu, Pb, and Zn from actual dredged harbor sediment. H2O2 pre-oxidation led to a change in the fractionation of Cu bound to organic matter and the sulfide fraction in the Fe-Mn oxides to the exchangeable fraction, but was not effective at removing metals. In contrast, EDTA pre-washing changed the Fe-Mn oxide-bound fractions of Cu and Pb into easily extractable fractions; 20.1, 27.5, and 32.8% of Cu, Pb, and Zn were removed, respectively. During EK treatment, metals were transported toward the anode by electromigration of negatively charged complexes such as metal-EDTA and metal-citrate. However, EK treatment did not significantly enhance the removal of metals because metals accumulated near the anodic region with an increase in the exchangeable fraction due to the short EK operating duration and low voltage gradient. Therefore, it is necessary to extend the EK operating duration and/or increase the voltage gradient for effective transportation and removal of metals from sediment.

  19. Broadband short-range surface plasmon structures for absorption enhancement in organic photovoltaics.

    PubMed

    Bai, Wenli; Gan, Qiaoqiang; Song, Guofeng; Chen, Lianghui; Kafafi, Zakya; Bartoli, Filbert

    2010-11-08

    We theoretically demonstrate a polarization-independent nanopatterned ultra-thin metallic structure supporting short-range surface plasmon polariton (SRSPP) modes to improve the performance of organic solar cells. The physical mechanism and the mode distribution of the SRSPP excited in the cell device were analyzed, and reveal that the SRSPP-assisted broadband absorption enhancement peak could be tuned by tailoring the parameters of the nanopatterned metallic structure. Three-dimensional finite-difference time domain calculations show that this plasmonic structure can enhance the optical absorption of polymer-based photovoltaics by 39% to 112%, depending on the nature of the active layer (corresponding to an enhancement in short-circuit current density by 47% to 130%). These results are promising for the design of organic photovoltaics with enhanced performance.

  20. Mechanisms of enhanced mobilisation of trace metals by anionic surfactants in soil.

    PubMed

    Hernández-Soriano, Maria del Carmen; Degryse, Fien; Smolders, Erik

    2011-03-01

    Long-term applications of small concentrations of surfactants in soil via wastewater irrigation or pesticide application may enhance trace metal solubility. Mechanisms by which anionic surfactants (Aerosol 22, SDS and Biopower) affect trace metal solubility were assessed using batch, incubation and column experiments. In batch experiments on seven soils, the concentrations of Cu, Cd, Ni and Zn in the dissolved fraction of soils increased up to 100-fold at the high application rates, but increased less than 1.5-fold below the critical micelle concentration. Dissolved metal concentrations were less than 20% affected by surfactants in long-term incubations (70 days) up to the largest dose of 200 mg C kg(-1) soil. Leaching soil columns with A22 (100-1000 mg C L(-1)) under unsaturated conditions increased trace metal concentrations in the leachates 2-4 fold over the control. Correlation analysis and speciation modelling showed that the increased solubility of metals upon surfactant application was more related to the solubilisation of soil organic matter from soil than to complexation of the metals with the surfactant. Organic matter from soil was solubilised in response to a decrease of solution Ca(2+) as a result of Ca-surfactant precipitation. At environmentally relevant concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.

  1. Metallacarboranes: Towards promising hydrogen storage metal organic framework

    NASA Astrophysics Data System (ADS)

    Singh, Abhishek; Sadrzadeh, Arta; Yakobson, Boris

    2011-03-01

    Using first principles calculations we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms bind hydrogen via Kubas interaction. The average binding energy of ~ 0.3 eV/H favorably lies within the reversible adsorption range The Sc and Ti are found to be the optimum metal atoms maximizing the number of stored H2 molecules. Depending upon the structure, metallacarboranes can adsorb up to 8 wt% of hydrogen, which exceeds DOE goal for 2015. Being integral part of the cage, TMs do not suffer from the aggregation problem. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks (MOF), thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption. A. K. Singh, A. Sadrzadeh, and B. I. Yakobson, Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks, JACS 132,14126 (2010).

  2. Mechanochemical synthesis of an yttrium based metal-organic framework.

    PubMed

    Singh, Niraj K; Hardi, Meenakshi; Balema, Viktor P

    2013-02-01

    For the first time a metal hydride has been used for the preparation of a metal-organic framework. MIL-78 has been synthesized by the solid-state mechanochemical reaction between yttrium hydride and trimesic acid. The process does not involve solvents and does not generate liquid by-products, thus proving the viability of the solid-state approach to the synthesis of MOFs.

  3. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    SciTech Connect

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-12-15

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn{sub 3}L{sub 3}(DMF){sub 2} (1) and Zn{sub 3}L{sub 3}(DMA){sub 2}(H{sub 2}O){sub 3} (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe{sup 3+} and Al{sup 3+} by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe{sup 3+}. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe{sup 3+} or Al{sup 3+}.

  4. Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

    DOEpatents

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-11-16

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

  5. Enhancement of light absorption in organic solar cells by using plasmonic gratings

    NASA Astrophysics Data System (ADS)

    Xiao, Xiao; Zhang, Zhiyou; Xie, Shiwei; Liu, Yu; Zhai, Yucui; Hu, Dejiao; Du, Jinglei

    2014-11-01

    Organic solar cells show a commercially viable future duo to their inherent advantages, such as light weight, flexibility, and so on. Recently, a lot of progress has been made in every domain of organic solar cells. Among these, plasmonic light trapping is regarded as a promising light management technology for improving the light absorption in organic active layer. In this work, we numerically investigate the light enhancement in organic solar cell by embedding metal gratings as electrodes, including the anode and cathode. The absorption enhancement mechanism is analyzed, and the effects of grating parameters and incident angle are also investigated systematically. The results show the plasmonic gratings, especially the bottom grating, have an obvious improvement for light harvesting in organic layer, and an optical enhancement factor about 100% is obtained.

  6. Energy Storage during Compression of Metal-Organic Frameworks.

    PubMed

    Miao, Yu-Run; Su, Zhi; Suslick, Kenneth S

    2017-04-05

    Practical applications of metal-organic framework (MOF) materials require an in-depth understanding of their mechanical properties. We have investigated the mechanical properties and energy absorption behavior of single crystals of four isostructural UiO-type MOFs under uniaxial compression. In situ nanocompression experiments were used to measure the mechanical behavior of individual MOF nanocrystals under compression within a transmission electron microscope. The plasticity and endothermicity during deformation of MOFs shows a surprising potential for absorption and dissipation of mechanical shock. At compressive stress below 2 GPa, relatively small amounts of energy (<0.3 kJ/g) are absorbed by the compression of these MOFs. As the stress was increased, however, the energy absorption was significantly enhanced. Above 2 GPa, the energy absorption typically reaches 3-4 kJ/g; for comparison, the energy release in the explosion of TNT is ∼4 kJ/g. Gram for gram, MOFs can absorb as much energy as a high explosive can release.

  7. Heavy metals, organics and radioactivity in soil of western Serbia.

    PubMed

    Dugalic, Goran; Krstic, Dragana; Jelic, Miodrag; Nikezic, Dragoslav; Milenkovic, Biljana; Pucarevic, Mira; Zeremski-Skoric, Tijana

    2010-05-15

    Western Serbia is a region well-known for potato production. Concentrations of selected metals, polycyclic aromatic hydrocarbons (PAHs) and radioactivity were measured in the soil in order to evaluate the quality and characteristics. The examined soils (Luvisol and Pseudogley) showed unsuitable agrochemical characteristics (acid reaction, low content of organic matter and potassium). Some samples contained Ni, Mn and Cr above the maximal permissible concentration (MPC). The average concentration of total PAHs was 1.92 mg/kg, which is larger than the maximal permissible concentration in Serbia but below the threshold values in the European Union for food production. The average radioactivity of (238)U, (226)Ra, (232)Th, (40)K and the fission product (137)Cs were 60.4+/-26.2, 33.2+/-13.4, 49.1+/-18.5, 379+/-108 and 36.4+/-23.3 Bq/kg. Enhanced radioactivity in the soils was found. The total absorbed dose rate in air above the soil at 1m height calculated for western Serbia was 73.4 nGy/h and the annual effective dose was 90 microSv, which are similar to earlier reports for the study region.

  8. Metal Organic-Chemical Vapor Deposition fabrication of semiconductor lasers

    NASA Astrophysics Data System (ADS)

    Thomas, C.

    1980-08-01

    The metal organic chemical vapor deposition (MO-CVD) process was studied and implemented in detail. Single crystal GaAs, and Ga(x)Al(1-x)As films were grown on GaAs by depositing metal organic alkyl gallium compounds in the presence of an arsine mixture. The metal organic chemical vapor deposition process allowed formation of the semiconductor compound directly on the heated substrate in only one hot temperature zone. With MO-CVD, semiconductor films can be efficiently produced by a more economical, less complicated process which will lend itself more easily than past fabrication procedures, to high quantity, high quality reproduction techniques of semiconductor lasers. Clearly MO-CVD is of interest to the communication industry where semiconductor lasers are used extensively in fiber optic communication systems, and similarly to the solar energy business where GaAs substrates are used as photoelectric cells.

  9. Nonlinear optical properties of Pb-La metal-organic chelidamic acid frameworks

    NASA Astrophysics Data System (ADS)

    Tan, Min; Chen, Ruiqi; Yang, Sanjun; Liu, Qiming

    2017-04-01

    Chelidamic acid, acting as ligands, reacted with metal cation of lead and lanthanum. Both of them were dissolved in water and resulted in novel MOFs complexes by using solvothermal synthesis method. The complexes were characterized by the X-ray diffraction, UV-vis spectrophotometer and Z-scan measurements to investigate their morphology and optical properties. The Z-scan measurements indicated that the obtained lead metal-organic chelidamic acid frameworks showed 6.09 × 10-12 esu of χ(3). The special structure and properties, especially the empty f-electron orbital of the rare earth elements, were used to enhance optical nonlinearity. Using one-step solvothermal synthesis method, we added lanthanum into the lead-chelidamic acid metal organic complexes. By changing the spatial configuration of the ligand in the self-assembly process, novel structural complex metals of the lead-lanthanum metal-organic chelidamic acid frameworks have been successfully synthetized, and the third-order nonlinear susceptibility of χ(3)was enhanced to be 1.13 × 10-11 esu.

  10. Performance limits of plasmon-enhanced organic photovoltaics

    SciTech Connect

    Karatay, Durmus U.; Ginger, David S.; Salvador, Michael; Yao, Kai; Jen, Alex K.-Y.

    2014-07-21

    We use a combination of experiment and modeling to explore the promise and limitations of using plasmon-resonant metal nanoparticles to enhance the device performance of organic photovoltaics (OPVs). We focus on optical properties typical of the current generation of low-bandgap donor polymers blended with the fullerene (6,6)-phenyl C{sub 71}-butyric acid methyl ester (PC{sub 71}BM) and use the polymer poly(indacenodithiophene-co-phenanthro[9,10-b]quinoxaline) (PIDT-PhanQ) as our test case. We model the optical properties and performance of these devices both in the presence and absence of a variety of colloidal silver nanoparticles. We show that for these materials, device performance is sensitive to the relative z-position and the density of nanoparticles inside the active layer. Using conservative estimates of the internal quantum efficiency for the PIDT-PhanQ/PC{sub 71}BM blend, we calculate that optimally placed silver nanoparticles could yield an enhancement in short-circuit current density of over 31% when used with ∼ 80-nm-thick active layers, resulting in an absolute increase in power conversion efficiency of up to ∼2% for the device based on optical engineering.

  11. Effect of clays, metal oxides, and organic matter on rhamnolipid biosurfactant sorption by soil.

    PubMed

    Ochoa-Loza, Francisco J; Noordman, Wouter H; Jannsen, Dick B; Brusseau, Mark L; Maier, Raina M

    2007-01-01

    Rhamnolipids produced by Pseudomonas aeruginosa have been proposed as soil washing agents for enhanced removal of metal and organic contaminants from soil. A potential limitation for the application of rhamnolipids is sorption by soil matrix components. The objective of this study is to empirically determine the contribution of representative soil constituents (clays, metal oxides, and organic matter) to sorption of the rhamnolipid form most efficient at metal complexation (monorhamnolipid). Sorption studies show that monorhamnolipid (R1) sorption is concentration dependent. At low R1 concentrations that are relevant for enhancing organic contaminant biodegradation, R1 sorption followed the order: hematite (Fe(2)O(3))>kaolinite>MnO(2) approximately illite approximately Ca-montmorillonite>gibbsite (Al(OH)(3))>humic acid-coated silica. At high R1 concentrations, relevant for use in complexation/removal of metals or organics, R1 sorption followed the order: illite>humic acid-coated silica>Ca-montmorillonite>hematite>MnO(2)>gibbsite approximately kaolinite. These results allowed prediction of R1 sorption by a series of six soils. Finally, a comparison of R1 and R2 (dirhamnolipid) shows that the R1 form sorbs more strongly alone than when in a mixture of both the R1 and R2 forms. The information presented can be used to estimate, on an individual soil basis, the extent of rhamnolipid sorption. This is important for determining: (1) whether rhamnolipid addition is a feasible remediation option and (2) the amount of rhamnolipid required to efficiently remove the contaminant.

  12. Solution-Processed Metal Oxides as Efficient Carrier Transport Layers for Organic Photovoltaics.

    PubMed

    Choy, Wallace C H; Zhang, Di

    2016-01-27

    Carrier (electron and hole) transport layers (CTLs) are essential components for boosting the performance of various organic optoelectronic devices such as organic solar cells and organic light-emitting diodes. Considering the drawbacks of conventional CTLs (easily oxidized/unstable, demanding/costly fabrication, etc.), transition metal oxides with good carrier transport/extraction and superior stability have drawn extensive research interest as CTLs for next-generation devices. In recent years, many research efforts have been made toward the development of solution-based metal oxide CTLs with the focus on low- or even room-temperature processes, which can potentially be compatible with the deposition processes of organic materials and can significantly contribute to the low-cost and scale-up of organic devices. Here, the recent progress of different types of solution-processed metal oxide CTLs are systematically reviewed in the context of organic photovoltaics, from synthesis approaches to device performance. Different approaches for further enhancing the performance of solution-based metal oxide CTLs are also discussed, which may push the future development of this exciting field.

  13. Metal hybrid nanoparticles for catalytic organic and photochemical transformations.

    PubMed

    Song, Hyunjoon

    2015-03-17

    In order to understand heterogeneous catalytic reactions, model catalysts such as a single crystalline surface have been widely studied for many decades. However, catalytic systems that actually advance the reactions are three-dimensional and commonly have multiple components including active metal nanoparticles and metal oxide supports. On the other hand, as nanochemistry has rapidly been developed and been applied to various fields, many researchers have begun to discuss the impact of nanochemistry on heterogeneous catalysis. Metal hybrid nanoparticles bearing multiple components are structurally very close to the actual catalysts, and their uniform and controllable morphology is suitable for investigating the relationship between the structure and the catalytic properties in detail. In this Account, we introduce four typical structures of metal hybrid nanoparticles that can be used to conduct catalytic organic and photochemical reactions. Metal@silica (or metal oxide) yolk-shell nanoparticles, in which metal cores exist in internal voids surrounded by thin silica (or metal oxide) shells, exhibited extremely high thermal and chemical stability due to the geometrical protection of the silica layers against the metal cores. The morphology of the metal cores and the pore density of the hollow shells were precisely adjusted to optimize the reaction activity and diffusion rates of the reactants. Metal@metal oxide core-shell nanoparticles and inverted structures, where the cores supported the shells serving an active surface, exhibited high activity with no diffusion barriers for the reactants and products. These nanostructures were used as effective catalysts for various organic and gas-phase reactions, including hydrogen transfer, Suzuki coupling, and steam methane reforming. In contrast to the yolk- and core-shell structures, an asymmetric arrangement of distinct domains generated acentric dumbbells and tipped rods. A large domain of each component added multiple

  14. Metal-Organic Frameworks as Platforms for Functional Materials.

    PubMed

    Cui, Yuanjing; Li, Bin; He, Huajun; Zhou, Wei; Chen, Banglin; Qian, Guodong

    2016-03-15

    Discoveries of novel functional materials have played very important roles to the development of science and technologies and thus to benefit our daily life. Among the diverse materials, metal-organic framework (MOF) materials are rapidly emerging as a unique type of porous and organic/inorganic hybrid materials which can be simply self-assembled from their corresponding inorganic metal ions/clusters with organic linkers, and can be straightforwardly characterized by various analytical methods. In terms of porosity, they are superior to other well-known porous materials such as zeolites and carbon materials; exhibiting extremely high porosity with surface area up to 7000 m(2)/g, tunable pore sizes, and metrics through the interplay of both organic and inorganic components with the pore sizes ranging from 3 to 100 Å, and lowest framework density down to 0.13 g/cm(3). Such unique features have enabled metal-organic frameworks to exhibit great potentials for a broad range of applications in gas storage, gas separations, enantioselective separations, heterogeneous catalysis, chemical sensing and drug delivery. On the other hand, metal-organic frameworks can be also considered as organic/inorganic self-assembled hybrid materials, we can take advantages of the physical and chemical properties of both organic and inorganic components to develop their functional optical, photonic, and magnetic materials. Furthermore, the pores within MOFs can also be utilized to encapsulate a large number of different species of diverse functions, so a variety of functional MOF/composite materials can be readily synthesized. In this Account, we describe our recent research progress on pore and function engineering to develop functional MOF materials. We have been able to tune and optimize pore spaces, immobilize specific functional groups, and introduce chiral pore environments to target MOF materials for methane storage, light hydrocarbon separations, enantioselective recognitions

  15. Metals in sediments and benthic organisms in the Mersey estuary

    NASA Astrophysics Data System (ADS)

    Langston, W. J.

    1986-08-01

    Concentrations of twelve metals were determined in sediments, seaweed ( Fucus vesiculosus), winkles ( Littorina littorea), polychaetes ( Nereis diversicolor), suspension feeding bivalves ( Mytilus edulis, Cerastoderma edule) and deposit feeding bivalves ( Macoma balthica, Scrobicularia plana) collected from the Mersey estuary between April 1980 and June 1984. Sediments and organisms in the Mersey are moderately contaminated with most of the metals measured, but mercury concentrations are consistently higher than in other United Kingdom estuaries. Comparisons with other sites in the North West of England indicate that mercury residues in organisms, though primarily dependent on sediment concentrations, are also influenced by complexation with particulate organic matter which reduces the availability of mercury. The biological availability of arsenic in Mersey sediments is similarly influenced by complexation with iron oxyhydroxides. Nereis diversicolor and Macoma balthica are the most suitable indicator species in terms of abundance and widespread distribution along the estuary, and, for the majority of metals, tissue concentrations increase upstream, reflecting corresponding gradients in sediment contamination. However mid-estuarine peaks for tin, chromium copper and nickel in Nereis indicate more localised inputs to the estuary. Correlations between lead in sediments and organisms are poor; it is suggested that hydrophilic alkyl lead compounds may be the predominant biologically available forms. Progressive reductions in mercury contamination in sediments and mercury and lead in organisms have occurred in recent years, which coincide with efforts to reduce inputs of these metals to teh Mersey estuary.

  16. Species sensitivity analysis of heavy metals to freshwater organisms.

    PubMed

    Xin, Zheng; Wenchao, Zang; Zhenguang, Yan; Yiguo, Hong; Zhengtao, Liu; Xianliang, Yi; Xiaonan, Wang; Tingting, Liu; Liming, Zhou

    2015-10-01

    Acute toxicity data of six heavy metals [Cu, Hg, Cd, Cr(VI), Pb, Zn] to aquatic organisms were collected and screened. Species sensitivity distributions (SSD) curves of vertebrate and invertebrate were constructed by log-logistic model separately. The comprehensive comparisons of the sensitivities of different trophic species to six typical heavy metals were performed. The results indicated invertebrate taxa to each heavy metal exhibited higher sensitivity than vertebrates. However, with respect to the same taxa species, Cu had the most adverse effect on vertebrate, followed by Hg, Cd, Zn and Cr. When datasets from all species were included, Cu and Hg were still more toxic than the others. In particular, the toxicities of Pb to vertebrate and fish were complicated as the SSD curves of Pb intersected with those of other heavy metals, while the SSD curves of Pb constructed by total species no longer crossed with others. The hazardous concentrations for 5 % of the species (HC5) affected were derived to determine the concentration protecting 95 % of species. The HC5 values of the six heavy metals were in the descending order: Zn > Pb > Cr > Cd > Hg > Cu, indicating toxicities in opposite order. Moreover, potential affected fractions were calculated to assess the ecological risks of different heavy metals at certain concentrations of the selected heavy metals. Evaluations of sensitivities of the species at various trophic levels and toxicity analysis of heavy metals are necessary prior to derivation of water quality criteria and the further environmental protection.

  17. Inorganic metal oxide/organic polymer nanocomposites and method thereof

    DOEpatents

    Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

    2004-03-30

    A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal inorganic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophillic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the composite material, providing superb mixing of the component phases in the energetic nanocomposite.

  18. Metal enhanced fluorescence of Ag-nanoshell dimer

    NASA Astrophysics Data System (ADS)

    Liaw, Jiunn-Woei; Chen, Huang-Chih; Chen, Bae-Renn; Kuo, Mao-Kuen

    2014-04-01

    The plasmon modes of Ag-nanoshell dimer on metal enhanced fluorescence (MEF) are studied theoretically. The amplified excitation rate of a dimer (two identical Ag nanoshells) illuminated by a plane wave for exciting a molecule located at the gap center is calculated. Subsequently, the apparent quantum yield of the emission of the excited molecule affected by the dimer is investigated. The multiple multipole method is used for the both simulations. Finally, the enhancement factor of the dimer on the overall photoluminescence of the molecule in terms of the two parameters is evaluated. Our results show that Ag-nanoshell dimer is a dual-band photoluminescence enhancer for MEF at the bonding dipole and quadrupole modes. The former is broadband, and the latter narrowband. Both bands depend on the gap size. Moreover, the average enhancement factor of Ag-nanoshell dimer for MEF with a Stokes shift is discussed.

  19. Metal-enhanced fluorescence: effect of surface coating

    NASA Astrophysics Data System (ADS)

    Lismont, M.; François, A.; Dreesen, L.; Monro, T. M.

    2014-03-01

    Metal Enhanced Fluorescence (MEF), a phenomenon arising when a fluorophore is in closed proximity to a metallic structure such as metallic films or nanostructures, is seen as a way to increase the amount of reactive oxygen species produced by the irradiation of the protoporphyrin IX (PpIX), a photosensitizer commonly used in photodynamic therapy. Here, we show a study of the distance-dependent of MEF by applying multiple layers of polyelectrolyte (PE) on silver nanoparticles (AgNPs) to progressively increase the distance between AgNPs and PpIX, covalently bond to the last polyelectrolyte layer as well as exploring the use of AgNPs of different sizes ranging from 40 to 100 nm. Up to four fold increase of PpIX fluorescence was observed when this photosensitizing agent is bounded onto 100 nm sized Ag NPs. The effective corresponding distance between AgNPs and PpIX is three layers of PE.

  20. Application of Terahertz Field Enhancement Effect in Metal Microstructures

    NASA Astrophysics Data System (ADS)

    Nakajima, M.; Kurihara, T.; Tadokoro, Y.; Kang, B.; Takano, K.; Yamaguchi, K.; Watanabe, H.; Oto, K.; Suemoto, T.; Hangyo, M.

    2016-12-01

    Applications of high-field terahertz pulses are attractive in physics and terahertz technology. In this study, two applications related to high-intensity terahertz pulses are demonstrated. The field enhancement effect by subwavelength metallic microstructures is utilized for terahertz excitation measurement. The spin precession dynamics in magnetic materials was induced by a terahertz magnetic field. Spin precession was amplified by one order of magnitude in amplitude by the enhanced magnetic terahertz field in orthoferrite ErFeO3 with metal microstructures. The induced spin dynamics was analyzed and explained by LLG-LCR model. Moreover, a detection method for terahertz pulses was developed using a cholesteric liquid crystal at room temperature without any electronic devices. The beam profile of terahertz pulses was visualized and compared to other methods such as the knife edge method using pyroelectric detector and micro-bolometer array. The liquid crystal terahertz imager is very simple and has good applicability as a portable terahertz-sensing card.

  1. Carbon Nanotube Bonding Strength Enhancement Using Metal "Wicking" Process

    NASA Technical Reports Server (NTRS)

    Lamb, James L.; Dickie, Matthew R.; Kowalczyk, Robert S.; Liao, Anna; Bronikowski, Michael J.

    2012-01-01

    Carbon nanotubes grown from a surface typically have poor bonding strength at the interface. A process has been developed for adding a metal coat to the surface of carbon nano tubes (CNTs) through a wicking process, which could lead to an enhanced bonding strength at the interface. This process involves merging CNTs with indium as a bump-bonding enhancement. Classical capillary theory would not normally allow materials that do not wet carbon or graphite to be drawn into the spacings by capillary action because the contact angle is greater than 90 degrees. However, capillary action can be induced through JPL's ability to fabricate oriented CNT bundles to desired spacings, and through the use of deposition techniques and temperature to control the size and mobility of the liquid metal streams and associated reservoirs. A reflow and plasma cleaning process has also been developed and demonstrated to remove indium oxide, and to obtain smooth coatings on the CNT bundles.

  2. Silver-copper alloy nanoparticles for metal enhanced luminescence

    NASA Astrophysics Data System (ADS)

    Chowdhury, Sanchari; Bhethanabotla, Venkat R.; Sen, Rajan

    2009-09-01

    Large metal enhanced luminescence was realized at the vicinity of easily fabricated Ag-Cu alloy nanoparticles upon tuning of their surface plasmon resonance spectra by changing only one experimental variable—the annealing temperature, for maximum spectral overlap with the emission and excitation spectra of the luminophores. We observed strong emission enhancement of luminophores (141.48±19.20 times for Alexa Fluor 488 and 23.91±12.37 times for Alexa Fluor 594) at the vicinity of these Ag-Cu nanoparticles, which is significantly larger than for pure Ag nanoparticles. We present theoretical calculations to provide insights into these experimental findings.

  3. Plasmonic Enhancement of the Ellipsometric Measurement of Thin Metal Lines

    NASA Astrophysics Data System (ADS)

    O'Mullane, Samuel

    In semiconductor manufacturing, defect analysis and process control are extremely important for optimal device performance and yield enhancement. One in-line tool used for quick optical characterization is the ellipsometer. Because it is nondestructive and largely automated, ellipsometers have become key tools in this process. Scatterometry based optical critical dimension (OCD) analysis is the full optical modeling of ellipsometric measurements using regression-based structures. Specifically for metallic gratings, OCD has a couple of challenges. First, the sensitivity to changes in the width of the metal lines is decreasing for smaller widths. Second, the main scatterometry spectral simulation method (rigorous coupled wave analysis, RCWA) can produce wildly inaccurate results if convergence is not maintained. The research that will follow demonstrates full convergence using RCWA and finite element method (FEM) simulations for metal gratings of this sort. Additionally, the main focus will be on design improvements to these metal gratings to boost sensitivity to their widths. The foundation of this improvement is plasmonic activity, realized for the first time in copper interconnect test structures. Both surface plasmon and localized plasmon activity will be discussed and seen in simulation spectra. The largest sensitivity improvement is due to localized plasmons which depend significantly on all feature dimensions of the metal grating. Importantly, the new cross-grating test structure design has increasing sensitivity with decreasing width. The proposed enhancement to sensitivity for these small metal lines is demonstrated through agreement between RCWA and FEM simulations. Due to considerably different methods and formulation, these simulations would only agree for physically measurable phenomena and converged spectra for each method.

  4. Broadband enhanced transmission of acoustic waves through serrated metal gratings

    NASA Astrophysics Data System (ADS)

    Qi, Dong-Xiang; Fan, Ren-Hao; Deng, Yu-Qiang; Peng, Ru-Wen; Wang, Mu; Jiangnan University Collaboration

    In this talk, we present our studies on broadband properties of acoustic waves through metal gratings. We have demonstrated that serrated metal gratings, which introduce gradient coatings, can give rise to broadband transmission enhancement of acoustic waves. Here, we have experimentally and theoretically studied the acoustic transmission properties of metal gratings with or without serrated boundaries. The average transmission is obviously enhanced for serrated metal gratings within a wide frequency range, while the Fabry-Perot resonance is significantly suppressed. An effective medium hypothesis with varying acoustic impedance is proposed to analyze the mechanism, which was verified through comparison with finite-element simulation. The serrated boundary supplies gradient mass distribution and gradient normal acoustic impedance, which could efficiently reduce the boundary reflection. Further, by increasing the region of the serrated boundary, we present a broadband high-transmission grating for wide range of incident angle. Our results may have potential applications to broadband acoustic imaging, acoustic sensing and new acoustic devices. References: [1] Dong-Xiang Qi, Yu-Qiang Deng, Di-Hu Xu, Ren-Hao Fan, Ru-Wen Peng, Ze-Guo Chen, Ming-Hui Lu, X. R. Huang and Mu Wang, Appl. Phys. Lett. 106, 011906 (2015); [2] Dong-Xiang Qi, Ren-Hao Fan, Ru-Wen Peng, Xian-Rong Huang, Ming-Hui Lu, Xu Ni, Qing Hu, and Mu Wang, Applied Physics Letters 101, 061912 (2012).

  5. Ultrasound enhanced process for extracting metal species in supercritical fluids

    DOEpatents

    Wai, Chien M.; Enokida, Youichi

    2006-10-31

    Improved methods for the extraction or dissolution of metals, metalloids or their oxides, especially lanthanides, actinides, uranium or their oxides, into supercritical solvents containing an extractant are disclosed. The disclosed embodiments specifically include enhancing the extraction or dissolution efficiency with ultrasound. The present methods allow the direct, efficient dissolution of UO2 or other uranium oxides without generating any waste stream or by-products.

  6. Solution-based metal enhanced fluorescence with gold and gold/silver core-shell nanorods

    NASA Astrophysics Data System (ADS)

    Ren, Zebin; Li, Xiaoyi; Guo, Jingxia; Wang, Ruibo; Wu, Yanni; Zhang, Mingdi; Li, Caixia; Han, Qingyan; Dong, Jun; Zheng, Hairong

    2015-12-01

    Metal enhanced fluorescence of Oxazine720 fluorophore with gold and gold/silver core-shell nanorods is investigated experimentally in aqueous solution system. Metallic nanorods are synthesized for providing proper localized surface plasmon resonance and necessary enhancement to the fluorophore molecule. The experimental observation shows that the fluorescence enhancement increases firstly and then decreases when the concentration of metallic nanorods increases, which is resulted by the competition between enhanced emission and inner-filtering effect. Further investigation with different amounts of metallic nanorods shows that the relationship between metal enhanced fluorescence and spectral correlation strongly depends on the concentration of metallic nanorods.

  7. Enhancing conductivity of metallic carbon nanotube networks by transition metal adsorption

    SciTech Connect

    Ketolainen, T. Havu, V.; Puska, M. J.

    2015-02-07

    The conductivity of carbon nanotube thin films is mainly determined by carbon nanotube junctions, the resistance of which can be reduced by several different methods. We investigate electronic transport through carbon nanotube junctions in a four-terminal configuration, where two metallic single-wall carbon nanotubes are linked by a group 6 transition metal atom. The transport calculations are based on the Green’s function method combined with the density-functional theory. The transition metal atom is found to enhance the transport through the junction near the Fermi level. However, the size of the nanotube affects the improvement in the conductivity. The enhancement is related to the hybridization of chromium and carbon atom orbitals, which is clearly reflected in the character of eigenstates near the Fermi level. The effects of chromium atoms and precursor molecules remaining adsorbed on the nanotubes outside the junctions are also examined.

  8. Performance enhancement of organic photovoltaic devices enabled by Au nanoarrows inducing surface plasmonic resonance effect.

    PubMed

    Li, Shujun; Li, Zhiqi; Zhang, Xinyuan; Zhang, Zhihui; Liu, Chunyu; Shen, Liang; Guo, Wenbin; Ruan, Shengping

    2016-09-21

    The surface plasmon resonance (SPR) effect of metal nanoparticles is widely employed in organic solar cells to enhance device performance. However, the light-harvesting improvement is highly dependent on the shape of the metal nanoparticles. In this study, the significantly enhanced performance upon incorporation of Au nanoarrows in solution-processed organic photovoltaic devices is demonstrated. Incorporating Au nanoarrows into the ZnO cathode buffer layer results in superior broadband optical absorption improvement and a power conversion efficiency of 7.82% is realized with a 27.3% enhancement compared with the control device. The experimental and theoretical results indicate that the introduction of Au nanoarrows not only increases optical trapping by the SPR effect but also facilitates exciton generation, dissociation, and charge transport inside the thin film device.

  9. Charge transport and absorption study of metal nanoparticle plasmonics for organic photovoltaics

    NASA Astrophysics Data System (ADS)

    Xue, Mei; Zhu, Jinfeng; Shen, Huajun; Kim, Seongku; Ho, Jack J.; Qasem, Hussam Aldeen S.; Otaibi, Zaid S. Al; Wang, Kang L.; Device Research Laboratory, Ucla Team; Kacst/California Institute Of Excellence On Green Nanotechnology Team

    2011-03-01

    A hybrid plasmonic nanostructure of an optically sensitive heterojunction organic film incorporating metal nanoparticles is fabricated. From the Charge Extraction in Linearly Increasing Voltage (CELIV) measurements, the mobility of this hybrid plasmonic nanostructure has been experimentally extracted to be at least one order of the magnitude higher than that of the organic film without metal nanoparticles. The measured absorption spectrum also shows the increasing of the intensity by around 28% as well as the broadening of the spectrum. The theoretical calculation confirms this broadband optical absorption enhancement results from localized surface plasmon resonance. The optimization of the density of the metal nanoparticles has been done to achieve the best performance for the photovoltaic devices. This work is supported in part by KACST/California Institute of Excellence on Green Nanotechnology.

  10. Intrinsic electrical conductivity of nanostructured metal-organic polymer chains

    PubMed Central

    Hermosa, Cristina; Vicente Álvarez, Jose; Azani, Mohammad-Reza; Gómez-García, Carlos J.; Fritz, Michelle; Soler, Jose M.; Gómez-Herrero, Julio; Gómez-Navarro, Cristina; Zamora, Félix

    2013-01-01

    One-dimensional conductive polymers are attractive materials because of their potential in flexible and transparent electronics. Despite years of research, on the macro- and nano-scale, structural disorder represents the major hurdle in achieving high conductivities. Here we report measurements of highly ordered metal-organic nanoribbons, whose intrinsic (defect-free) conductivity is found to be 104 S m−1, three orders of magnitude higher than that of our macroscopic crystals. This magnitude is preserved for distances as large as 300 nm. Above this length, the presence of structural defects (~ 0.5%) gives rise to an inter-fibre-mediated charge transport similar to that of macroscopic crystals. We provide the first direct experimental evidence of the gapless electronic structure predicted for these compounds. Our results postulate metal-organic molecular wires as good metallic interconnectors in nanodevices. PMID:23591876

  11. SEQUESTERING AGENTS FOR ACTIVE CAPS - REMEDIATION OF METALS AND ORGANICS

    SciTech Connect

    Knox, A; Michael Paller, M; Danny D. Reible, D; Xingmao Ma, X; Ioana G. Petrisor, I

    2007-05-10

    This research evaluated organoclays, zeolites, phosphates, and a biopolymer as sequestering agents for inorganic and organic contaminants. Batch experiments were conducted to identify amendments and mixtures of amendments for metal and organic contaminants removal and retention. Contaminant removal was evaluated by calculating partitioning coefficients. Metal retention was evaluated by desorption studies in which residue from the removal studies was extracted with 1 M MgCl{sub 2} solution. The results indicated that phosphate amendments, some organoclays, and the biopolymer, chitosan, were very effective sequestering agents for metals in fresh and salt water. Organoclays were very effective sorbents for phenanthrene, pyrene, and benzo(a)pyrene. Partitioning coefficients for the organoclays were 3000-3500 ml g{sup -1} for benzo(a)pyrene, 400-450 ml g{sup -1} for pyrene, and 50-70 ml g{sup -1} for phenanthrene. Remediation of sites with a mixture of contaminants is more difficult than sites with a single contaminant because metals and organic contaminants have different fate and transport mechanisms in sediment and water. Mixtures of amendments (e.g., organoclay and rock phosphate) have high potential for remediating both organic and inorganic contaminants under a broad range of environmental conditions, and have promise as components in active caps for sediment remediation.

  12. Metal-organic frameworks: Shuttling in the solid state

    NASA Astrophysics Data System (ADS)

    Olson, Mark A.

    2015-06-01

    Incorporating mechanically interlocked molecular shuttles within a metal-organic framework that has enough free space in the crystal lattice to permit volume-conserving translational motion sets the stage for defect-free molecular-electronic device fabrication and more.

  13. Omar Yaghi on Chemistry and Metal Organic Frameworks

    SciTech Connect

    Omar Yaghi

    2012-07-23

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  14. Omar Yaghi on Chemistry and Metal Organic Frameworks

    ScienceCinema

    Omar Yaghi

    2016-07-12

    In this edited version of the hour long talk, Omar Yaghi, director of the Molecular Foundry, sat down in conversation with Jeff Miller, head of Public Affairs, on July 11th, 2012 to discuss his fascination with the hidden world of chemistry and his work on Metal Organic Frameworks.

  15. Method of making metal-doped organic foam products

    DOEpatents

    Rinde, James A.

    1981-01-01

    Organic foams having a low density and very small cell size and method for roducing same in either a metal-loaded or unloaded (nonmetal loaded) form are described. Metal-doped foams are produced by soaking a polymer gel in an aqueous solution of desired metal salt, soaking the gel successively in a solvent series of decreasing polarity to remove water from the gel and replace it with a solvent of lower polarity with each successive solvent in the series being miscible with the solvents on each side and being saturated with the desired metal salt, and removing the last of the solvents from the gel to produce the desired metal-doped foam having desired density cell size, and metal loading. The unloaded or metal-doped foams can be utilized in a variety of applications requiring low density, small cell size foam. For example, rubidium-doped foam made in accordance with the invention has utility in special applications, such as in x-ray lasers.

  16. Microporous metal-organic frameworks for storage and separation of small hydrocarbons.

    PubMed

    He, Yabing; Zhou, Wei; Krishna, Rajamani; Chen, Banglin

    2012-12-18

    Hydrocarbons are very important energy resources and raw materials for some industrially important products and fine chemicals. There is a need for the discovery of better materials that offer enhanced capacities for safe storage of hydrocarbons. Furthermore, the development of improved separation technologies will lead to significant reduction in energy requirements and costs. In this feature article, we provide an overview of the current status of the emerging microporous metal-organic frameworks for the storage and separation of small hydrocarbons.

  17. Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

    PubMed

    Chang, Ting-Hsiang; Kung, Chung-Wei; Chen, Hsin-Wei; Huang, Tzu-Yen; Kao, Sheng-Yuan; Lu, Hsin-Che; Lee, Min-Han; Boopathi, Karunakara Moorthy; Chu, Chih-Wei; Ho, Kuo-Chuan

    2015-11-25

    Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell.

  18. Metal-organic framework templated inorganic sorbents for rapid and efficient extraction of heavy metals.

    PubMed

    Abney, C W; Gilhula, J C; Lu, K; Lin, W

    2014-12-17

    An innovative wet-treatment with Na2 S transforms two indium metal-organic frameworks (MOFs) into a series of porous inorganic sorbents. These MOF-templated materials display remarkable affinity for heavy metals with saturation occurring in less than 1 h. The saturation capacity for Hg(II) exceeds 2 g g(-1) , more than doubling the best thiol-functionalized sorbents in the literature.

  19. Hydrogen storage in Pd nanocrystals covered with a metal-organic framework.

    PubMed

    Li, Guangqin; Kobayashi, Hirokazu; Taylor, Jared M; Ikeda, Ryuichi; Kubota, Yoshiki; Kato, Kenichi; Takata, Masaki; Yamamoto, Tomokazu; Toh, Shoichi; Matsumura, Syo; Kitagawa, Hiroshi

    2014-08-01

    Hydrogen is an essential component in many industrial processes. As a result of the recent increase in the development of shale gas, steam reforming of shale gas has received considerable attention as a major source of H2, and the more efficient use of hydrogen is strongly demanded. Palladium is well known as a hydrogen-storage metal and an effective catalyst for reactions related to hydrogen in a variety of industrial processes. Here, we present remarkably enhanced capacity and speed of hydrogen storage in Pd nanocrystals covered with the metal-organic framework (MOF) HKUST-1 (copper(II) 1,3,5-benzenetricarboxylate). The Pd nanocrystals covered with the MOF have twice the storage capacity of the bare Pd nanocrystals. The significantly enhanced hydrogen storage capacity was confirmed by hydrogen pressure-composition isotherms and solid-state deuterium nuclear magnetic resonance measurements. The speed of hydrogen absorption in the Pd nanocrystals is also enhanced by the MOF coating.

  20. Enhancement stabilization of heavy metals (Zn, Pb, Cr and Cu) during vermifiltration of liquid-state sludge.

    PubMed

    Yang, Jian; Zhao, Chunhui; Xing, Meiyan; Lin, Yanan

    2013-10-01

    This paper illustrated the potential effect of earthworms on heavy metal stabilization after vermifiltration of liquid-state sludge. Significant enhancement of organics degradation in sludge caused an increase of heavy metal concentrations in VF effluent sludge. However, the analysis of heavy metal chemical speciation indicated earthworms made unstable fractions of heavy metals transformed into stable fractions. Further investigation using principal component analysis revealed that transformations of heavy metal fractions were mainly due to the changes in sludge physico-chemical properties of pH, soluble chemical oxygen demand and available phosphorus. The bioassay of earthworms indicated that only zinc was accumulated by earthworms because the unstable fraction was its main chemical speciation. Furthermore, risk analysis demonstrated that earthworm activities weakened heavy metal risk due to the formation of stable fractions although their total concentrations increased. These results indicated that earthworms in vermifilter had a positive role in stabilizing heavy metals in sewage sludge.

  1. Development of environmentally-benign wood preservatives based on the combination of organic biocides with antioxidants and metal chelators.

    PubMed

    Schultz, Tor P; Nicholas, Darrel D

    2002-11-01

    Wood extractives can be envisaged to protect heartwood by at least three different mechanisms, i.e. fungicide, free radical scavengers/antioxidants and as metal chelators. In short-term laboratory decay tests using two different wood species and decay fungi, the combination of different organic fungicides with various antioxidants and/or metal chelators gave enhanced activity as compared to the organic biocide alone, with the best results usually obtained with all three compounds. Outdoor ground-contact stakes treated with a biocide and antioxidant combination and exposed for 30 months also gave enhanced protection against both decay fungi and termites. It was concluded that the combination of an organic biocide with metal chelating and/or antioxidant additives gives enhanced protection to wood against fungi as compared to the biocide alone and, consequently, it may be possible to develop environmentally-benign wood preservative systems based on this idea.

  2. A Green Strategy to Prepare Metal Oxide Superstructure from Metal-Organic Frameworks

    PubMed Central

    Song, Yonghai; Li, Xia; Wei, Changting; Fu, Jinying; Xu, Fugang; Tan, Hongliang; Tang, Juan; Wang, Li

    2015-01-01

    Metal or metal oxides with diverse superstructures have become one of the most promising functional materials in sensor, catalysis, energy conversion, etc. In this work, a novel metal-organic frameworks (MOFs)-directed method to prepare metal or metal oxide superstructure was proposed. In this strategy, nodes (metal ions) in MOFs as precursors to form ordered building blocks which are spatially separated by organic linkers were transformed into metal oxide micro/nanostructure by a green method. Two kinds of Cu-MOFs which could reciprocally transform by changing solvent were prepared as a model to test the method. Two kinds of novel CuO with three-dimensional (3D) urchin-like and 3D rods-like superstructures composed of nanoparticles, nanowires and nanosheets were both obtained by immersing the corresponding Cu-MOFs into a NaOH solution. Based on the as-formed CuO superstructures, a novel and sensitive nonenzymatic glucose sensor was developed. The small size, hierarchical superstructures and large surface area of the resulted CuO superstructures eventually contribute to good electrocatalytic activity of the prepared sensor towards the oxidation of glucose. The proposed method of hierarchical superstructures preparation is simple, efficient, cheap and easy to mass production, which is obviously superior to pyrolysis. It might open up a new way for hierarchical superstructures preparation. PMID:25669731

  3. Metallated porphyrin based porous organic polymers as efficient electrocatalysts

    NASA Astrophysics Data System (ADS)

    Lu, Guolong; Zhu, Youlong; Xu, Kongliang; Jin, Yinghua; Ren, Zhiyong Jason; Liu, Zhenning; Zhang, Wei

    2015-10-01

    Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(ii) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ~100% constant ORR current over 50 000 s in both alkaline and acidic media. Pyrolysis of CoPOP at various temperatures (600 °C, 800 °C, and 1000 °C) yields the materials consisting of graphitic carbon layers and cobalt nanoparticles, which show greatly enhanced catalytic activity compared to the as-synthesized CoPOP. Among them, CoPOP-800/C pyrolyzed at 800 °C shows the highest specific surface area and ORR activity, displaying the most positive half-wave potential (0.825 V vs. RHE) and the largest limited diffusion current density (5.35 mA cm-2) in an alkaline medium, which are comparable to those of commercial Pt/C (20 wt%) (half-wave potential 0.829 V vs. RHE, limited diffusion current density 5.10 mA cm-2). RDE and RRDE experiments indicate that CoPOP-800/C directly reduces molecular oxygen to water through a 4-e- pathway in both alkaline and acidic media. More importantly, CoPOP-800/C exhibits excellent durability and methanol-tolerance under acidic and alkaline conditions, which surpass the Pt/C (20 wt%) system.Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(ii) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ~100% constant ORR current over 50 000 s in both

  4. Energy transfer in monodisperse quantum dot solids in the presence of self-organized array of metallic nanoparticles

    NASA Astrophysics Data System (ADS)

    Sadeghi, S. M.; West, R. G.

    2013-03-01

    We examined the interdot energy transfer between monodisperse quantum dots under different degrees of plasmonic effects (plasmonic field enhancement and Forster energy transfer from quantum dots to metallic nanoparticles). For this we studied emission of CdSe/ZnS quantum dots deposited on substrates containing self-organized arrays of gold nanoislands with radially distributed sizes gradually reduced from the centers of the substrates to their sides. The results suggest how metallic nanoparticles can be used to enhance interdot energy transfer in monodisperse quantum dots and how this process can explain some of the spectral changes seen in the emission of quantum dots when they are close to the metallic nanoparticles.

  5. Effect of organic substituents on the adsorption of carbon dioxide on a metal-organic framework

    NASA Astrophysics Data System (ADS)

    Thu Ha, Nguyen Thi; Lefedova, O. V.; Ha, Nguyen Ngoc

    2017-01-01

    The adsorption of carbon dioxide on the MOF-5 metal-organic framework and modifications of it obtained by replacing the hydrogen atoms in the organic ligands with electron donor (-CH3,-OCH3) or electron acceptor groups (-CN,-NO2) is investigated using the grand canonical Monte Carlo (GCMC) method and density functional theory (DFT). It is shown that the adsorption of carbon dioxide molecules on the structures of metal-organic frameworks is most likely on Zn4O clusters, and that the adsorption of carbon dioxide is of a physical nature. The presence of substituents-CH3,-OCH3,-CN in metal-organic frameworks increases their capacity to adsorb carbon dioxide, while that of nitro groups (-NO2) has the opposite effect.

  6. Enhancement of Thermal Conductance at Metal-Dielectric Interfaces Using Subnanometer Metal Adhesion Layers

    NASA Astrophysics Data System (ADS)

    Jeong, Minyoung; Freedman, Justin P.; Liang, Hongliang Joe; Chow, Cheng-Ming; Sokalski, Vincent M.; Bain, James A.; Malen, Jonathan A.

    2016-01-01

    We show that the use of subnanometer adhesion layers significantly enhances the thermal interface conductance at metal-dielectric interfaces. A metal-dielectric interface between Au and sapphire (Al2O3) is considered using Cu (low optical loss) and Cr (high optical loss) as adhesion layers. To enable high throughput measurements, each adhesion layer is deposited as a wedge such that a continuous range of thicknesses could be sampled. Our measurements of thermal interface conductance at the metal-Al2O3 interface made using frequency-domain thermoreflectance show that a 1-nm-thick adhesion layer of Cu or Cr is sufficient to enhance the thermal interface conductance by more than a factor of 2 or 4, respectively, relative to the pure Au/Al2O3 interface. The enhancement agrees with the diffuse-mismatch-model-based predictions of accumulated thermal conductance versus adhesion-layer thickness assuming that it contributes phonons with wavelengths less than its thickness, while those with longer wavelengths transmit directly from the Au.

  7. Hollow metal nanostructures for enhanced plasmonics (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Genç, Aziz; Patarroyo, Javier; Sancho-Parramon, Jordi; Duchamp, Martial; Gonzalez, Edgar; Bastus, Neus G.; Houben, Lothar; Dunin-Borkowski, Rafal; Puntes, Victor F.; Arbiol, Jordi

    2016-03-01

    Complex metal nanoparticles offer a great playground for plasmonic nanoengineering, where it is possible to cover plasmon resonances from ultraviolet to near infrared by modifying the morphologies from solid nanocubes to nanoframes, multiwalled hollow nanoboxes or even nanotubes with hybrid (alternating solid and hollow) structures. We experimentally show that structural modifications, i.e. void size and final morphology, are the dominant determinants for the final plasmonic properties, while compositional variations allow us to get a fine tuning. EELS mappings of localized surface plasmon resonances (LSPRs) reveal an enhanced plasmon field inside the voids of hollow AuAg nanostructures along with a more homogeneous distributions of the plasmon fields around the nanostructures. With the present methodology and the appropriate samples we are able to compare the effects of hybridization at the nanoscale in hollow nanostructures. Boundary element method (BEM) simulations also reveal the effects of structural nanoengineering on plasmonic properties of hollow metal nanostructures. Possibility of tuning the LSPR properties of hollow metal nanostructures in a wide range of energy by modifying the void size/shell thickness is shown by BEM simulations, which reveals that void size is the dominant factor for tuning the LSPRs. As a proof of concept for enhanced plasmonic properties, we show effective label free sensing of bovine serum albumin (BSA) with some of our hollow nanostructures. In addition, the different plasmonic modes observed have also been studied and mapped in 3D.

  8. Photoelectrochemical water splitting enhanced by self-assembled metal nanopillars embedded in an oxide semiconductor photoelectrode

    PubMed Central

    Kawasaki, Seiji; Takahashi, Ryota; Yamamoto, Takahisa; Kobayashi, Masaki; Kumigashira, Hiroshi; Yoshinobu, Jun; Komori, Fumio; Kudo, Akihiko; Lippmaa, Mikk

    2016-01-01

    Production of chemical fuels by direct solar energy conversion in a photoelectrochemical cell is of great practical interest for developing a sustainable energy system. Various nanoscale designs such as nanowires, nanotubes, heterostructures and nanocomposites have been explored to increase the energy conversion efficiency of photoelectrochemical water splitting. Here we demonstrate a self-organized nanocomposite material concept for enhancing the efficiency of photocarrier separation and electrochemical energy conversion. Mechanically robust photoelectrodes are formed by embedding self-assembled metal nanopillars in a semiconductor thin film, forming tubular Schottky junctions around each pillar. The photocarrier transport efficiency is strongly enhanced in the Schottky space charge regions while the pillars provide an efficient charge extraction path. Ir-doped SrTiO3 with embedded iridium metal nanopillars shows good operational stability in a water oxidation reaction and achieves over 80% utilization of photogenerated carriers under visible light in the 400- to 600-nm wavelength range. PMID:27255209

  9. Photoelectrochemical water splitting enhanced by self-assembled metal nanopillars embedded in an oxide semiconductor photoelectrode

    NASA Astrophysics Data System (ADS)

    Kawasaki, Seiji; Takahashi, Ryota; Yamamoto, Takahisa; Kobayashi, Masaki; Kumigashira, Hiroshi; Yoshinobu, Jun; Komori, Fumio; Kudo, Akihiko; Lippmaa, Mikk

    2016-06-01

    Production of chemical fuels by direct solar energy conversion in a photoelectrochemical cell is of great practical interest for developing a sustainable energy system. Various nanoscale designs such as nanowires, nanotubes, heterostructures and nanocomposites have been explored to increase the energy conversion efficiency of photoelectrochemical water splitting. Here we demonstrate a self-organized nanocomposite material concept for enhancing the efficiency of photocarrier separation and electrochemical energy conversion. Mechanically robust photoelectrodes are formed by embedding self-assembled metal nanopillars in a semiconductor thin film, forming tubular Schottky junctions around each pillar. The photocarrier transport efficiency is strongly enhanced in the Schottky space charge regions while the pillars provide an efficient charge extraction path. Ir-doped SrTiO3 with embedded iridium metal nanopillars shows good operational stability in a water oxidation reaction and achieves over 80% utilization of photogenerated carriers under visible light in the 400- to 600-nm wavelength range.

  10. When hole extraction determines charge transfer across metal-organic-metal structure

    NASA Astrophysics Data System (ADS)

    Govor, L. V.; Reiter, G.; Parisi, J.

    2016-03-01

    We examined the charge transfer in metal-organic-metal structure, where the contact resistance of the extracting interface is larger than the resistance of the organic crystalline material and the resistance of the injecting interface. If direct tunneling (low voltage) and Fowler-Nordheim tunnelling (high voltage) across both interfaces take place, part of the injected holes remains located in the organic crystal because of the blocking action of the extracting interface, but not because of traps within the organic crystalline material (which was negligible). If Fowler-Nordheim tunneling across the injecting interface and direct tunneling across the extracting interface take place for high voltages, the latter leads to the deviation of the total current-voltage characteristic from the power law I∼ Vγ with γ>2 to Ohm's law with γ≃1.0 .

  11. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOEpatents

    Brigmon, Robin L.; Story, Sandra; Altman, Denis J.; Berry, Christopher J.

    2011-05-03

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  12. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOEpatents

    Brigmon, Robin L [North Augusta, SC; Story, Sandra [Greenville, SC; Altman, Denis J [Evans, GA; Berry, Christopher J [Aiken, SC

    2011-03-15

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  13. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOEpatents

    Brigmon, Robin L.; Story, Sandra; Altman, Denis; Berry, Christopher J.

    2009-01-06

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  14. Surfactant biocatalyst for remediation of recalcitrant organics and heavy metals

    DOEpatents

    Brigmon, Robin L [North Augusta, SC; Story, Sandra [Greenville, SC; Altman,; Denis, J [Evans, GA; Berry, Christopher J [Aiken, SC

    2011-03-29

    Novel strains of isolated and purified bacteria have been identified which have the ability to degrade petroleum hydrocarbons including a variety of PAHs. Several isolates also exhibit the ability to produce a biosurfactant. The combination of the biosurfactant-producing ability along with the ability to degrade PAHs enhances the efficiency with which PAHs may be degraded. Additionally, the biosurfactant also provides an additional ability to bind heavy metal ions for removal from a soil or aquatic environment.

  15. Fatigue-Resistance Enhancements by Glass-Forming Metallic Films

    SciTech Connect

    Liu, F. X.; Liaw, Peter K; Jiang, W. H.; Chiang, C L; Gao, Yanfei; Guan, Y F; Chu, J. P.; Rack, P. D.

    2007-01-01

    Zr-based glass-forming metallic films were coated on a 316L stainless steel and a Ni-based alloy by the magnetron-sputter deposition. Four-point-bending fatigue tests were conducted on those coated materials with the film surface on the tensile side. Results showed that the fatigue life and fatigue-endurance limit of the materials could be considerably improved, and the enhancements vary with the maximum applied stress and the substrate material. Fractographs showed that the film remained well adhered to the substrate even after the severe plastic deformation. Surface-roughness measurements indicated the improvement of the surface finishes due to the deposition of the glass-forming film. Nanoindentation test results suggested that the thin film exhibited both high yield strength and good ductility. The reduction of the surface roughness, good adhesion between the film and the substrate, and the excellent strength and ductility of the glass-forming metallic film are the major factors for the fatigue-resistance enhancements of the coated material. A micromechanical model is developed to illustrate the mechanisms of fatigue-resistance enhancements through the interaction between the amorphous film and the substrate slip bands.

  16. The evolution of galaxies. III - Metal-enhanced star formation

    NASA Technical Reports Server (NTRS)

    Talbot, R. J., Jr.; Arnett, W. D.

    1973-01-01

    The problem of the paucity of low-metal-abundance low-mass stars is discussed. One alternative to the variable-initial-mass-function (VIMF) solution is proposed. It is shown that this solution - metal-enhanced star formation - satisfies the classical test which prompted the VIMF hypothesis. Furthermore, with no additional parameters it provides improved fits to other tests - e.g., inhomogeneities in the abundances in young stars, concordance of all nucleo-cosmochronologies, and a required yield of heavy-element production which is consistent with current stellar evolution theory. In this model the age of the Galaxy is 18.6 plus or minus 5.7 b.y.

  17. Metal/Semiconductor hybrid nanostructures for plasmon-enhanced applications.

    PubMed

    Jiang, Ruibin; Li, Benxia; Fang, Caihong; Wang, Jianfang

    2014-08-20

    Hybrid nanostructures composed of semiconductor and plasmonic metal components are receiving extensive attention. They display extraordinary optical characteristics that are derived from the simultaneous existence and close conjunction of localized surface plasmon resonance and semiconduction, as well as the synergistic interactions between the two components. They have been widely studied for photocatalysis, plasmon-enhanced spectroscopy, biotechnology, and solar cells. In this review, the developments in the field of (plasmonic metal)/semiconductor hybrid nanostructures are comprehensively described. The preparation of the hybrid nanostructures is first presented according to the semiconductor type, as well as the nanostructure morphology. The plasmonic properties and the enabled applications of the hybrid nanostructures are then elucidated. Lastly, possible future research in this burgeoning field is discussed.

  18. Geometrically enhanced extraordinary magnetoresistance in semiconductor-metal hybrids

    NASA Astrophysics Data System (ADS)

    Hewett, T. H.; Kusmartsev, F. V.

    2010-12-01

    Extraordinary magnetoresistance (EMR) arises in hybrid systems consisting of semiconducting material with an embedded metallic inclusion. We have investigated such systems with the use of finite-element modeling, with our results showing good agreement to existing experimental data. We show that this effect can be dramatically enhanced by over four orders of magnitude as a result of altering the geometry of the conducting region. The significance of this result lies in its potential application to EMR magnetic field sensors utilizing more familiar semiconducting materials with nonoptimum material parameters, such as silicon. Our model has been extended further with a geometry based on the microstructure of the silver chalcogenides, consisting of a randomly sized and positioned metallic network with interspersed droplets. This model has shown a large and quasilinear magnetoresistance analogous to experimental findings.

  19. Influence of dissimilatory metal reduction on fate of organic and metal contaminants in the subsurface

    USGS Publications Warehouse

    Lovely, Derek R.; Anderson, Robert T.

    2000-01-01

    Geobacter become dominant members of the microbial community when Fe(III)-reducing conditions develop as the result of organic contamination, or when Fe(III) reduction is artificially stimulated. These results suggest that further understanding of the ecophysiology of Geobacter species would aid in better prediction of the natural attenuation of organic contaminants under anaerobic conditions and in the design of strategies for the bioremediation of subsurface metal contamination.

  20. Influence of dissimilatory metal reduction on fate of organic and metal contaminants in the subsurface

    NASA Astrophysics Data System (ADS)

    Lovley, Derek R.; Anderson, Robert T.

    Dissimilatory Fe(III)-reducing microorganisms have the ability to destroy organic contaminants under anaerobic conditions by oxidizing them to carbon dioxide. Some Fe(III)-reducing microorganisms can also reductively dechlorinate chlorinated contaminants. Fe(III)-reducing microorganisms can reduce a variety of contaminant metals and convert them from soluble forms to forms that are likely to be immobilized in the subsurface. Studies in petroleum-contaminated aquifers have demonstrated that Fe(III)-reducing microorganisms can be effective agents in removing aromatic hydrocarbons from groundwater under anaerobic conditions. Laboratory studies have demonstrated the potential for Fe(III)-reducing microorganisms to remove uranium from contaminated groundwaters. The activity of Fe(III)-reducing microorganisms can be stimulated in several ways to enhance organic contaminant oxidation and metal reduction. Molecular analyses in both field and laboratory studies have demonstrated that microorganisms of the genus Geobacter become dominant members of the microbial community when Fe(III)-reducing conditions develop as the result of organic contamination, or when Fe(III) reduction is artificially stimulated. These results suggest that further understanding of the ecophysiology of Geobacter species would aid in better prediction of the natural attenuation of organic contaminants under anaerobic conditions and in the design of strategies for the bioremediation of subsurface metal contamination. Des micro-organismes simulant la réduction du fer ont la capacité de détruire des polluants organiques dans des conditions anérobies en les oxydant en dioxyde de carbone. Certains micro-organismes réducteurs de fer peuvent aussi dé-chlorer par réduction des polluants chlorés. Des micro-organismes réducteurs de fer peuvent réduire tout un ensemble de métaux polluants et les faire passer de formes solubles à des formes qui sont susceptibles d'être immobilisées dans le milieu

  1. Metal-Organic Frameworks as Catalysts for Oxidation Reactions.

    PubMed

    Dhakshinamoorthy, Amarajothi; Asiri, Abdullah M; Garcia, Hermenegildo

    2016-06-06

    This Concept is aimed at describing the current state of the art in metal-organic frameworks (MOFs) as heterogeneous catalysts for liquid-phase oxidations, focusing on three important substrates, namely, alkenes, alkanes and alcohols. Emphases are on the nature of active sites that have been incorporated within MOFs and on future targets to be set in this area. Thus, selective alkene epoxidation with peroxides or oxygen catalyzed by constitutional metal nodes of MOFs as active sites are still to be developed. Moreover, no noble metal-free MOF has been reported to date that can act as a general catalyst for the aerobic oxidation of primary and secondary aliphatic alcohols. In contrast, in the case of alkanes, a target should be to tune the polarity of MOF internal pores to control the outcome of the autooxidation process, resulting in the selective formation of alcohol/ketone mixtures at high conversion.

  2. Metalation of a Mesoporous Three-Dimensional Covalent Organic Framework.

    PubMed

    Baldwin, Luke A; Crowe, Jonathan W; Pyles, David A; McGrier, Psaras L

    2016-11-23

    Constructing metalated three-dimensional (3D) covalent organic frameworks is a challenging synthetic task. Herein, we report the synthesis and characterization of a highly porous (SABET = 5083 m(2) g(-1)) 3D COF with a record low density (0.13 g cm(-3)) containing π-electron conjugated dehydrobenzoannulene (DBA) units. Metalation of DBA-3D-COF 1 with Ni to produce Ni-DBA-3D-COF results in a minimal reduction in the surface area (SABET = 4763 m(2) g(-1)) of the material due to the incorporation of the metal within the cavity of the DBA units, and retention of crystallinity. Both 3D DBA-COFs also display great uptake capacities for ethane and ethylene gas.

  3. Metal chelate fluorescence enhancement in micellar media and its applications to niobium and tantalum ultratrace determinations

    SciTech Connect

    Sanz-Medel, A.; Alonso, J.I.G.; Gonzalez, E.B.

    1985-07-01

    The fluorescence intensities of niobium and tantalum complexes with several fluorimetric organic reagents enhanced by micellar solutions have been examined. Flavone derivatives (morin and quercetin) produced the more intense fluorescing reactions in a cationic micellar medium and are studied in detail. Effects upon fluorescence of the nature of the tensoactive material used have been investigated. The charge of the micelle, presence of homomicelles in solution, and chemical structure of the cationic surfactant and lumophoric reagent proved to be the decisive factors which influence enhancement of fluorescence of a metal chelate by a surfactant. The dramatic effects of the appropriate organizing medium and of sulfate ions on fluorescence of the Nb(V) and Ta(V) complexes with morin and quercetin are discussed in an effort to elucidate what trends may exist in the fluorescence enhancement of metal chelates by micelles. A general reaction mechanism, for those systems studied, is proposed. Analytical applications of such micelle-enhanced reactions to the fluorimetric determination of ultratraces of Nb(V) and Ta(V) are also shown. 24 references, 10 figures, 3 tables.

  4. Enhanced Structural Organization in Covalent Organic Frameworks Through Fluorination.

    PubMed

    Alahakoon, Sampath B; McCandless, Gregory T; Karunathilake, Arosha A K; Thompson, Christina M; Smaldone, Ronald A

    2017-01-30

    Here, we report a structure-function study of imine covalent organic frameworks (COFs) comparing a series of novel fluorine-containing monomers to their non-fluorinated analogues. We found that the fluorine-containing monomers produced 2D-COFs with not only greatly improved surface areas (over 2000 m(2)  g(-1) compared to 760 m(2)  g(-1) for the non-fluorinated analogue), but also with improved crystallinity and larger, more defined pore diameters. We then studied the formation of these COFs under varying reaction times and temperatures to obtain a greater insight into their mechanism of formation.

  5. Recent progress in the synthesis of metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Sun, Yujia; Zhou, Hong-Cai

    2015-10-01

    Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  6. Recent progress in the synthesis of metal-organic frameworks.

    PubMed

    Sun, Yujia; Zhou, Hong-Cai

    2015-10-01

    Metal-organic frameworks (MOFs) have attracted considerable attention for various applications due to their tunable structure, porosity and functionality. In general, MOFs have been synthesized from isolated metal ions and organic linkers under hydrothermal or solvothermal conditions via one-spot reactions. The emerging precursor approach and kinetically tuned dimensional augmentation strategy add more diversity to this field. In addition, to speed up the crystallization process and create uniform crystals with reduced size, many alternative synthesis routes have been explored. Recent advances in microwave-assisted synthesis and electrochemical synthesis are presented in this review. In recent years, post-synthetic approaches have been shown to be powerful tools to synthesize MOFs with modified functionality, which cannot be attained via de novo synthesis. In this review, some current accomplishments of post-synthetic modification (PSM) based on covalent transformations and coordinative interactions as well as post-synthetic exchange (PSE) in robust MOFs are provided.

  7. Impact of metal and anion substitutions on the hydrogen storage properties of M-BTT metal-organic frameworks.

    PubMed

    Sumida, Kenji; Stück, David; Mino, Lorenzo; Chai, Jeng-Da; Bloch, Eric D; Zavorotynska, Olena; Murray, Leslie J; Dincă, Mircea; Chavan, Sachin; Bordiga, Silvia; Head-Gordon, Martin; Long, Jeffrey R

    2013-01-23

    Microporous metal-organic frameworks are a class of materials being vigorously investigated for mobile hydrogen storage applications. For high-pressure storage at ambient temperatures, the M(3)[(M(4)Cl)(3)(BTT)(8)](2) (M-BTT; BTT(3-) = 1,3,5-benzenetristetrazolate) series of frameworks are of particular interest due to the high density of exposed metal cation sites on the pore surface. These sites give enhanced zero-coverage isosteric heats of adsorption (Q(st)) approaching the optimal value for ambient storage applications. However, the Q(st) parameter provides only a limited insight into the thermodynamics of the individual adsorption sites, the tuning of which is paramount for optimizing the storage performance. Here, we begin by performing variable-temperature infrared spectroscopy studies of Mn-, Fe-, and Cu-BTT, allowing the thermodynamics of H(2) adsorption to be probed experimentally. This is complemented by a detailed DFT study, in which molecular fragments representing the metal clusters within the extended solid are simulated to obtain a more thorough description of the structural and thermodynamic aspects of H(2) adsorption at the strongest binding sites. Then, the effect of substitutions at the metal cluster (metal ion and anion within the tetranuclear cluster) is discussed, showing that the configuration of this unit indeed plays an important role in determining the affinity of the framework toward H(2). Interestingly, the theoretical study has identified that the Zn-based analogs would be expected to facilitate enhanced adsorption profiles over the compounds synthesized experimentally, highlighting the importance of a combined experimental and theoretical approach to the design and synthesis of new frameworks for H(2) storage applications.

  8. Smart Metal-Organic Framework Coatings: Triggered Antibiofilm Compound Release.

    PubMed

    Claes, Birgit; Boudewijns, Tom; Muchez, Laurens; Hooyberghs, Geert; Van der Eycken, Erik V; Vanderleyden, Jozef; Steenackers, Hans P; De Vos, Dirk E

    2017-02-08

    Metal-organic frameworks (MOFs) have a large potential for delivery of active molecules. Here, a MOF coating is investigated as a smart host matrix for triggered release of antibiofilm compounds. In addition to a coating consisting of the regular Fe-terephthalate MIL-88B(Fe), a new hydrophobic MIL-88B(Fe) coating is synthesized in hydrothermal conditions using palmitic acid as a lattice terminating group. These porous materials are used as a host matrix for the antibiofilm compound 5-(4-chlorophenyl)-N-(2-isobutyl)-2-aminoimidazole, which has a specific biofilm-inhibiting effect at concentrations at which no activity against planktonic cells is detected. The stability of MIL-88B(Fe) in distilled water and tryptic soy broth medium is investigated, together with the ability of iron(III) chelators to serve as a trigger for controlled decomposition of MIL-88B(Fe) by metal complexation. Organic iron chelators are used to mimic the iron chelating function of siderophores, which are specific molecules excreted by biofilm-forming bacteria. Trisodium citrate is able to chelate metal ions from the junctions of the framework. By sequestration of these metal ions, the host matrix is partially degraded, resulting in an antibiofilm compound release. Finally, the antibiofilm properties against Salmonella Typhimurium are validated by monitoring biofilm growth on MOF layers either loaded or not with aminoimidazole. A strong proof-of-concept is shown for efficient inhibition of biofilm growth through triggered antibiofilm compound release.

  9. A multistimuli-responsive photochromic metal-organic gel.

    PubMed

    Wei, Shi-Chao; Pan, Mei; Li, Kang; Wang, Sujuan; Zhang, Jianyong; Su, Cheng-Yong

    2014-04-02

    A photochromic metal-organic gel with thermo-, photo-, and anion-responsive behavior is obtained. Unusually, heating of the Al-ligand solution leads to gel formation and cooling to room temperature reverses the process to reform the solution. The gel is sensitive to weakly coordinating anions. Additionally, reversible photochromic transformations take place both in the solution and gel states, accompanied by reversibly switched luminescence.

  10. Metal-Organic Frameworks for Thin-Layer Chromatographic Applications.

    PubMed

    Schenk, Claudia; Kutzscher, Christel; Drache, Franziska; Helten, Stella; Senkovska, Irena; Kaskel, Stefan

    2017-01-25

    Preparation of thin-layer chromatographic (TLC) plates based on metal-organic frameworks (MOFs) as porous stationary phases is described. DUT-67 (DUT = Dresden University of Technology), a zirconium based MOF, was used in combination with a fluorescent indicator as stationary phase for analyzing a small selection of a wide spectrum of relevant analytes. The successful separation of benzaldehyde from trans-cinnamaldehyde and 4-aminophenol from 2-aminotoluene is reported as a model system using optimized eluent mixtures containing acetic acid.

  11. Toxic Industrial Chemical Removal by Isostructural Metal-Organic Frameworks

    DTIC Science & Technology

    2011-01-01

    ISOSTRUCTURAL METAL-ORGANIC FRAMEWORKS Gregory W. Peterson RESEARCH AND TECHNOLOGY DIRECTORATE T. Grant Glover Bryan J. Schindler SCIENCE...APPLICATIONS INTERNATIONAL CORPORATION Gunpowder, MD 21010-0068 David Britt Omar Yaghi UNIVERSITY OF CALIFORNIA Los Angeles, CA 90095-1569 January 2011...Frameworks 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Peterson, Gregory W. (ECBC); Glover, T. Grant; Schindler

  12. Pneumocystis melanins confer enhanced organism viability.

    PubMed

    Icenhour, Crystal R; Kottom, Theodore J; Limper, Andrew H

    2006-06-01

    Pneumocystis continues to represent an important opportunistic fungal pathogen of those with compromised immunity. Thus, it is crucial to identify factors that affect its viability and pathogenicity. We previously reported the first identification of melanins in Pneumocystis. In the present study, we sought to further characterize these components and define the function for these melanins. Melanins extracted from Pneumocystis and melanized Pneumocystis cells were analyzed by electron spin resonance spectroscopy, revealing spectra consistent with melanins from other fungi. Immunofluorescence assays using anti-melanin monoclonal antibodies showed that melanins are widely present across Pneumocystis host species, including mouse-, ferret-, and human-derived Pneumocystis organisms, as well as Pneumocystis carinii derived from rat. Using immunoelectron microscopy, melanins were found to localize to the cell wall and cytoplasm of P. carinii cysts, as well as to intracystic bodies within mature cysts. Next, the role of melanins on the maintenance of Pneumocystis viability was determined by using quantitative reverse transcription-PCR measurement of the heat shock protein mRNA under adverse environmental conditions. Using a new method to promote the melanization of Pneumocystis, we observed that strongly melanized Pneumocystis retained viability to a greater degree when exposed to UV irradiation or desiccation compared to less-pigmented organisms. These studies support our previous identification of Pneumocystis melanins across the genus, further characterize these Pneumocystis components, and demonstrate that melanins protect Pneumocystis from environmental stressors.

  13. Evaluating metal-organic frameworks for natural gas storage

    SciTech Connect

    Mason, JA; Veenstra, M; Long, JR

    2014-01-01

    Metal-organic frameworks have received significant attention as a new class of adsorbents for natural gas storage; however, inconsistencies in reporting high-pressure adsorption data and a lack of comparative studies have made it challenging to evaluate both new and existing materials. Here, we briefly discuss high-pressure adsorption measurements and review efforts to develop metal-organic frameworks with high methane storage capacities. To illustrate the most important properties for evaluating adsorbents for natural gas storage and for designing a next generation of improved materials, six metal-organic frameworks and an activated carbon, with a range of surface areas, pore structures, and surface chemistries representative of the most promising adsorbents for methane storage, are evaluated in detail. High-pressure methane adsorption isotherms are used to compare gravimetric and volumetric capacities, isosteric heats of adsorption, and usable storage capacities. Additionally, the relative importance of increasing volumetric capacity, rather than gravimetric capacity, for extending the driving range of natural gas vehicles is highlighted. Other important systems-level factors, such as thermal management, mechanical properties, and the effects of impurities, are also considered, and potential materials synthesis contributions to improving performance in a complete adsorbed natural gas system are discussed.

  14. Evolution of form in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Lee, Jiyoung; Kwak, Ja Hun; Choe, Wonyoung

    2017-01-01

    Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal-organic materials (MOMs), an emerging class of porous materials consisting of metal-organic frameworks (MOFs) and metal-organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF. Moreover, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs. We anticipate that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.

  15. Fluorine in a Carbon-enhanced Metal-poor Star

    NASA Astrophysics Data System (ADS)

    Schuler, Simon C.; Cunha, Katia; Smith, Verne V.; Sivarani, Thirupathi; Beers, Timothy C.; Lee, Young Sun

    2007-09-01

    The fluorine abundance of the carbon-enhanced metal-poor (CEMP) star HE 1305+0132 has been derived by analysis of the molecular HF (1-0) R9 line at 2.3357 μm in a high-resolution (R=50,000) spectrum obtained with the Phoenix spectrometer and Gemini-South telescope. Our abundance analysis makes use of a CNO-enhanced ATLAS12 model atmosphere characterized by a metallicity and CNO enhancements determined utilizing medium-resolution (R=3000) optical and near-IR spectra. The effective iron abundance is found to be [Fe/H]=-2.5, making HE 1305+0132 the most Fe-deficient star, by more than an order of magnitude, for which the abundance of fluorine has been measured. Using spectral synthesis, we derive a supersolar fluorine abundance of A(19F)=4.96+/-0.21, corresponding to a relative abundance of [F/Fe]=+2.90. A single line of the Phillips C2 system is identified in our Phoenix spectrum, and along with multiple lines of the first-overtone vibration-rotation CO (3-1) band head, C and O abundances of A(12C)=8.57+/-0.11 and A(16O)=7.04+/-0.14 are derived. We consider the striking fluorine overabundance in the framework of the nucleosynthetic processes thought to be responsible for the C-enhancement of CEMP stars and conclude that the atmosphere of HE 1305+0132 was polluted via mass transfer by a primary companion during its asymptotic giant branch phase. This is the first study of fluorine in a CEMP star, and it demonstrates that this rare nuclide can be a key diagnostic of nucleosynthetic processes in the early Galaxy.

  16. Functionalization of plasmonic metamaterials utilizing metal-organic framework thin films

    NASA Astrophysics Data System (ADS)

    Jakšić, Zoran; Popović, Zora; Djerdj, Igor; Jaćimović, Željko K.; Radulović, Katarina

    2012-05-01

    We considered theoretically and experimentally a strategy to functionalize plasmonic metamaterials utilizing either a metal-organic framework (MOF) or inorganic-organic hybrids for application in adsorption-based gas sensing. MOFs are one-dimensional (1D), 2D or 3D crystalline compounds that simultaneously contain metal ions or ion clusters and organic moieties, forming thus porous networks ensuring an increased effective surface for adsorption. Metamaterials can enhance plasmonic sensor performance through metal-dielectric nanocompositing that simultaneously tailors the electromagnetic response and boosts adsorption of the targeted analyte through the use of nanopores. To perform functionalization, it is necessary to integrate one or several layers of MOF nanocrystals with the metamaterial scaffold. The simplest approach is to use dip or drop coating or the layer-by-layer technique. The scaffolds that we considered included freestanding, ultrathin membranes and sandwich structures with nanoaperture arrays. For this investigation, we used a non-aqueous sol-gel route to synthesize vanadium oxyanthracene carboxylate, a novel material with 1D crystal structure. Our results suggest that preferential concentration of analyte within the MOF pores may ensure improved adsorption and thus sensor sensitivity enhancement. Also, one may increase selectivity by introducing nanoparticle fillers or by utilizing other functionalizing materials such as catalysts or ligands.

  17. Improving thermoelectric efficiency in organic-metal nanocomposites via extra-low thermal boundary conductance

    NASA Astrophysics Data System (ADS)

    Jin, Yansha; Nola, Sam; Pipe, Kevin P.; Shtein, Max

    2013-11-01

    In organic semiconductors, the Wiedemann-Franz law is often violated, potentially enabling independent control over electrical and thermal conductivities, as observed here with the organic-metal nanocomposites. This effect is attributed to the interface between metal particles and organic matrix materials impeding thermal transport. Thermal conductivity (kth) can be decoupled from electrical conductivity (σe) in the composite of an archetypal organic semiconductor (Copper Phthalocyanine, CuPc) and silver, with thermal boundary conductance as low as 13 MW/m2K at the interface. We show that kth decreases with volume fraction occupied by silver nanoparticles (xAg%) in the dilute limit, reaching a minimum value at a concentration xAg%(min)=18%, while σe exceeds that of the pure organic semiconductor. Further modeling indicates that ZT values of organic-inorganic nanocomposites can be potentially enhanced 10 fold around xf%(min), compared to ZT of the pure compounds. These findings suggest a novel pathway for the future design of organic thermoelectric materials.

  18. Solubility Enhanced Oxidation of Hydrophobic Organic Contaminants

    NASA Astrophysics Data System (ADS)

    Boving, T. B.; Eberle, D. E.; Ball, R.

    2012-12-01

    In-situ chemical oxidation (ISCO) is a remediation technique considered to be effective at overcoming some of the limitations of conventional subsurface treatment processes for volatile and semi-volatile organic contaminants (VOC, SVOC). ISCO reactions occur predominately in the aqueous phase and as a result, contaminant availability is a major limiting factor, i.e. contaminants with higher aqueous solubility's are typically more accessible for oxidation than more hydrophobic, sorbed compounds. The purpose of this study was to determine the feasibility of a new integrated desorption-oxidation process for the remediation of contaminated waters and sediments. Specifically, this study examined the potential of using hydroxypropyl-β-cyclodextrin (HPCD), a modified cyclic sugar, and a blend of oxidants commercially known as OxyZone® (U.S. patent No. 7,667,087) for the remediation of polycyclic aromatic hydrocarbons (PAH). Laboratory scale batch experiments confirmed prior studies that HPCD increases the aqueous concentration of these contaminants, making a greater mass of contaminant available for subsequent oxidation. When exposed to the same amount of oxidant, the mass of PAH destroyed increased linearly with increasing HPCD concentration. Relative to PAH saturated solutions without HPCD, 11 times more PAH mass was destroyed when a PAH saturated 15 g/L HPCD solution was treated with the same mass of oxidant. Destruction of the aqueous phase contaminants followed first order exponential decay kinetics in both deionized water and HPCD solutions. However, the destruction of complexed PAH was slower than for uncomplexed PAH. The cause of this is likely due to the preferential destruction of the HPCD molecule by the oxidant, followed by the subsequent oxidation of the PAH. The destruction of the cyclodextrin was minimized by modifying the oxidant formulation. Overall, these findings establish the potential of utilizing HPCD and OxyZone® as an integrated desorption

  19. Early holocene trace metal enrichment in organic lake sediments, Baffin Island, Arctic Canada

    SciTech Connect

    Wolfe, A.P.; Haertling, J.W.

    1997-02-01

    Trace metals having accumulated in preindustrial ({sup 14}C dated) sediments from two small, acid-sensitive, arctic lakes show unexpected stratigraphic trends. Concentrations of Cu, Cr, Pb, Ni, and Zn have successive maxima in early to mid-Holocene sediments, of amplitudes comparable to lakes affected by loading from industrial atmospheric fallout. These profiles contrast sharply the concentrations of elements primarily associated with catchment erosion (Ti, V, Zr), and are attributed to the enhanced transport of organic-bound trace metals from the catchments to the lakes in the early Holocene. Paleoliminological conditions conferred effective sedimentary sinks for each of the enriched elements, although a certain degree of diagenetic mobilization is also observed. The study verifies that natural conditions may, under specific circumstances, produce sediment chemical signatures of potentially toxic metals that bear similarities to those reported from lakes adversely impacted by atmospheric pollution. 31 refs., 4 figs., 1 tab.

  20. Metallic coatings for enhancement of thermal contact conductance

    NASA Astrophysics Data System (ADS)

    Lambert, M. A.; Fletcher, L. S.

    1994-04-01

    The reliability of standard electronic modules may be improved by decreasing overall module temperature. This may be accomplished by enhancing the thermal contact conductance at the interface between the module frame guide rib and the card rail to which the module is clamped. Some metallic coatings, when applied to the card rail, would deform under load, increasing the contact area and associated conductance. This investigation evaluates the enhancements in thermal conductance afforded by vapor deposited silver and gold coatings. Experimental thermal conductance measurements were made for anodized aluminum 6101-T6 and electroless nickel-plated copper C11000-H03 card materials to the aluminum A356-T61 rail material. Conductance values for the electroless nickel-plated copper junction ranged from 600 to 2800 W/m(exp 2)K and those for the anodized aluminum junction ranged from 25 to 91 W/m(exp 2)K for contact pressures of 0.172-0.862 MPa and mean junction temperatures of 20-100 C. Experimental thermal conductance values of vapor deposited silver- and gold-coated aluminum A356-T61 rail surfaces indicate thermal enhancements of 1.25-2.19 for the electroless nickel-plated copper junctions and 1.79-3.41 for the anodized aluminum junctions. The silver and gold coatings provide significant thermal enhancement; however, these coating-substrate combinations are susceptible to galvanic corrosion under some conditions.

  1. Metallic coatings for enhancement of thermal contact conductance

    SciTech Connect

    Lambert, M.A.; Fletcher, L.S. )

    1994-04-01

    The reliability of standard electronic modules may be improved by decreasing overall module temperature. This may be accomplished by enhancing the thermal contact conductance at the interface between the module frame guide rib and the card rail to which the module is clamped. Some metallic coatings, when applied to the card rail, would deform under load, increasing the contact area and associated conductance. This investigation evaluates the enhancements in thermal conductance afforded by vapor deposited silver and gold coatings. Experimental thermal conductance measurements were made for anodized aluminum 6101-T6 and electroless nickel-plated copper C11000-H03 card materials to the aluminum A356-T61 rail material. Conductance values for the electroless nickel-plated copper junction ranged from 600 to 2800 W/m(exp 2)K and those for the anodized aluminum junction ranged from 25 to 91 W/m(exp 2)K for contact pressures of 0.172-0.862 MPa and mean junction temperatures of 20-100 C. Experimental thermal conductance values of vapor deposited silver- and gold-coated aluminum A356-T61 rail surfaces indicate thermal enhancements of 1.25-2.19 for the electroless nickel-plated copper junctions and 1.79-3.41 for the anodized aluminum junctions. The silver and gold coatings provide significant thermal enhancement; however, these coating-substrate combinations are susceptible to galvanic corrosion under some conditions. 25 refs.

  2. LITHIUM ABUNDANCES IN CARBON-ENHANCED METAL-POOR STARS

    SciTech Connect

    Masseron, Thomas; Johnson, Jennifer A.; Lucatello, Sara; Karakas, Amanda; Plez, Bertrand; Beers, Timothy C.; Christlieb, Norbert E-mail: jaj@astronomy.ohio-state.edu

    2012-05-20

    Carbon-enhanced metal-poor (CEMP) stars are believed to show the chemical imprints of more massive stars (M {approx}> 0.8 M{sub Sun }) that are now extinct. In particular, it is expected that the observed abundance of Li should deviate in these stars from the standard Spite lithium plateau. We study here a sample of 11 metal-poor stars and a double-lined spectroscopic binary with -1.8 < [Fe/H] < -3.3 observed with the Very Large Telescope/UVES spectrograph. Among these 12 metal-poor stars, there are 8 CEMP stars for which we measure or constrain the Li abundance. In contrast to previous arguments, we demonstrate that an appropriate regime of dilution permits the existence of 'Li-Spite plateau and C-rich' stars, whereas some of the 'Li-depleted and C-rich' stars call for an unidentified additional depletion mechanism that cannot be explained by dilution alone. We find evidence that rotation is related to the Li depletion in some CEMP stars. Additionally, we report on a newly recognized double-lined spectroscopic binary star in our sample. For this star, we develop a new technique from which estimates of stellar parameters and luminosity ratios can be derived based on a high-resolution spectrum alone, without the need for input from evolutionary models.

  3. Directional and enhanced spontaneous emission with a corrugated metal probe

    NASA Astrophysics Data System (ADS)

    Shen, Hongming; Lu, Guowei; He, Yingbo; Cheng, Yuqing; Liu, Haitao; Gong, Qihuang

    2014-06-01

    A three-dimensional corrugated metal tapered probe with surface corrugated gratings at the tip apex is proposed and investigated theoretically, which leads to an obvious emission beaming effect of spontaneous emission from a single emitter near the probe. In contrast with conventional apertureless metal probes, where only the enhancement of an optical near-field is concerned, the corrugated probe is able to manipulate local excitation intensity and far-field emission direction simultaneously. The angular emission from a single dipole source, being placed close to the corrugated probe, falls into a cone with a maximum directivity angle of +/-11.6°, which improves the collection efficiency 25-fold. Such a probe simultaneously increases the localized field intensity to about twice as strong as the conventional bare tip. In addition, the radiation pattern is sensitive to the working wavelength and the dipole to tip-apex separation. These findings make a promising route to the development of plasmonic spontaneous emission manipulation based on corrugated tapered antenna--for instance, tip-enhanced spectroscopy, single-molecule sensing, and single-photon source .

  4. High-internal-phase emulsions stabilized by metal-organic frameworks and derivation of ultralight metal-organic aerogels

    PubMed Central

    Zhang, Bingxing; Zhang, Jianling; Liu, Chengcheng; Peng, Li; Sang, Xinxin; Han, Buxing; Ma, Xue; Luo, Tian; Tan, Xiuniang; Yang, Guanying

    2016-01-01

    To design high-internal-phase emulsion (HIPE) systems is of great interest from the viewpoints of both fundamental researches and practical applications. Here we demonstrate for the first time the utilization of metal-organic framework (MOF) for HIPE formation. By stirring the mixture of water, oil and MOF at room temperature, the HIPE stabilized by the assembly of MOF nanocrystals at oil-water interface could be formed. The MOF-stabilized HIPE provides a novel route to produce highly porous metal-organic aerogel (MOA) monolith. After removing the liquids from the MOF-stabilized HIPE, the ultralight MOA with density as low as 0.01 g·cm−3 was obtained. The HIPE approach for MOA formation has unique advantages and is versatile in producing different kinds of ultralight MOAs with tunable porosities and structures. PMID:26892258

  5. Refolding of horseradish peroxidase is enhanced in presence of metal cofactors and ionic liquids.

    PubMed

    Bae, Sang-Woo; Eom, Doyoung; Mai, Ngoc Lan; Koo, Yoon-Mo

    2016-03-01

    The effects of various refolding additives, including metal cofactors, organic co-solvents, and ionic liquids, on the refolding of horseradish peroxidase (HRP), a well-known hemoprotein containing four disulfide bonds and two different types of metal centers, a ferrous ion-containing heme group and two calcium atoms, which provide a stabilizing effect on protein structure and function, were investigated. Both metal cofactors (Ca(2+) and hemin) and ionic liquids have positive impact on the refolding of HRP. For instance, the HRP refolding yield remarkably increased by over 3-fold upon addition of hemin and calcium chloride to the refolding buffer as compared to that in the conventional urea-containing refolding buffer. Moreover, the addition of ionic liquids [EMIM][Cl] to the hemin and calcium cofactor-containing refolding buffer further enhanced the HRP refolding yield up to 80% as compared to 12% in conventional refolding buffer at relatively high initial protein concentration (5 mg/ml). These results indicated that refolding method utilizing metal cofactors and ionic liquids could enhance the yield and efficiency for metalloprotein.

  6. Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies

    NASA Astrophysics Data System (ADS)

    Cong, Shan; Yuan, Yinyin; Chen, Zhigang; Hou, Junyu; Yang, Mei; Su, Yanli; Zhang, Yongyi; Li, Liang; Li, Qingwen; Geng, Fengxia; Zhao, Zhigang

    2015-07-01

    Surface-enhanced Raman spectroscopy (SERS) represents a very powerful tool for the identification of molecular species, but unfortunately it has been essentially restricted to noble metal supports (Au, Ag and Cu). While the application of semiconductor materials as SERS substrate would enormously widen the range of uses for this technique, the detection sensitivity has been much inferior and the achievable SERS enhancement was rather limited, thereby greatly limiting the practical applications. Here we report the employment of non-stoichiometric tungsten oxide nanostructure, sea urchin-like W18O49 nanowire, as the substrate material, to magnify the substrate-analyte molecule interaction, leading to significant magnifications in Raman spectroscopic signature. The enrichment of surface oxygen vacancy could bring additional enhancements. The detection limit concentration was as low as 10-7 M and the maximum enhancement factor was 3.4 × 105, in the rank of the highest sensitivity, to our best knowledge, among semiconducting materials, even comparable to noble metals without `hot spots'.

  7. Controlling the magnetism of adsorbed metal-organic molecules

    NASA Astrophysics Data System (ADS)

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-01

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule’s magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  8. Controlling the magnetism of adsorbed metal-organic molecules.

    PubMed

    Kuch, Wolfgang; Bernien, Matthias

    2017-01-18

    Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

  9. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series.

    PubMed

    Rodríguez-Albelo, L Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A Rabdel; Calero, Sofia; Navarro, Jorge A R

    2017-02-15

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  10. Interplay between defects, disorder and flexibility in metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Bennett, Thomas D.; Cheetham, Anthony K.; Fuchs, Alain H.; Coudert, François-Xavier

    2017-01-01

    Metal-organic frameworks are a novel family of chemically diverse materials, which are of interest across engineering, physics, chemistry, biology and medicine-based disciplines. Since the development of the field in its current form more than two decades ago, priority has been placed on the synthesis of new structures. However, more recently, a clear trend has emerged in shifting the emphasis from material design to exploring the chemical and physical properties of structures already known. In particular, although such nanoporous materials were traditionally seen as rigid crystalline structures, there is growing evidence that large-scale flexibility, the presence of defects and long-range disorder are not the exception in metal-organic frameworks, but the rule. Here we offer some perspective into how these concepts are perhaps inescapably intertwined, highlight recent advances in our understanding and discuss how a consideration of the interfaces between them may lead to enhancements of the materials' functionalities.

  11. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    NASA Astrophysics Data System (ADS)

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A. R.

    2017-02-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  12. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    PubMed Central

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A.R.

    2017-01-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects. PMID:28198376

  13. Improved Method Being Developed for Surface Enhancement of Metallic Materials

    NASA Technical Reports Server (NTRS)

    Gabb, Timothy P.; Telesman, Jack; Kantzos, Peter T.

    2001-01-01

    Surface enhancement methods induce a layer of beneficial residual compressive stress to improve the impact (FOD) resistance and fatigue life of metallic materials. A traditional method of surface enhancement often used is shot peening, in which small steel spheres are repeatedly impinged on metallic surfaces. Shot peening is inexpensive and widely used, but the plastic deformation of 20 to 40 percent imparted by the impacts can be harmful. This plastic deformation can damage the microstructure, severely limiting the ductility and durability of the material near the surface. It has also been shown to promote accelerated relaxation of the beneficial compressive residual stresses at elevated temperatures. Low-plasticity burnishing (LPB) is being developed as an improved method for the surface enhancement of metallic materials. LPB is being investigated as a rapid, inexpensive surface enhancement method under NASA Small Business Innovation Research contracts NAS3-98034 and NAS3-99116, with supporting characterization work at NASA. Previously, roller burnishing had been employed to refine surface finish. This concept was adopted and then optimized as a means of producing a layer of compressive stress of high magnitude and depth, with minimal plastic deformation (ref. 1). A simplified diagram of the developed process is given in the following figure. A single pass of a smooth, free-rolling spherical ball under a normal force deforms the surface of the material in tension, creating a compressive layer of residual stress. The ball is supported in a fluid with sufficient pressure to lift the ball off the surface of the retaining spherical socket. The ball is only in mechanical contact with the surface of the material being burnished and is free to roll on the surface. This apparatus is designed to be mounted in the conventional lathes and vertical mills currently used to machine parts. The process has been successfully applied to nickel-base superalloys by a team from the

  14. Single molecule fluorescence studies of ribosome dynamics: An application of metal enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Bharill, Shashank

    Metal enhanced fluorescence (MEF), in which a surface plasmon near a noble metal alters the spectral properties of an organic fluorophore, has been reported to increase fluorescence intensity without a concomitant increase in photobleaching rate. The fluorescence intensities of Cy3- and Cy5-labeled ribosomal initiation complexes (ICs) near 50 nm silver particles were increased 4 - 7-fold compared to ICs in the absence of silver colloids. Photobleaching lifetime was not significantly decreased, resulting in 4 - 5.5-fold enhancement in total photon emission prior to photobleaching. Fluorophores showing enhanced fluorescence were located within ˜280 nm of the colloidal particles, as detected by light scattering and scanning probe microscopy. Aggregates of silver particles or larger colloids themselves produced wavelength-shifted luminescence similar to fluorescence, presumably due to resonant extinction between nearby metal particles. Intensity fluctuations above shot noise, at 0.1 - 5 Hz, were greater from slides containing colloidal particles than from plain glass. Overall signal to noise ratio was similar or slightly better near the silver particles. Proximity to silver particles did not compromise ribosome function, as measured by codon-dependent binding of fluorescent tRNA to the A site of fluorescent labeled ribosomes, dynamics of fluorescence resonance energy transfer between adjacent tRNAs in the ribosomal A and P sites, and elongation factor G catalyzed translocation.

  15. Controlled Encapsulation of Functional Organic Molecules within Metal-Organic Frameworks: In Situ Crystalline Structure Transformation.

    PubMed

    Guan, Jinju; Hu, Yu; Wang, Yu; Li, Hongfeng; Xu, Zhiling; Zhang, Tao; Wu, Peng; Zhang, Suoying; Xiao, Gengwu; Ji, Wenlan; Li, Linjie; Zhang, Meixuan; Fan, Yun; Li, Lin; Zheng, Bing; Zhang, Weina; Huang, Wei; Huo, Fengwei

    2017-01-23

    Functional organic molecules/metal-organic frameworks composites can be obtained by in situ crystalline structure transformation from ZIF-L to ZIF-8-L under double solvent conditions. Interestingly, the as-prepared molecules/ZIF-8-L composites with the leaf-like morphology exhibit good fluorescence properties and size selectivity in fluorescent quenchers due to the molecular sieving effect of the well-defined microporous ZIF-8-L.

  16. Metal-organic framework templated synthesis of ultrathin, well-aligned metallic nanowires.

    PubMed

    Volosskiy, Boris; Niwa, Kenta; Chen, Yu; Zhao, Zipeng; Weiss, Nathan O; Zhong, Xing; Ding, Mengning; Lee, Chain; Huang, Yu; Duan, Xiangfeng

    2015-03-24

    With well-defined porous structures and dimensions, metal-organic frameworks (MOFs) can function as versatile templates for the growth of metallic nanostructures with precisely controlled shapes and sizes. Using MOFs as templates, metallic nanostructures can be grown without the need of bulky surfactants and thus preserve their intrinsic surface. Additionally, the high surface area of MOFs can also ensure that the surface of the template metallic nanostructures is readily accessible, which is critical for the proper function of catalysts or sensors. The hybrid metal@MOF structures have been demonstrated to exhibit useful properties not found in either component separately. Here we report the growth of ultrafine metallic nanowires inside one-dimensional MOF pores with well-controlled shape and size. Our study shows that solvent selection plays an important role in controlling precursor loading and the reduction rate inside the MOF pores for the formation of the nanowires. The growth of the well-aligned, ultrathin nanowires was monitored and characterized by transmission electron microscopy, X-ray diffraction, UV-vis spectroscopy, fluorescence studies, and Brunauer-Emmet-Teller surface area analysis.

  17. Reusable oxidation catalysis using metal-monocatecholato species in a robust metal-organic framework.

    PubMed

    Fei, Honghan; Shin, JaeWook; Meng, Ying Shirley; Adelhardt, Mario; Sutter, Jörg; Meyer, Karsten; Cohen, Seth M

    2014-04-02

    An isolated metal-monocatecholato moiety has been achieved in a highly robust metal-organic framework (MOF) by two fundamentally different postsynthetic strategies: postsynthetic deprotection (PSD) and postsynthetic exchange (PSE). Compared with PSD, PSE proved to be a more facile and efficient functionalization approach to access MOFs that could not be directly synthesized under solvothermal conditions. Metalation of the catechol functionality residing in the MOFs resulted in unprecedented Fe-monocatecholato and Cr-monocatecholato species, which were characterized by X-ray absorption spectroscopy, X-band electron paramagnetic resonance spectroscopy, and (57)Fe Mössbauer spectroscopy. The resulting materials are among the first examples of Zr(IV)-based UiO MOFs (UiO = University of Oslo) with coordinatively unsaturated active metal centers. Importantly, the Cr-metalated MOFs are active and efficient catalysts for the oxidation of alcohols to ketones using a wide range of substrates. Catalysis could be achieved with very low metal loadings (0.5-1 mol %). Unlike zeolite-supported, Cr-exchange oxidation catalysts, the MOF-based catalysts reported here are completely recyclable and reusable, which may make them attractive catalysts for 'green' chemistry processes.

  18. Carbon Dioxide Separation with Novel Microporous Metal Organic Frameworks

    SciTech Connect

    Richard Willis; Annabelle Benin; John Low; Ganesh Venimadhavan; Syed Faheem; David Lesch; Adam Matzger; Randy Snurr

    2008-02-04

    The goal of this program was to develop a low cost novel sorbent to remove carbon dioxide from flue gas and gasification streams in electric utilities. Porous materials named metal-organic frameworks (MOFs) were found to have good capacity and selectivity for the capture of carbon dioxide. Several materials from the initial set of reference MOFs showed extremely high CO{sub 2} adsorption capacities and very desirable linear isotherm shapes. Sample preparation occurred at a high level, with a new family of materials suitable for intellectual property protection prepared and characterized. Raman spectroscopy was shown to be useful for the facile characterization of MOF materials during adsorption and especially, desorption. Further, the development of a Raman spectroscopic-based method of determining binary adsorption isotherms was initiated. It was discovered that a stronger base functionality will need to be added to MOF linkers in order to enhance CO{sub 2} selectivity over other gases via a chemisorption mechanism. A concentrated effort was expended on being able to accurately predict CO{sub 2} selectivities and on the calculation of predicted MOF surface area values from first principles. A method of modeling hydrolysis on MOF materials that correlates with experimental data was developed and refined. Complimentary experimental data were recorded via utilization of a combinatorial chemistry heat treatment unit and high-throughput X-ray diffractometer. The three main Deliverables for the project, namely (a) a MOF for pre-combustion (e.g., IGCC) CO{sub 2} capture, (b) a MOF for post-combustion (flue gas) CO{sub 2} capture, and (c) an assessment of commercial potential for a MOF in the IGCC application, were completed. The key properties for MOFs to work in this application - high CO{sub 2} capacity, good adsorption/desorption rates, high adsorption selectivity for CO{sub 2} over other gases such as methane and nitrogen, high stability to contaminants, namely

  19. Metal-organic frameworks with dynamic interlocked components

    NASA Astrophysics Data System (ADS)

    Vukotic, V. Nicholas; Harris, Kristopher J.; Zhu, Kelong; Schurko, Robert W.; Loeb, Stephen J.

    2012-06-01

    The dynamics of mechanically interlocked molecules such as rotaxanes and catenanes have been studied in solution as examples of rudimentary molecular switches and machines, but in this medium, the molecules are randomly dispersed and their motion incoherent. As a strategy for achieving a higher level of molecular organization, we have constructed a metal-organic framework material using a [2]rotaxane as the organic linker and binuclear Cu(II) units as the nodes. Activation of the as-synthesized material creates a void space inside the rigid framework that allows the soft macrocyclic ring of the [2]rotaxane to rotate rapidly, unimpeded by neighbouring molecular components. Variable-temperature 13C and 2H solid-state NMR experiments are used to characterize the nature and rate of the dynamic processes occurring inside this unique material. These results provide a blueprint for the future creation of solid-state molecular switches and molecular machines based on mechanically interlocked molecules.

  20. Transition metal oxides for organic electronics: energetics, device physics and applications.

    PubMed

    Meyer, Jens; Hamwi, Sami; Kröger, Michael; Kowalsky, Wolfgang; Riedl, Thomas; Kahn, Antoine

    2012-10-23

    During the last few years, transition metal oxides (TMO) such as molybdenum tri-oxide (MoO(3) ), vanadium pent-oxide (V(2) O(5) ) or tungsten tri-oxide (WO(3) ) have been extensively studied because of their exceptional electronic properties for charge injection and extraction in organic electronic devices. These unique properties have led to the performance enhancement of several types of devices and to a variety of novel applications. TMOs have been used to realize efficient and long-term stable p-type doping of wide band gap organic materials, charge-generation junctions for stacked organic light emitting diodes (OLED), sputtering buffer layers for semi-transparent devices, and organic photovoltaic (OPV) cells with improved charge extraction, enhanced power conversion efficiency and substantially improved long term stability. Energetics in general play a key role in advancing device structure and performance in organic electronics; however, the literature provides a very inconsistent picture of the electronic structure of TMOs and the resulting interpretation of their role as functional constituents in organic electronics. With this review we intend to clarify some of the existing misconceptions. An overview of TMO-based device architectures ranging from transparent OLEDs to tandem OPV cells is also given. Various TMO film deposition methods are reviewed, addressing vacuum evaporation and recent approaches for solution-based processing. The specific properties of the resulting materials and their role as functional layers in organic devices are discussed.

  1. Photonic confinement in laterally structured metal-organic microcavities

    NASA Astrophysics Data System (ADS)

    Mischok, Andreas; Brückner, Robert; Sudzius, Markas; Reinhardt, Christoph; Lyssenko, Vadim G.; Fröb, Hartmut; Leo, Karl

    2014-08-01

    We investigate the formation of optical modes in organic microcavities with an incorporated perforated silver layer. The metal leads to a formation of Tamm-plasmon-polaritons and thus separates the sample into metal-free or metal-containing areas, supporting different resonances. This mode splitting is exploited to confine photons in elliptic holes and triangular cuts, forming distinctive standing wave patterns showing the strong lateral confinement. A comparison with a Maxwell-Bloch based rate equation model clearly shows the nonlinear transition into the lasing regime. The concentration of the electric field density and inhibition of lateral loss channels in turn decreases the lasing threshold by up to one order of magnitude, to 0.1 nJ. By spectroscopic investigation of such a triangular wedge, we observe the transition from the unperturbed cavity state to a strongly confined complex transversal mode. Such a structured silver layer can be utilized in future for charge carrier injection in an electrically driven organic solid state laser.

  2. Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins.

    PubMed

    Liu, Yan; Li, Zijian; Yuan, Guozan; Xia, Qingchun; Yuan, Chen; Cui, Yong

    2016-12-19

    A homochiral 3D porous metal-organic framework was assembled from a chiral dicarboxylic acid-functionalized Cu(salen)-based catalyst and could serve as an efficient heterogeneous catalyst for aziridination and allylic amination of olefins. Besides easy separation and reuse of the catalyst, the chiral framework confinement could impart substrate size selectivity, enhance catalyst activity, and induce product enantioselectivity.

  3. Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment.

    PubMed

    Wu, Xiaoling; Ge, Jun; Yang, Cheng; Hou, Miao; Liu, Zheng

    2015-09-07

    The one-step and facile synthesis of multi-enzyme-containing metal-organic framework (MOF) nanocrystals in aqueous solution at 25 °C was reported in this study. The GOx&HRP/ZIF-8 nanocomposite displayed high catalytic efficiency, high selectivity and enhanced stability due to the protecting effect of the framework.

  4. Enhanced performance of dicationic ionic liquid electrolytes by organic solvents

    NASA Astrophysics Data System (ADS)

    Li, Song; Zhang, Pengfei; Fulvio Pasquale, F.; Hillesheim Patrick, C.; Feng, Guang; Dai, Sheng; Cummings Peter, T.

    2014-07-01

    The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.

  5. Metal inhibition on the reactivity of manganese dioxide toward organic contaminant oxidation in relation to metal adsorption and ionic potential.

    PubMed

    Jiang, Jing; Wang, Zhuopu; Chen, Yang; He, Anfei; Li, Jianliang; Sheng, G Daniel

    2017-03-01

    Coexisting metal ions may significantly inhibit the oxidative reactivity of manganese oxides toward organic contaminants in metal-organic multi-pollutant waters. While the metal inhibition on the oxidation of organic contaminants by manganese oxides has previously been reported, the extent of the inhibition in relation to metal properties has not been established. Six alkali, alkaline, and transition metals, as well as two testing metals were evaluated for their abilities to inhibit the reactivity of birnessite. Regardless of the pathways of phenol and diuron oxidation (polymerization vs. breakdown), the extent of metal inhibition depended mainly on the metal itself and its concentration. The observed metal inhibition efficiency followed the order of Mn(2+) > Co(2+) > Cu(2+) > Al(3+) > Mg(2+) > K(+), consistent with metal adsorption on birnessite. The first-order organic oxidation rate constant (kobs) was linearly negatively correlated with metal adsorption (qe) on birnessite. These observations demonstrated that the metal inhibition efficiency was determined by metal adsorption on birnessite. The slopes of the kobs-qe varied among metals and followed the order of K(+) > Ca(2+) > Mg(2+) > Mn(2+) > Cd(2+) > Co(2+) > Cu(2+) > Al(3+). These slopes defined intrinsic inhibitory abilities of metals. As metals were adsorbed hydrated on birnessite, the intrinsic inhibitory ability was significantly linearly correlated with ionic potentials of metals, leading to a single straight line. Metals with multiple d electrons in the outermost orbit with polarizing energy that promotes hydrolysis sat slightly below the line, and vice versa.

  6. Solvothermal Metal Metathesis on a Metal-Organic Framework with Constricted Pores and the Study of Gas Separation.

    PubMed

    Li, Liangjun; Xue, Haitao; Wang, Ying; Zhao, Pinhui; Zhu, Dandan; Jiang, Min; Zhao, Xuebo

    2015-11-18

    Metal-organic frameworks (MOFs) with constricted pores can increase the adsorbate density of gas and facilitate effective CO2 separation from flue gas or natural gas due to their enhanced overlapping of potential fields of the pores. Herein, an MOF with constricted pores, which was formed by narrow channels and blocks of functional groups, was fabricated from the assembly of a methyl-functionalized ligand and Zn(II) centers (termed NPC-7-Zn). Structural analysis of the as-synthesized NPC-7-Zn reveals a series of zigzag pores with pore diameters of ∼0.7 nm, which could be favorable for CO2 traps. For reinforcing the framework stability, a solvothermal metal metathesis on the pristine MOF NPC-7-Zn was performed, and a new Cu(II) MOF (termed NPC-7-Cu) with an identical framework was produced. The influence of the reaction temperatures on the metal metathesis process was investigated. The results show that the constricted pores in NPC-7-Zn can induce kinetic issues that largely slow the metal metathesis process at room temperature. However, this kinetic issue can be solved by applying higher reaction temperatures. The modified MOF NPC-7-Cu exhibits significant improvements in framework stability and thus leads to a permanent porosity for this framework. The constricted pore structure enables enhanced potential fields for these pores, rendering this MOF with high adsorbate densities for CO2 and high adsorption selectivity for a CO2/N2 gas mixture. The adsorption kinetic studies reveal that CH4 has a faster diffusion rate constant than CO2, showing a surface diffusion controlled mechanism for CO2 and CH4 adsorption.

  7. Quantum dynamical simulations of local field enhancement in metal nanoparticles.

    PubMed

    Negre, Christian F A; Perassi, Eduardo M; Coronado, Eduardo A; Sánchez, Cristián G

    2013-03-27

    Field enhancements (Γ) around small Ag nanoparticles (NPs) are calculated using a quantum dynamical simulation formalism and the results are compared with electrodynamic simulations using the discrete dipole approximation (DDA) in order to address the important issue of the intrinsic atomistic structure of NPs. Quite remarkably, in both quantum and classical approaches the highest values of Γ are located in the same regions around single NPs. However, by introducing a complete atomistic description of the metallic NPs in optical simulations, a different pattern of the Γ distribution is obtained. Knowing the correct pattern of the Γ distribution around NPs is crucial for understanding the spectroscopic features of molecules inside hot spots. The enhancement produced by surface plasmon coupling is studied by using both approaches in NP dimers for different inter-particle distances. The results show that the trend of the variation of Γ versus inter-particle distance is different for classical and quantum simulations. This difference is explained in terms of a charge transfer mechanism that cannot be obtained with classical electrodynamics. Finally, time dependent distribution of the enhancement factor is simulated by introducing a time dependent field perturbation into the Hamiltonian, allowing an assessment of the localized surface plasmon resonance quantum dynamics.

  8. Transformation of metal-organic frameworks for molecular sieving membranes

    NASA Astrophysics Data System (ADS)

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-04-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively.

  9. Transformation of metal-organic frameworks for molecular sieving membranes

    PubMed Central

    Li, Wanbin; Zhang, Yufan; Zhang, Congyang; Meng, Qin; Xu, Zehai; Su, Pengcheng; Li, Qingbiao; Shen, Chong; Fan, Zheng; Qin, Lei; Zhang, Guoliang

    2016-01-01

    The development of simple, versatile strategies for the synthesis of metal-organic framework (MOF)-derived membranes are of increasing scientific interest, but challenges exist in understanding suitable fabrication mechanisms. Here we report a route for the complete transformation of a series of MOF membranes and particles, based on multivalent cation substitution. Through our approach, the effective pore size can be reduced through the immobilization of metal salt residues in the cavities, and appropriate MOF crystal facets can be exposed, to achieve competitive molecular sieving capabilities. The method can also be used more generally for the synthesis of a variety of MOF membranes and particles. Importantly, we design and synthesize promising MOF membranes candidates that are hard to achieve through conventional methods. For example, our CuBTC/MIL-100 membrane exhibits 89, 171, 241 and 336 times higher H2 permeance than that of CO2, O2, N2 and CH4, respectively. PMID:27090597

  10. Plasmonic Enhancement of Raman Signal using Complex Metallic Nanostructures based on DNA Origami

    NASA Astrophysics Data System (ADS)

    Finkelstein, Gleb

    2015-03-01

    DNA-based nanostructures, such as ``DNA origami,'' have recently emerged as one of the leading techniques for precise positioning of nanoscale materials in fields ranging from computer science to biomedical engineering. The origami is composed of a single scaffold DNA strand to which smaller ``staple`` strands are attached through DNA complementarity. The staples help to fold the scaffold strand into the designed structure of a predetermined shape. The resulting templates are highly addressable and have proven to be versatile tools for site-specific placement of various nanocomponents, such as metallic nanoparticles, quantum dots, fluorophores, etc. Building upon massively paralleled assembly mechanism of the origami and its ability to position nanocomponents, one may hope to utilize it for biosensing purposes. One attractive goal is the Raman spectroscopy, which provides a highly specific chemical fingerprint. Unfortunately, the Raman scattering cross section is small; Surface Enhanced Raman Spectroscopy (SERS) enhances the otherwise weak Raman signal by trapping the analyte molecules in the regions of intense electric field produced near rough metallic surfaces. These ``hot spots`` can be understood as resulting from localized surface plasmon modes resonantly exited by the incident laser excitation. We have earlier shown that metallic nanoparticles controllably attached to DNA origami can be further enlarged via an in-solution metallization; this technique allowed us to build metallic structures of complex topology. Recently, we have performed Raman spectroscopy of molecules attached to these metallic assemblies. Specifically, DNA origami is first used to organize the metallic structures, followed by a covalent attachment of Raman-active molecules to the metal. We found that the substrates with four nanoparticles per origami produce a strongly enhanced Raman signal compared to the control samples with only one nanoparticle per origami for the same particle

  11. Plasmonic effect-enhanced Ag nanodisk incorporated ZnO/Si metal-semiconductor-metal photodetectors

    NASA Astrophysics Data System (ADS)

    Kumar, Manjeet; Kojori, Hossein Shokri; Kim, Sung Jin; Park, Hyeong-Ho; Kim, Joondong; Yun, Ju-Hyung

    2016-10-01

    In this work, we present the enhancement of ultraviolet (UV) photodetection of Ag-ZnO thin film deposited by radio frequency magnetron sputtering. The surface morphological, optical, structural, and electrical properties of the deposited thin films were investigated by various characterization techniques. With this Ag-ZnO thin film structure and proper geometry of metal-semiconductor-metal (MSM) interdigitated structure design, photocurrent enhancement has been accomplished. MSM-photodetectors (PDs) using structures of Ag-ZnO gave a 30 times higher magnitude photocurrent at 340 nm of the wavelength. Plasmon-induced hot electrons contributed to improved spectral response to the UV region, while absorption and scattering effect enhanced broadband improvement to a response in the VIS-IR spectrum range. The improvement of Ag-ZnO PD in comparison with ZnO is attributed to the surface plasmon effect using Ag nanodisks. These results indicate that Ag-ZnO thin films can serve as excellent ultraviolet-PD and a very promising candidate for practical applications.

  12. Hydrogen storage by physisorption on Metal Organic Frameworks

    NASA Astrophysics Data System (ADS)

    Dailly, Anne

    2008-03-01

    Cryo-adsorption systems based on materials with high specific surface areas have the main advantage that they can store and release hydrogen with fast kinetics and high reversibility over multiples cycles. Recently Metal Organic Frameworks (MOFs) have been proposed as promising adsorbents for hydrogen. These crystallographically well organized hybrid solids resulting from the three dimensional connection of inorganic clusters using organic linkers show the largest specific surface areas of all known crystalline solids. The determination of the relationships between physical properties (chemistry, structure, surface area ) of the MOFs and their hydrogen storage behavior is a key step in the characterization of these materials, if they are to be designed for hydrogen storage applications. Excess hydrogen sorption measurements for different MOFs will be presented. We show that maximum hydrogen uptake at high pressure and 77K does not always scale with the specific surface area. A linear correlation trend only apply within a class of specific materials and breaks down when the surface area measurement does not represent the surface sites that are available to H2. The influence of pore size and shape will also be discussed by comparing several MOFs with different structure types. The hydrogen adsorption and binding energy at low pressure are strongly dependent on the metal ions and the pore size.

  13. Fabrication of Porous Matrix Membrane (PMM) Using Metal-Organic Framework as Green Template for Water Treatment

    PubMed Central

    Lee, Jian-Yuan; Tang, Chuyang Y.; Huo, Fengwei

    2014-01-01

    Pressure-driven membranes with high porosity can potentially be fabricated by removing template, such as low water stability metal-organic frameworks (MOFs) or other nanoparticles, in polymeric matrix. We report on the use of benign MOFs as green template to enhance porosity and interconnectivity of the water treatment membranes. Significantly enhanced separation performance was observed which might be attributed to the mass transfer coefficient of the substrate layer increased in ultrafiltration (UF) application. PMID:24435326

  14. Composites for removing metals and volatile organic compounds and method thereof

    DOEpatents

    Coronado, Paul R.; Coleman, Sabre J.; Reynolds, John G.

    2006-12-12

    Functionalized hydrophobic aerogel/solid support structure composites have been developed to remove metals and organic compounds from aqueous and vapor media. The targeted metals and organics are removed by passing the aqueous or vapor phase through the composite which can be in molded, granular, or powder form. The composites adsorb the metals and the organics leaving a purified aqueous or vapor stream. The species-specific adsorption occurs through specific functionalization of the aerogels tailored towards specific metals and/or organics. After adsorption, the composites can be disposed of or the targeted metals and/or organics can be reclaimed or removed and the composites recycled.

  15. Optical metal-organic framework sensor for selective discrimination of some toxic metal ions in water.

    PubMed

    Shahat, Ahmed; Hassan, Hassan M A; Azzazy, Hassan M E

    2013-09-02

    This paper reports the development of a facile and effective approach, based on the use of Zr-based metal-organic frameworks (UiO-66) sensor with micropores geometry, shape and particle morphology for the visual detection and removal of ultra-traces of some toxic metal ions such as Bi(III), Zn(II), Pb(II), Hg(II) and Cd(II). UiO-66 was used as selective carriers for accommodating hydrophobic chromophore probes such as dithizone (DZ) without coupling agent for sensitive and selective discrimination of trace level of toxic analytes. The developed UiO-66 sensor was utilized for the detection of ultra-traces of some toxic metal ions with the naked eye. The new sensor displays high sensitivity and selectivity of a wide range of detectable metals analytes up to 10(-10) mol dm(-3) in solution, in a rapid analyte uptake response (seconds). The developed sensor is stable, cost effective, easy to prepare, and would be useful for rapid detection and removal of ultra-traces of toxic metal ions in water samples.

  16. Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

    NASA Technical Reports Server (NTRS)

    Loo, B. H.; Lee, Y. G.; Frazier, D. O.

    1986-01-01

    Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

  17. Engineering Metallic Nanoparticles for Enhancing and Probing Catalytic Reactions.

    PubMed

    Collins, Gillian; Holmes, Justin D

    2016-07-01

    Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs.

  18. Polyamino acid functionalized membranes for metal capture and nanofiltration of organics: Modeling and experimental verification

    NASA Astrophysics Data System (ADS)

    Hestekin, Jamie Allen

    2000-10-01

    Passive membranes have been used for separations ranging from seawater desalination via reverse osmosis to the separation of particles with microfiltration membranes. However the attachment of macromolecules, with multiple functional sites, to microfiltration membranes allows for more selective separations. For these reasons, we have designed a novel membrane system, consisting of cellulose-based microfiltration membranes functionalized with polyamino acids (2,500--15,000 MW). Because of the high carboxyl content of the polyamino acids, these membranes have been shown to be extremely useful for the separation of heavy metals from aqueous solutions. The primary objective of this research was to establish the sorption mechanisms of functionalized microfiltration membranes and use these mechanisms to predict the rate behavior of metal transport through these membranes. Both cellulose acetate and pure cellulose were used as membrane support materials. Extensive experiments (pH 3--6) were conducted (under convective flow mode) with the derivatized membranes involving the heavy metals: lead, cadmium, nickel, copper, and selected mixtures with calcium in aqueous solutions. Metal sorption results were found to be a function of derivatization (aldehydes) density of membranes and degree of attachment of the polyfunctional groups, number of functional groups per chain, membrane surface area, and the type of metals to be sorbed. We have obtained metal sorption capacities as high as 1.5 g metal/g membrane. As opposed to homogeneous solution systems, the molar sorption capacities of the functional carboxyl sites are significantly enhanced in the membrane pores because of counterion condensation resulting partly from the extremely high charge densities in the membrane pores. This phenomenon was incorporated in a kinetic model for the prediction of sorption behavior. The model studied the effect of pore size, polyamino acid attachment density, pH, and metal type. Finally, in

  19. Postsynthetic Tuning of Metal-Organic Frameworks for Targeted Applications.

    PubMed

    Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong; Howarth, Ashlee J; Farha, Omar K; Hupp, Joseph T

    2017-02-08

    Metal-organic frameworks (MOFs) are periodic, hybrid, atomically well-defined porous materials that typically form by self-assembly and consist of inorganic nodes (metal ions or clusters) and multitopic organic linkers. MOFs as a whole offer many intriguing properties, including ultrahigh porosity, tunable chemical functionality, and low density. These properties point to numerous potential applications, including gas storage, chemical separations, catalysis, light harvesting, and chemical sensing, to name a few. Reticular chemistry, or the linking of molecular building blocks into predetermined network structures, has been employed to synthesize thousands of MOFs. Given the vast library of candidate nodes and linkers, the number of potentially synthetically accessible MOFs is enormous. Nevertheless, a powerful complementary approach to obtain specific structures with desired chemical functionality is to modify known MOFs after synthesis. This approach is particularly useful when incorporation of particular chemical functionalities via direct synthesis is challenging or impossible. The challenges may stem from limited stability or solubility of precursors, unwanted secondary reactivity of precursors, or incompatibility of functional groups with the conditions needed for direct synthesis. MOFs can be postsynthetically modified by replacing the metal nodes and/or organic linkers or via functionalization of the metal nodes and/or organic linkers. Here we describe some of our efforts toward the development and application of postsynthetic strategies for imparting desired chemical functionalities in MOFs of known topology. The techniques include methods for functionalizing MOF nodes, i.e., solvent-assisted ligand incorporation (SALI) and atomic layer deposition in MOFs (AIM) as well as a method to replace structural linkers, termed solvent-assisted linker exchange (SALE), also known as postsynthethic exchange (PSE). For each functionalization strategy, we first describe

  20. The surface chemistry of metal-organic frameworks.

    PubMed

    McGuire, Christina V; Forgan, Ross S

    2015-03-28

    Metal-organic frameworks (MOFs) have received particular attention over the last 20 years as a result of their attractive properties offering potential applications in a number of areas. Typically, these characteristics are tuned by functionalisation of the bulk of the MOF material itself. This Feature Article focuses instead on modification of MOF particles at their surfaces only, which can also offer control over the bulk properties of the material. The differing surface modification techniques available to the synthetic chemist will be discussed, with a focus on the effect of surface modification of MOFs on their fundamental properties and application in adsorption, catalysis, drug delivery and other areas.

  1. Surface functionalization of metal organic frameworks for mixed matrix membranes

    DOEpatents

    Albenze, Erik; Lartey, Michael; Li, Tao; Luebke, David R.; Nulwala, Hunaid B.; Rosi, Nathaniel L.; Venna, Surendar R.

    2017-03-21

    Mixed Matrix Membrane (MMM) are composite membranes for gas separation and comprising a quantity of inorganic filler particles, in particular metal organic framework (MOF), dispersed throughout a polymer matrix comprising one or more polymers. This disclosure is directed to MOF functionalized through addition of a pendant functional group to the MOF, in order to improve interaction with a surrounding polymer matrix in a MMM. The improved interaction aids in avoiding defects in the MMM due to incompatible interfaces between the polymer matrix and the MOF particle, in turn increasing the mechanical and gas separation properties of the MMM. The disclosure is also directed to a MMM incorporating the surface functionalized MOF.

  2. Embedded insulated metallic nanopatterns for enhanced optical absorption and photovoltaics

    NASA Astrophysics Data System (ADS)

    Ye, Fan; Burns, Michael J.; Naughton, Michael J.

    2012-02-01

    Recently, we have shown embedded metallic nanopatterns (EMN) in ultrathin PV films to be candidates for high efficiency thin-film solar cells, owing to prominent metamaterial/plasmonic-enhanced light trapping, as compared to unpatterned, surface- or bottom-patterned [1]. We also showed that hot electron effects emerge in ultrathin a-Si-based solar cells [2]. The EMN in the semiconductor layer, however, can also serve as a source of recombination for photogenerated electrons and holes, leading to decreased current. Here, we propose the idea of an embedded insulated metallic nanopattern (EIMN) to efficiently avoid the recombination effect while maintaining high light absorption in an ultrathin film format in which hot electron physics can contribute. Simulations show that an EIMN with a 10 nm layer of dielectric insulation provides essentially the same absorption as its EMN counterpart. Measurements on several EMN structures will be presented. This EIMN architecture may provide a practical route to high efficiency, hot electron solar cell technology using ultrathin films.[1]F. Ye, M.J. Burns, M.J. Naughton, Proc. SPIE 8111, 811103 (2011).[2]K. Kempa, M.J. Naughton, Z.F. Ren, A. Herczynski, T. Kirkpatrick, J. Rybczynski, Y. Gao, Appl. Phys. Lett. 95, 233121(2009)

  3. Photocurrent enhancements of organic solar cells by altering dewetting of plasmonic Ag nanoparticles

    NASA Astrophysics Data System (ADS)

    Fleetham, Tyler; Choi, Jea-Young; Choi, Hyung Woo; Alford, Terry; Jeong, Doo Seok; Lee, Taek Sung; Lee, Wook Seong; Lee, Kyeong-Seok; Li, Jian; Kim, Inho

    2015-09-01

    Incorporation of metal nanoparticles into active layers of organic solar cells is one of the promising light trapping approaches. The size of metal nanoparticles is one of key factors to strong light trapping, and the size of thermally evaporated metal nanoparticles can be tuned by either post heat treatment or surface modification of substrates. We deposited Ag nanoparticles on ITO by varying nominal thicknesses, and post annealing was carried out to increase their size in radius. PEDOT:PSS was employed onto the ITO substrates as a buffer layer to alter the dewetting behavior of Ag nanoparticles. The size of Ag nanoparticles on PEDOT:PSS were dramatically increased by more than three times compared to those on the ITO substrates. Organic solar cells were fabricated on the ITO and PEDOT:PSS coated ITO substrates with incorporation of those Ag nanoparticles, and their performances were compared. The photocurrents of the cells with the active layers on PEDOT:PSS with an optimal choice of the Ag nanoparticles were greatly enhanced whereas the Ag nanoparticles on the ITO substrates did not lead to the photocurrent enhancements. The origin of the photocurrent enhancements with introducing the Ag nanoparticles on PEDOT:PSS are discussed.

  4. "Heterogeneity within order" in metal-organic frameworks.

    PubMed

    Furukawa, Hiroyasu; Müller, Ulrich; Yaghi, Omar M

    2015-03-09

    Metal-organic frameworks (MOFs) are constructed by linking inorganic units with organic linkers to make extended networks. Though more than 20 000 MOF structures have been reported most of these are ordered and largely composed of a limited number of different kinds building units, and very few have multiple different building units (heterogeneous). Although heterogeneity and multiplicity is a fundamental characteristic of biological systems, very few synthetic materials incorporate heterogeneity without losing crystalline order. Thus, the question arises: how do we introduce heterogeneity into MOFs without losing their ordered structure? This Review outlines strategies for varying the building units within both the backbone of the MOF and its pores to produce the heterogeneity that is sought after. The impact this heterogeneity imparts on the properties of a MOF is highlighted. We also provide an update on the MOF industry as part of this themed issue for the 150th anniversary of BASF.

  5. Sulfate Reduction Remediation of a Metals Plume Through Organic Injection

    SciTech Connect

    Phifer, M.A.

    2003-03-11

    Laboratory testing and a field-scale demonstration for the sulfate reduction remediation of an acidic/metals/sulfate groundwater plume at the Savannah River Site has been conducted. The laboratory testing consisted of the use of anaerobic microcosms to test the viability of three organic substrates to promote microbially mediated sulfate reduction. Based upon the laboratory testing, soybean oil and sodium lactate were selected for injection during the subsequent field-scale demonstration. The field-scale demonstration is currently ongoing. Approximately 825 gallons (3,123 L) of soybean oil and 225 gallons (852 L) of 60 percent sodium lactate have been injected into an existing well system within the plume. Since the injections, sulfate concentrations in the injection zone have significantly decreased, sulfate-reducing bacteria concentrations have significantly increased, the pH has increased, the Eh has decreased, and the concentrations of many metals have decreased. Microbially mediated sulfate reduction has been successfully promoted for the remediation of the acidic/metals/sulfate plume by the injection of soybean oil and sodium lactate within the plume.

  6. Growth, physiological and molecular traits in Salicaceae trees investigated for phytoremediation of heavy metals and organics.

    PubMed

    Marmiroli, Marta; Pietrini, Fabrizio; Maestri, Elena; Zacchini, Massimo; Marmiroli, Nelson; Massacci, Angelo

    2011-12-01

    Worldwide, there are many large areas moderately contaminated with heavy metals and/or organics that have not been remediated due to the high cost and technical drawbacks of currently available technologies. Methods with a good potential for coping with these limitations are emerging from phytoremediation techniques, using, for example, specific amendments and/or plants selected from various candidates proven in several investigations to be reasonably efficient in extracting heavy metals from soil or water, or in co-metabolizing organics with bacteria flourishing or inoculated in their rhizospheres. Populus and Salix spp., two genera belonging to the Salicaceae family, include genotypes that can be considered among the candidates for this phytoremediation approach. This review shows the recent improvements in analytical tools based on the identification of useful genetic diversity associated with classical growth, physiological and biochemical traits, and the importance of plant genotype selection for enhancing phytoremediation efficiency. Particularly interesting are studies on the application of the phytoremediation of heavy metals and of chlorinated organics, in which microorganisms selected for their degradation capabilities were bioaugmented in the rhizosphere of Salicaceae planted at a high density for biomass and bioenergy production.

  7. Highly sensitive detection of dipicolinic acid with a water-dispersible terbium-metal organic framework.

    PubMed

    Bhardwaj, Neha; Bhardwaj, Sanjeev; Mehta, Jyotsana; Kim, Ki-Hyun; Deep, Akash

    2016-12-15

    The sensitive detection of dipicolinic acid (DPA) is strongly associated with the sensing of bacterial organisms in food and many types of environmental samples. To date, the demand for a sensitive detection method for bacterial toxicity has increased remarkably. Herein, we investigated the DPA detection potential of a water-dispersible terbium-metal organic framework (Tb-MOF) based on the fluorescence quenching mechanism. The Tb-MOF showed a highly sensitive ability to detect DPA at a limit of detection of 0.04nM (linear range of detection: 1nM to 5µM) and also offered enhanced selectivity from other commonly associated organic molecules. The present study provides a basis for the application of Tb-MOF for direct, convenient, highly sensitive, and specific detection of DPA in the actual samples.

  8. Enhanced fluorescence cell imaging with metal-coated slides

    NASA Astrophysics Data System (ADS)

    Le Moal, Eric; Fort, Emmanuel; Lévêque-Fort, Sandrine; Janin, Anne; Murata, Hideyuki; Cordelières, Fabrice P.

    2007-07-01

    The last decade has witnessed momentous advances in fluorescence microscopy. The introduction of novel fluorescent markers, together with the development of original microscopy techniques, made it possible to study biomolecular interactions in living cells and to examine the structure and function of living tissues. The emergence of these innovative techniques had a remarkable impact on all the life sciences. However, many biological and medical applications involve the detection of minute quantities of biomolecules, and are limited by the signal weakness in common observation conditions. Here, we show that silver and gold-coated microscope slides can be used as mirror substrates to efficiently improve detection sensitivity when fluorescence microscopy is applied to micrometer-thick biological samples. We report a fourfold enhancement of the fluorescence signal and a noticeable strengthening of the image contrast, when mirror substrates are used with standard air microscope objectives. We demonstrate that metal-coated substrates provide the means to get sensitivity-enhanced fluorescence detection with dry optics, while keeping a wide field observation and a large depth of field. This is a crucial advantage for automated and high-throughput applications to cell and tissue diagnostic analysis.

  9. The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of Metal-Organic Frameworks

    PubMed Central

    Burneo, Iván; Stylianou, Kyriakos C.; Imaz, Inhar; Maspoch, Daniel

    2016-01-01

    We have prepared three distinct polyamino acid-based metal-organic frameworks (MOFs) with different chirality and porosity using the same chemistry, by simply modifying the enantiomeric ratio of the chiral organic ligand used. PMID:25253285

  10. A metal-free organic-inorganic aqueous flow battery.

    PubMed

    Huskinson, Brian; Marshak, Michael P; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R; Galvin, Cooper J; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

    2014-01-09

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br(-) redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals

  11. Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating

    PubMed Central

    Sun, B. A.; Chen, S. H.; Lu, Y. M.; Zhu, Z. G.; Zhao, Y. L.; Yang, Y.; Chan, K. C.; Liu, C. T.

    2016-01-01

    Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability. PMID:27271435

  12. Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating.

    PubMed

    Sun, B A; Chen, S H; Lu, Y M; Zhu, Z G; Zhao, Y L; Yang, Y; Chan, K C; Liu, C T

    2016-06-08

    Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability.

  13. Origin of Shear Stability and Compressive Ductility Enhancement of Metallic Glasses by Metal Coating

    NASA Astrophysics Data System (ADS)

    Sun, B. A.; Chen, S. H.; Lu, Y. M.; Zhu, Z. G.; Zhao, Y. L.; Yang, Y.; Chan, K. C.; Liu, C. T.

    2016-06-01

    Metallic glasses (MGs) are notorious for the poor macroscopic ductility and to overcome the weakness various intrinsic and extrinsic strategies have been proposed in past decades. Among them, the metal coating is regarded as a flexible and facile approach, yet the physical origin is poorly understood due to the complex nature of shear banding process. Here, we studied the origin of ductile enhancement in the Cu-coating both experimentally and theoretically. By examining serrated shear events and their stability of MGs, we revealed that the thin coating layer plays a key role in stopping the final catastrophic failure of MGs by slowing down shear band dynamics and thus retarding its attainment to a critical instable state. The mechanical analysis on interplay between the coating layer and shear banding process showed the enhanced shear stability mainly comes from the lateral tension of coating layer induced by the surface shear step and the bonding between the coating layer and MGs rather than the layer thickness is found to play a key role in contributing to the shear stability.

  14. Construction of stable Ta3N5/g-C3N4 metal/non-metal nitride hybrids with enhanced visible-light photocatalysis

    NASA Astrophysics Data System (ADS)

    Jiang, Yinhua; Liu, Peipei; Chen, YeCheng; Zhou, Zhengzhong; Yang, Haijian; Hong, Yuanzhi; Li, Fan; Ni, Liang; Yan, Yongsheng; Gregory, Duncan H.

    2017-01-01

    In this paper, a novel Ta3N5/g-C3N4 metal/non-metal nitride hybrid was successfully synthesized by a facile impregnation method. The photocatalytic activity of Ta3N5/g-C3N4 hybrid nitrides was evaluated by the degradation of organic dye rhodamine B (RhB) under visible light irradiation, and the result indicated that all Ta3N5/g-C3N4 samples exhibited distinctly enhanced photocatalytic activities for the degradation of RhB than pure g-C3N4. The optimal Ta3N5/g-C3N4 composite sample, with Ta3N5 mass ratio of 2%, demonstrated the highest photocatalytic activity, and its degradation rate constant was 2.71 times as high as that of pure g-C3N4. The enhanced photocatalytic activity of this Ta3N5/g-C3N4 metal/metal-free nitride was predominantly attributed to the synergistic effect which increased visible-light absorption and facilitated the efficient separation of photoinduced electrons and holes. The Ta3N5/g-C3N4 hybrid nitride exhibited excellent photostability and reusability. The possible mechanism for improved photocatalytic performance was proposed. Overall, this work may provide a facile way to synthesize the highly efficient metal/metal-free hybrid nitride photocatalysts with promising applications in environmental purification and energy conversion.

  15. Post-Synthetic Modification of Porphyrin-Encapsulating Metal-Organic Materials by Cooperative Addition of Inorganic Salts to Enhance CO2/CH4 Selectivity

    SciTech Connect

    Zhang, Zhenjie; Gao, Wen-Yang; Wojtas, Lukasz; Ma, Shengqian; Eddaoudi, Mohamed; Zaworotko, Michael J

    2012-11-26

    Keeping MOM: Reaction of biphenyl-3,4',5-tricarboxylate and Cd(NO3)2 in the presence of meso-tetra(N-methyl-4-pyridyl)porphine tetratosylate afforded porph@MOM-11, a microporous metal–organic material (MOM) that encapsulates cationic porphyrins and solvent in alternating open channels. Porph@MOM-11 has cation and anion binding sites that facilitate cooperative addition of inorganic salts (such as M+Cl-) in a stoichiometric fashion.

  16. Metal-organic frameworks for thermoelectric energy-conversion applications

    SciTech Connect

    Talin, Albert Alec; Jones, Reese E.; Hopkins, Patrick E.

    2016-11-07

    Motivated by low cost, low toxicity, mechanical flexibility, and conformability over complex shapes, organic semiconductors are currently being actively investigated as thermoelectric (TE) materials to replace the costly, brittle, and non-eco-friendly inorganic TEs for near-ambient-temperature applications. Metal–organic frameworks (MOFs) share many of the attractive features of organic polymers, including solution processability and low thermal conductivity. A potential advantage of MOFs and MOFs with guest molecules (Guest@MOFs) is their synthetic and structural versatility, which allows both the electronic and geometric structure to be tuned through the choice of metal, ligand, and guest molecules. This could solve the long-standing challenge of finding stable, high-TE-performance n-type organic semiconductors, as well as promote high charge mobility via the long-range crystalline order inherent in these materials. In this paper, we review recent advances in the synthesis of MOF and Guest@MOF TEs and discuss how the Seebeck coefficient, electrical conductivity, and thermal conductivity could be tuned to further optimize TE performance.

  17. Metal-organic frameworks for thermoelectric energy-conversion applications

    DOE PAGES

    Talin, Albert Alec; Jones, Reese E.; Hopkins, Patrick E.

    2016-11-07

    Motivated by low cost, low toxicity, mechanical flexibility, and conformability over complex shapes, organic semiconductors are currently being actively investigated as thermoelectric (TE) materials to replace the costly, brittle, and non-eco-friendly inorganic TEs for near-ambient-temperature applications. Metal–organic frameworks (MOFs) share many of the attractive features of organic polymers, including solution processability and low thermal conductivity. A potential advantage of MOFs and MOFs with guest molecules (Guest@MOFs) is their synthetic and structural versatility, which allows both the electronic and geometric structure to be tuned through the choice of metal, ligand, and guest molecules. This could solve the long-standing challenge of findingmore » stable, high-TE-performance n-type organic semiconductors, as well as promote high charge mobility via the long-range crystalline order inherent in these materials. In this paper, we review recent advances in the synthesis of MOF and Guest@MOF TEs and discuss how the Seebeck coefficient, electrical conductivity, and thermal conductivity could be tuned to further optimize TE performance.« less

  18. Enhancing Critical Thinking through Creation of Learning Organizations within the Confines of an Overarching Mechanistic Organization

    DTIC Science & Technology

    2015-05-01

    standardized tasks – Centralized decision - making processes – Higher efficiencies through lessened variation and improved predictability – Restricted...responsive to changes in the environment – Learns from mistake – Adapts to new realities more readily – Better decision - making in non-problematic...Enhancing Critical Thinking through Creation of Learning Organizations within the Confines of an Overarching Mechanistic Organization David Riel

  19. Modeling Adsorption and Reactions of Organic Molecules at Metal Surfaces

    PubMed Central

    2014-01-01

    Conspectus The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdWsurf method that accurately accounts for the collective electronic

  20. Modeling adsorption and reactions of organic molecules at metal surfaces.

    PubMed

    Liu, Wei; Tkatchenko, Alexandre; Scheffler, Matthias

    2014-11-18

    CONSPECTUS: The understanding of adsorption and reactions of (large) organic molecules at metal surfaces plays an increasingly important role in modern surface science and technology. Such hybrid inorganic/organic systems (HIOS) are relevant for many applications in catalysis, light-emitting diodes, single-molecule junctions, molecular sensors and switches, and photovoltaics. Obviously, the predictive modeling and understanding of the structure and stability of such hybrid systems is an essential prerequisite for tuning their electronic properties and functions. At present, density-functional theory (DFT) is the most promising approach to study the structure, stability, and electronic properties of complex systems, because it can be applied to both molecules and solids comprising thousands of atoms. However, state-of-the-art approximations to DFT do not provide a consistent and reliable description for HIOS, which is largely due to two issues: (i) the self-interaction of the electrons with themselves arising from the Hartree term of the total energy that is not fully compensated in approximate exchange-correlation functionals, and (ii) the lack of long-range part of the ubiquitous van der Waals (vdW) interactions. The self-interaction errors sometimes lead to incorrect description of charge transfer and electronic level alignment in HIOS, although for molecules adsorbed on metals these effects will often cancel out in total energy differences. Regarding vdW interactions, several promising vdW-inclusive DFT-based methods have been recently demonstrated to yield remarkable accuracy for intermolecular interactions in the gas phase. However, the majority of these approaches neglect the nonlocal collective electron response in the vdW energy tail, an effect that is particularly strong in condensed phases and at interfaces between different materials. Here we show that the recently developed DFT+vdW(surf) method that accurately accounts for the collective electronic

  1. Control of light absorption in organic solar cells using semi-transparent metal electrodes

    NASA Astrophysics Data System (ADS)

    Neutzner, Stefanie; van de Groep, Jorik; Bakulin, Artem A.; Bakker, Huib J.

    2013-09-01

    In this contribution we combine optical modeling and device fabrication/characterization techniques to demonstrate that semitransparent metal electrodes can improve light harvesting in organic photovoltaic (OPV) devices. We show that inverted P3HT:PCBM solar cells using a thin ~8 nm silver film as a front electrode outperform the ITO-based devices, despite the lower transmittance of silver films in comparison to ITO. The variation of silver thickness allows tailoring the field distribution inside the cell, which leads to a broad resonance window where the absorption is enhanced. Thereby the short-circuit current was increased by 84% and the solar-cell efficiency was doubled. These results show that semitransparent metal electrodes can be efficiently used for light trapping and also form a very promising alternative to ITO in OPV devices. The stacked silver electrodes used in this work are flexible and can be easily produced on a large scale, including printing techniques.

  2. Metal-inorganic-organic matrices as efficient sorbents for hydrogen storage.

    PubMed

    Azzouz, Abdelkrim; Nousir, Saadia; Bouazizi, Nabil; Roy, René

    2015-03-01

    Stabilization of metal nanoparticles (MNPs) without re-aggregation is a major challenge. An unprecedented strategy is developed for achieving high dispersion of copper(0) or palladium(0) on montmorillonite-supported diethanolamine or thioglycerol. This results in novel metal-inorganic-organic matrices (MIOM) that readily capture hydrogen at ambient conditions, with easy release under air stream. Hydrogen retention appears to involve mainly physical interactions, slightly stronger on thioglycerol-based MIOM (S-MIOM). Thermal enhancement of desorption suggests also a contribution of chemical interactions. The increase of hydrogen uptake with prolonged contact times arises from diffusion hindrance, which appears to be beneficial by favoring hydrogen entrapment. Even with compact structures, MIOMs act as efficient sorbents with much higher efficiency factor (1.14-1.17 mmol H 2 m(-2)) than many other sophisticated adsorbents reported in the literature. This opens new prospects for hydrogen storage and potential applications in microfluidic hydrogenation reactions.

  3. Metal nanocrystal/metal-organic framework core/shell nanostructure from selective self-assembly induced by localization of metal ion precursors on nanocrystal surface.

    PubMed

    Ohhashi, Takashi; Tsuruoka, Takaaki; Matsuyama, Tetsuhiro; Takashima, Yohei; Nawafune, Hidemi; Minami, Hideto; Akamatsu, Kensuke

    2015-08-01

    Metal nanocrystal/metal-organic framework core/shell nanostructures have been constructed using metal ion-trapped nanocrystals as scaffolds through a selective self-assembly of framework components on the nanocrystal surfaces. The resulting nanostructures exhibit unique catalytic activity toward nitrophenol analogs.

  4. Ag nanoparticle-blended plasmonic organic solar cells: performance enhancement or detraction?

    NASA Astrophysics Data System (ADS)

    Wu, Bo; Mathews, Nripan; Sum, Tze Chien

    2014-03-01

    The blending of metallic nanoparticles into the active layer of organic solar cells in a bid to enhance their light absorption and device performance has led to controversial reports of both efficiency enhancement and degradation. Herein, through comprehensive transient absorption spectroscopy, we present clear evidence of traps being responsible for performance degradation of poly (3-hexylthiophene): [6,6]-phenyl-C 61-butyric acid methyl ester organic photovoltaic devices incorporated with oleylamine-capped silver nanoparticles. Although the presence of the metallic nanoparticles leads to more excitons being generated in the active layer, higher losses suffered by the polaron population through trap-assisted recombination strongly limits the device performance. Device modeling based on a single mid-gap trap state introduced by the AgNPs can well reproduce the current-voltage curves of the plasmonic organic solar cells - in agreement with the transient absorption findings. These new insights into the photophysics and charge dynamics of plasmonic organic solar cells would help resolve the existing controversy and provide clear guidelines for device design and fabrication.

  5. Preparation of Pickering emulsions stabilized by metal organic frameworks using oscillatory woven metal micro-screen.

    PubMed

    Sabouni, R; Gomaa, H G

    2015-06-14

    Uniform Pickering emulsions stabilized by metal organic frameworks (MOFs) MIL-101 and ZIF-8 nanoparticles (NPs) were successfully prepared using an oscillatory woven metal microscreen (WMMS) emulsification system in the presence and the absence of surfactants. The effects of operating and system parameters including the frequency and amplitude of oscillation, the type of nano-particle and/or surfactant on the droplet size and coefficient of variance of the prepared emulsions are investigated. The results showed that both the hydrodynamics of the system and the hydrophobic/hydrophilic nature of the NP influenced the interfacial properties of the oil-water interface during droplet formation and after detachment, which in turn affected the final droplet size and distribution. Comparison between the measured and predicted droplet size using a simple torque balance (TB) model is discussed.

  6. A metal-free organic-inorganic aqueous flow battery

    SciTech Connect

    Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

  7. Bioremediation of metals, organic and mixed contaminants with microbial mats

    SciTech Connect

    Bender, J.

    1995-12-31

    Microbial mats are natural heterotrophic and autotrophic communities dominated by cyanobacteria (blue-green algae). They are self-organized laminated structures annealed tightly together by slimy secretions from various microbial components. The surface slime of the mats effectively immobilizes the ecosystem to a variety of substrates, thereby stabilizing the most efficient internal microbial structure. Cyanobacteria mats are generated for bioremediation applications by enriching a water surface with ensiled grass clippings. These constructed mats have been used to reduce selenate to elemental selenium, remove Pb, Cd, Cu, Zn, Co, Cr, Fe and Mn from water and to remove Pb from sediments of shallow laboratory ponds. Uranium, U{sup 238}, was removed from groundwater samples at the rate of 3.19 Mg/m{sup 2}/h. Degradation of recalcitrant organic contaminants by mats is relatively rapid under both dark and light conditions. The following contaminants have been degraded in water and/or soil media by constructed mats: TNT, chrysene, naphthalene, hexadecane, phenanthrene, PCB, TCE, pulp and paper mill wastes, and three pesticides: chlordane, carbofuran and paraquat. Radio-labeled experiments with mat-treated carbofuran, petroleum distillates, TNT, chlordane, PCB and TCE show that these compounds are mineralized by the constructed mats. Mats applied to mixed contaminant solutions (TCE + Zn and TNT + pb) sequestered the metal while mineralizing the TCE. Remediation rates of the organic and inorganic components were the same in mixed solution as they were in single application.

  8. Metal-organic framework materials based on icosahedral boranes and carboranes

    DOEpatents

    Mirkin, Chad A.; Hupp, Joseph T.; Farha, Omar K.; Spokoyny, Alexander M.; Mulfort, Karen L.

    2010-11-02

    Disclosed herein are metal-organic frameworks of metals and boron rich ligands, such as carboranes and icosahedral boranes. Methods of synthesizing and using these materials in gas uptake are disclosed.

  9. Chelant-enhanced heavy metals uptake by Eucalyptus trees under controlled deficit irrigation

    NASA Astrophysics Data System (ADS)

    Fine, Pinchas; Rathod, Paresh; Beriozkin, Anna; Ein-Gal, Oz; Hass, Amir

    2014-05-01

    Enhancement of phytoremediation of heavy metal polluted soils employs organic ligands, aimed to solubilize, phytoextract and translocate metals into the canopy. The use of more persistent chelants (e.g. EDTA) is phasing out due to concerns over their role in the environment. We tested the hypothesis that controlled deficit irrigation (CDI) of the fast growing, salinity resistant Eucalyptus camaldulensis coupled with timely EDTA application enhances sediment phytoremediation while minimizing leaching of metal complexes below the root-zone. This was tested in 220-L lysimeters packed with sand mixed with metals polluted biosolids. One year old trees were brought under CDI with tap or RO water for two growing seasons. EDTA, EDDS and citric acid fertigation at 2 mM started in each May for 2.5-3.5 months, and prescribed soil leaching and sampling of tree leaves started thereafter. While all 3 chelants solubilized biosolids metal in batch extraction (EDDS often being the more efficient), EDTA was the only to increased metal concentrations both in the soil solution and in the Eucalyptus leaves. The average concentrations in the soil solution and in the leaves, in the EDTA vs. control (chelant-free) treatments, all respectively, were: Cd - 200 mg L-1 vs. 1.0, and 67 vs. 21 mg kg-1; Cu: 90 vs. 1.5 mg L-1, and 17 vs. 3.0 mg kg-1; Cr: 4.0 vs. 1.4 mg L-1, and 3.0 vs. 1.0 mg kg-1; Ni: 60 mg L-1 vs. 14, and 20 vs. 6.0 mg kg-1; Pb: >44 vs. 0.1 mg L-1, and 9.0 vs. 1.0 mg kg-1; and Zn: 650 vs. 4.0 mg L-1 and 200 vs. 70 mg kg-1. While EDDS was undetectable in all the leachates, EDTA concentrated to up to 100 mM. At 10 mM soil solution concentration, EDDS half-life in acclimated lysimeter media was 5-11 days and that of EDTA was ≥27-d. The study suggests that sustainable phytostabilization and phytoextraction of heavy metals are achievable under CDI with EDTA augmentation at low dose. This was yet futile with the biodegradable EDDS and citric acid. CDI with RO water further widened

  10. Structure and properties of an amorphous metal-organic framework.

    PubMed

    Bennett, Thomas D; Goodwin, Andrew L; Dove, Martin T; Keen, David A; Tucker, Matthew G; Barney, Emma R; Soper, Alan K; Bithell, Erica G; Tan, Jin-Chong; Cheetham, Anthony K

    2010-03-19

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300 degrees C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400 degrees C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  11. Structure and Properties of an Amorphous Metal-Organic Framework

    NASA Astrophysics Data System (ADS)

    Bennett, Thomas D.; Goodwin, Andrew L.; Dove, Martin T.; Keen, David A.; Tucker, Matthew G.; Barney, Emma R.; Soper, Alan K.; Bithell, Erica G.; Tan, Jin-Chong; Cheetham, Anthony K.

    2010-03-01

    ZIF-4, a metal-organic framework (MOF) with a zeolitic structure, undergoes a crystal-amorphous transition on heating to 300°C. The amorphous form, which we term a-ZIF, is recoverable to ambient conditions or may be converted to a dense crystalline phase of the same composition by heating to 400°C. Neutron and x-ray total scattering data collected during the amorphization process are used as a basis for reverse Monte Carlo refinement of an atomistic model of the structure of a-ZIF. The structure is best understood in terms of a continuous random network analogous to that of a-SiO2. Optical microscopy, electron diffraction and nanoindentation measurements reveal a-ZIF to be an isotropic glasslike phase capable of plastic flow on its formation. Our results suggest an avenue for designing broad new families of amorphous and glasslike materials that exploit the chemical and structural diversity of MOFs.

  12. Heavy metals in organisms from the northern Tyrrhenian sea.

    PubMed

    Leonzio, C; Bacci, E; Focardi, S; Renzoni, A

    1981-09-01

    The concentrations of zinc, manganese, copper, cadmium, lead and mercury have been determined in soft tissues of four marine organisms (Mytilus galloprovincialis Lmk., Nephrops norvegicus L., Mullus barbatus L., Engraulis encrasicolus L.) collected seasonally from the winter of 1976 to the spring of 1980 in various areas of the Tyrrhenian Sea (western Mediterranean). In all four species levels of all metals, except mercury in all areas are alike while mercury levels vary and, furthermore, are higher than in specimens from other areas of the Mediterranean and also from other seas. The possible natural origin of the mercury from cinnabar (HgS) ore as well as the suitability of the four species as bioindicators is discussed.

  13. Coordinative alignment of molecules in chiral metal-organic frameworks.

    PubMed

    Lee, Seungkyu; Kapustin, Eugene A; Yaghi, Omar M

    2016-08-19

    A chiral metal-organic framework, MOF-520, was used to coordinatively bind and align molecules of varying size, complexity, and functionality. The reduced motional degrees of freedom obtained with this coordinative alignment method allowed the structures of molecules to be determined by single-crystal x-ray diffraction techniques. The chirality of the MOF backbone also served as a reference in the structure solution for an unambiguous assignment of the absolute configuration of bound molecules. Sixteen molecules representing four common functional groups (primary alcohol, phenol, vicinal diol, and carboxylic acid), ranging in complexity from methanol to plant hormones (gibberellins, containing eight stereocenters), were crystallized and had their precise structure determined. We distinguished single and double bonds in gibberellins, and we enantioselectively crystallized racemic jasmonic acid, whose absolute configuration had only been inferred from derivatives.

  14. Metal-organic frameworks for membrane-based separations

    NASA Astrophysics Data System (ADS)

    Denny, Michael S.; Moreton, Jessica C.; Benz, Lauren; Cohen, Seth M.

    2016-12-01

    As research into metal-organic frameworks (MOFs) enters its third decade, efforts are naturally shifting from fundamental studies to applications, utilizing the unique features of these materials. Engineered forms of MOFs, such as membranes and films, are being investigated to transform laboratory-synthesized MOF powders to industrially viable products for separations, chemical sensors and catalysts. Following encouraging demonstrations of gas separations using MOF-based membranes, liquid-phase separations are now being explored in an effort to build effective membranes for these settings. In this Review, we highlight MOF applications that are in their nascent stages, specifically liquid-phase separations using MOF-based mixed-matrix membranes. We also highlight the analytical techniques that provide important insights into these materials, particularly at surfaces and interfaces, to better understand MOFs and their interactions with other materials, which will ultimately lead to their use in advanced technologies.

  15. Metal-organic frameworks for Xe/Kr separation

    DOEpatents

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2013-08-27

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  16. Metal-organic frameworks for Xe/Kr separation

    DOEpatents

    Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang

    2014-07-22

    Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.

  17. Superexchange Charge Transport in Loaded Metal Organic Frameworks.

    PubMed

    Neumann, Tobias; Liu, Jianxi; Wächter, Tobias; Friederich, Pascal; Symalla, Franz; Welle, Alexander; Mugnaini, Veronica; Meded, Velimir; Zharnikov, Michael; Wöll, Christof; Wenzel, Wolfgang

    2016-07-26

    In the past, nanoporous metal-organic frameworks (MOFs) have been mostly studied for their huge potential with regard to gas storage and separation. More recently, the discovery that the electrical conductivity of a widely studied, highly insulating MOF, HKUST-1, improves dramatically when loaded with guest molecules has triggered a huge interest in the charge carrier transport properties of MOFs. The observed high conductivity, however, is difficult to reconcile with conventional transport mechanisms: neither simple hopping nor band transport models are consistent with the available experimental data. Here, we combine theoretical results and new experimental data to demonstrate that the observed conductivity can be explained by an extended hopping transport model including virtual hops through localized MOF states or molecular superexchange. Predictions of this model agree well with precise conductivity measurements, where experimental artifacts and the influence of defects are largely avoided by using well-defined samples and the Hg-drop junction approach.

  18. High methane storage capacity in aluminum metal-organic frameworks.

    PubMed

    Gándara, Felipe; Furukawa, Hiroyasu; Lee, Seungkyu; Yaghi, Omar M

    2014-04-09

    The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal-organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm(3) cm(-3) at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm(3) cm(-3) under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm(3) cm(-3), and between 5 and 80 bar, 230 cm(3) cm(-3).

  19. Metal-Organic Frameworks for CO2 Chemical Transformations.

    PubMed

    He, Hongming; Perman, Jason A; Zhu, Guangshan; Ma, Shengqian

    2016-12-01

    Carbon dioxide (CO2 ), as the primary greenhouse gas in the atmosphere, triggers a series of environmental and energy related problems in the world. Therefore, there is an urgent need to develop multiple methods to capture and convert CO2 into useful chemical products, which can significantly improve the environment and promote sustainable development. Over the past several decades, metal-organic frameworks (MOFs) have shown outstanding heterogeneous catalytic activity due in part to their high internal surface area and chemical functionalities. These properties and the ability to synthesize MOF platforms allow experiments to test structure-function relationships for transforming CO2 into useful chemicals. Herein, recent developments are highlighted for MOFs participating as catalysts for the chemical fixation and photochemical reduction of CO2 . Finally, opportunities and challenges facing MOF catalysts are discussed in this ongoing research area.

  20. Externally controlled spin state switching in metal-organic complexes.

    NASA Astrophysics Data System (ADS)

    Bagrets, Alexei; Meded, Velimir; Ruben, Mario; Evers, Ferdinand

    2009-03-01

    Recent transport experiments have demonstrated that a manipulation of the charge of individual molecules is feasible using electromigrated metal junctions [1] or electrochemical gates in conjunction with the STM [2]. Using elaborated density functional theory calculations, we will discuss a possibility to induce -- by means of charging or applied stress -- a switching between low and high spin states in certain metal-organic systems, [Fe(bpp)2]^2+ (bpp: bispyrazolyl pyridine) and [Mn(tpy)2]^2+ (tpy: terpyridine). Based upon a recent success of the single molecular conduction experiment through Ru(II) complex [3], we anticipate the transport properties of Fe(II) and Mn(II) complexes to be gate controlled via exploiting their spin degree of freedom. [1] E. A. Osorio et al., J. Phys.: Condens. Matter20, 374121 (2008); [2] F. Chen el al., Ann. Rev. Phys. Chem. 58, 535 (2007); Li et al., Nanotechnology 18, 044018 (2007). [3] M. Ruben, A. Landa, E. L"ortscher, H. Riel, M. Mayor, H. G"orls, H. Weber, A. Arnold, and F. Evers, Small (online), DOI: 10.1002/smll.200800390 (2008).

  1. Controlling Thermal Expansion: A Metal-Organic Frameworks Route.

    PubMed

    Balestra, Salvador R G; Bueno-Perez, Rocio; Hamad, Said; Dubbeldam, David; Ruiz-Salvador, A Rabdel; Calero, Sofia

    2016-11-22

    Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here, for the first time, for the use of metal-organic frameworks (MOFs) as platforms for controlling thermal expansion devices that can operate in the negative, zero, and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material, along with three molecules of similar size and known differences in terms of the nature of host-guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to display positive, zero, or negative thermal expansion. We analyze in depth the distortion mechanisms, beyond the ligand metal junction, to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs as a basic tool toward controlling the thermal expansion.

  2. Destruction of chemical warfare agents using metal-organic frameworks

    NASA Astrophysics Data System (ADS)

    Mondloch, Joseph E.; Katz, Michael J.; Isley, William C., III; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W.; Hall, Morgan G.; Decoste, Jared B.; Peterson, Gregory W.; Snurr, Randall Q.; Cramer, Christopher J.; Hupp, Joseph T.; Farha, Omar K.

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic ZrIV ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  3. Destruction of chemical warfare agents using metal-organic frameworks.

    PubMed

    Mondloch, Joseph E; Katz, Michael J; Isley, William C; Ghosh, Pritha; Liao, Peilin; Bury, Wojciech; Wagner, George W; Hall, Morgan G; DeCoste, Jared B; Peterson, Gregory W; Snurr, Randall Q; Cramer, Christopher J; Hupp, Joseph T; Farha, Omar K

    2015-05-01

    Chemical warfare agents containing phosphonate ester bonds are among the most toxic chemicals known to mankind. Recent global military events, such as the conflict and disarmament in Syria, have brought into focus the need to find effective strategies for the rapid destruction of these banned chemicals. Solutions are needed for immediate personal protection (for example, the filtration and catalytic destruction of airborne versions of agents), bulk destruction of chemical weapon stockpiles, protection (via coating) of clothing, equipment and buildings, and containment of agent spills. Solid heterogeneous materials such as modified activated carbon or metal oxides exhibit many desirable characteristics for the destruction of chemical warfare agents. However, low sorptive capacities, low effective active site loadings, deactivation of the active site, slow degradation kinetics, and/or a lack of tailorability offer significant room for improvement in these materials. Here, we report a carefully chosen metal-organic framework (MOF) material featuring high porosity and exceptional chemical stability that is extraordinarily effective for the degradation of nerve agents and their simulants. Experimental and computational evidence points to Lewis-acidic Zr(IV) ions as the active sites and to their superb accessibility as a defining element of their efficacy.

  4. CO2-Selective Nanoporous Metal-Organic Framework Microcantilevers

    PubMed Central

    Yim, Changyong; Lee, Moonchan; Yun, Minhyuk; Kim, Gook-Hee; Kim, Kyong Tae; Jeon, Sangmin

    2015-01-01

    Nanoporous anodic aluminum oxide (AAO) microcantilevers are fabricated and MIL-53 (Al) metal-organic framework (MOF) layers are directly synthesized on each cantilever surface by using the aluminum oxide as the metal ion source. Exposure of the MIL53-AAO cantilevers to various concentrations of CO2, N2, CO, and Ar induces changes in their deflections and resonance frequencies. The results of the resonance frequency measurements for the different adsorbed gas molecules are almost identical when the frequency changes are normalized by the molecular weights of the gases. In contrast, the deflection measurements show that only CO2 adsorption induces substantial bending of the MIL53-AAO cantilevers. This selective deflection of the cantilevers is attributed to the strong interactions between CO2 and the hydroxyl groups in MIL-53, which induce structural changes in the MIL-53 layers. Simultaneous measurements of the resonance frequency and the deflection are performed to show that the diffusion of CO2 into the nanoporous MIL-53 layers occurs very rapidly, whereas the binding of CO2 to hydroxyl groups occurs relatively slowly, which indicates that the adsorption of CO2 onto the MIL-53 layers and the desorption of CO2 from the MIL-53 layers are reaction limited. PMID:26035805

  5. Compliant Metal Enhanced Convection Cooled Reverse-Flow Annular Combustor

    NASA Technical Reports Server (NTRS)

    Paskin, Marc D.; Acosta, Waldo A.

    1994-01-01

    A joint Army/NASA program was conducted to design, fabricate, and test an advanced, reverse-flow, small gas turbine combustor using a compliant metal enhanced (CME) convection wall cooling concept. The objectives of this effort were to develop a design method (basic design data base and analysis) for the CME cooling technique and tben demonstrate its application to an advanced cycle, small, reverse-flow combustor with 3000 F (1922 K) burner outlet temperature (BOT). The CME concept offers significant improvements in wall cooling effectiveness resulting in a large reduction in cooling air requirements. Therefore, more air is available for control of burner outlet temperature pattern in addition to the benefit of improved efficiency, reduced emissions, and smoke levels. Rig test results demonstrated the benefits and viability of the CME concept meeting or exceeding the aerothermal performance and liner wall temperature characteristics of similar lower temperature-rise combustors, achieving 0.15 pattern factor at 3000 F (1922 K) BOT, while utilizing approximately 80 percent less cooling air than conventional, film-cooled combustion systems.

  6. Optical Relaxation Time Enhancement in Graphene-Passivated Metal Films

    PubMed Central

    Chugh, Sunny; Mehta, Ruchit; Man, Mengren; Chen, Zhihong

    2016-01-01

    Due to the small skin depth in metals at optical frequencies, their plasmonic response is strongly dictated by their surface properties. Copper (Cu) is one of the standard materials of choice for plasmonic applications, because of its high conductivity and CMOS compatibility. However, being a chemically active material, it gets easily oxidized when left in ambient environment, causing an inevitable degradation in its plasmonic resonance. Here, for the first time, we report a strong enhancement in the optical relaxation time in Cu by direct growth of few-layer graphene that is shown to act as an excellent passivation layer protecting Cu surface from any deterioration. Spectroscopic ellipsometry measurements reveal a 40–50% reduction in the total scattering rate in Cu itself, which is attributed to an improvement in its surface properties. We also study the impact of graphene quality and show that high quality graphene leads to an even larger improvement in electron scattering rate. These findings are expected to provide a big push towards graphene-protected Cu plasmonics. PMID:27461968

  7. Post Modification of Metal-Organic Framework and Their Application In Cancer Theranostics

    NASA Astrophysics Data System (ADS)

    Lakkakula, Hima bindu

    The research proposal aims to demonstrate that Metal-Organic Frameworks (MOFs) are mainly used for cancer theranostics which is the combination of both diagnostic and therapeutic functions. The research will emphasis on synthesis of Fe- MOFs by solvothermal nucleation, crystallization, characterization by microscopy and spectroscopy and evaluation with different lattice parameters and its morphology. Nowadays MOFs are used for the novel drug delivery purposes. The current published Fe- MOFs research focus is on the cancer theranostics by Indian medicines which will be impregnated into the MOFs and which will evaluate bioavailability and the chemotherapeutic activity of the drug. Nanotechnology provides the target specificity without affecting the healthy tissues. Other research problems to be addressed are the relationship between metal connectivity and ligand-based luminescence, MOF stability in an aqueous environment and activating it at increased temperature serves as a crucial role. The merits of this research are to increase the surface area and pore size of the drug so that the therapeutic efficacy can be improved. Moreover, the stabilization of metal-organic frameworks can also be enhanced with high surface area.

  8. Surfactant-enhanced remediation of organic contaminated soil and water.

    PubMed

    Paria, Santanu

    2008-04-21

    Surfactant based remediation technologies for organic contaminated soil and water (groundwater or surface water) is of increasing importance recently. Surfactants are used to dramatically expedite the process, which in turn, may reduce the treatment time of a site compared to use of water alone. In fact, among the various available remediation technologies for organic contaminated sites, surfactant based process is one of the most innovative technologies. To enhance the application of surfactant based technologies for remediation of organic contaminated sites, it is very important to have a better understanding of the mechanisms involved in this process. This paper will provide an overview of the recent developments in the area of surfactant enhanced soil and groundwater remediation processes, focusing on (i) surfactant adsorption on soil, (ii) micellar solubilization of organic hydrocarbons, (iii) supersolubilization, (iv) density modified displacement, (v) degradation of organic hydrocarbon in presence surfactants, (vi) partitioning of surfactants onto soil and liquid organic phase, (vii) partitioning of contaminants onto soil, and (viii) removal of organics from soil in presence of surfactants. Surfactant adsorption on soil and/or sediment is an important step in this process as it results in surfactant loss reduced the availability of the surfactants for solubilization. At the same time, adsorbed surfactants will retained in the soil matrix, and may create other environmental problem. The biosurfactants are become promising in this application due to their environmentally friendly nature, nontoxic, low adsorption on to soil, and good solubilization efficiency. Effects of different parameters like the effect of electrolyte, pH, soil mineral and organic content, soil composition etc. on surfactant adsorption are discussed here. Micellar solubilization is also an important step for removal of organic contaminants from the soil matrix, especially for low aqueous

  9. Process for the enhanced capture of heavy metal emissions

    DOEpatents

    Biswas, Pratim; Wu, Chang-Yu

    2001-01-01

    This invention is directed to a process for forming a sorbent-metal complex. The process includes oxidizing a sorbent precursor and contacting the sorbent precursor with a metallic species. The process further includes chemically reacting the sorbent precursor and the metallic species, thereby forming a sorbent-metal complex. In one particular aspect of the invention, at least a portion of the sorbent precursor is transformed into sorbent particles during the oxidation step. These sorbent particles then are contacted with the metallic species and chemically reacted with the metallic species, thereby forming a sorbent-metal complex. Another aspect of the invention is directed to a process for forming a sorbent metal complex in a combustion system. The process includes introducing a sorbent precursor into a combustion system and subjecting the sorbent precursor to an elevated temperature sufficient to oxidize the sorbent precursor and transform the sorbent precursor into sorbent particles. The process further includes contacting the sorbent particles with a metallic species and exposing the sorbent particles and the metallic species to a complex-forming temperature whereby the metallic species reacts with the sorbent particles thereby forming a sorbent-metal complex under UV irradiation.

  10. Enhanced reactive metal wall for dehalogenation of hydrocarbons

    DOEpatents

    Howson, P.E.; Mackenzie, P.D.; Horney, D.P.

    1996-08-06

    A method is provided for remediation of contaminated solutions using a tiered metal wall or column. The tiered metal wall or column has at least three zones with graduated sizes of reducing metal particles. Contaminated solutions pass through the tiered wall or column to dehalogenate contaminant halogenated hydrocarbons. 3 figs.

  11. Enhanced reactive metal wall for dehalogenation of hydrocarbons

    DOEpatents

    Howson, Paul E.; Mackenzie, Patricia D.; Horney, David P.

    1996-01-01

    A method is provided for remediation of contaminated solutions using a tiered metal wall or column. The tiered metal wall or column has at least three zones with graduated sizes of reducing metal particles. Contaminated solutions pass through the tiered wall or column to dehalogenate contaminant halogenated hydrocarbons.

  12. Effect of the additional anode layers on the absorption enhancement characteristic of plasmonic organic solar cells

    NASA Astrophysics Data System (ADS)

    Yoo, Sanghyuk; Kim, Jungho

    2014-12-01

    We numerically investigate the effect of additional anode layers on the absorption enhancement characteristic of pyramidal-grating plasmonic organic solar cells (OSCs) using the finite element method. The behaviors of the plasmonic absorption enhancement are compared between a “simple” structure consisting of only the active and metal cathode layers and a “practical” structure with the additional anode layers. The plasmonic absorption enhancement is identified by comparing the polarization-dependent absorbance spectra between the planar and plasmonic OSCs. When the active-layer thickness is small, the plasmonic resonance condition changes owing to the addition of the anode layers. When the active-layer thickness is large, the plasmonic resonance condition and corresponding absorption behavior show a slight difference irrespective of the inclusion of the additional anode layers. Therefore, the additional anode layers should be included in the optical analysis and design of plasmonic OSCs when the active-layer thickness is small.

  13. Influence of dissolved organic matter on the environmental fate of metals, nanoparticles, and colloids

    USGS Publications Warehouse

    Aiken, George R.; Hsu-Kim, Heileen; Ryan, Joseph N.

    2011-01-01

    We have known for decades that dissolved organic matter (DOM) plays a critical role in the biogeochemical cycling of trace metals and the mobility of colloidal particles in aquatic environments. In recent years, concerns about the ecological and human health effects of metal-based engineered nanoparticles released into natural waters have increased efforts to better define the nature of DOM interactions with metals and surfaces. Nanomaterials exhibit unique properties and enhanced reactivities that are not apparent in larger materials of the same composition1,2 or dissolved ions of metals that comprise the nanoparticles. These nanoparticle-specific properties generally result from the relatively large proportion of the atoms located at the surface, which leads to very high specific surface areas and a high proportion of crystal lattice imperfections relative to exposed surface area. Nanoscale colloids are ubiquitous in nature,2 and many engineered nanomaterials have analogs in the natural world. The properties of these materials, whether natural or manmade, are poorly understood, and new challenges have been presented in assessing their environmental fate. These challenges are particularly relevant in aquatic environments where interactions with DOM are key, albeit often overlooked, moderators of reactivity at the molecular and nanocolloidal scales.

  14. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture.

    PubMed

    Shekhah, Osama; Belmabkhout, Youssef; Chen, Zhijie; Guillerm, Vincent; Cairns, Amy; Adil, Karim; Eddaoudi, Mohamed

    2014-06-25

    Direct air capture is regarded as a plausible alternate approach that, if economically practical, can mitigate the increasing carbon dioxide emissions associated with two of the main carbon polluting sources, namely stationary power plants and transportation. Here we show that metal-organic framework crystal chemistry permits the construction of an isostructural metal-organic framework (SIFSIX-3-Cu) based on pyrazine/copper(II) two-dimensional periodic 4(4) square grids pillared by silicon hexafluoride anions and thus allows further contraction of the pore system to 3.5 versus 3.84 Å for the parent zinc(II) derivative. This enhances the adsorption energetics and subsequently displays carbon dioxide uptake and selectivity at very low partial pressures relevant to air capture and trace carbon dioxide removal. The resultant SIFSIX-3-Cu exhibits uniformly distributed adsorption energetics and offers enhanced carbon dioxide physical adsorption properties, uptake and selectivity in highly diluted gas streams, a performance, to the best of our knowledge, unachievable with other classes of porous materials.

  15. Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture

    PubMed Central

    Shekhah, Osama; Belmabkhout, Youssef; Chen, Zhijie; Guillerm, Vincent; Cairns, Amy; Adil, Karim; Eddaoudi, Mohamed

    2014-01-01

    Direct air capture is regarded as a plausible alternate approach that, if economically practical, can mitigate the increasing carbon dioxide emissions associated with two of the main carbon polluting sources, namely stationary power plants and transportation. Here we show that metal-organic framework crystal chemistry permits the construction of an isostructural metal-organic framework (SIFSIX-3-Cu) based on pyrazine/copper(II) two-dimensional periodic 44 square grids pillared by silicon hexafluoride anions and thus allows further contraction of the pore system to 3.5 versus 3.84 Å for the parent zinc(II) derivative. This enhances the adsorption energetics and subsequently displays carbon dioxide uptake and selectivity at very low partial pressures relevant to air capture and trace carbon dioxide removal. The resultant SIFSIX-3-Cu exhibits uniformly distributed adsorption energetics and offers enhanced carbon dioxide physical adsorption properties, uptake and selectivity in highly diluted gas streams, a performance, to the best of our knowledge, unachievable with other classes of porous materials. PMID:24964404

  16. Tunable electrical conductivity in metal-organic framework thin film devices

    SciTech Connect

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-05-24

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  17. Tunable electrical conductivity in metal-organic framework thin film devices

    SciTech Connect

    Talin, Albert Alec; Allendorf, Mark D.; Stavila, Vitalie; Leonard, Francois

    2016-08-30

    A composition including a porous metal organic framework (MOF) including an open metal site and a guest species capable of charge transfer that can coordinate with the open metal site, wherein the composition is electrically conductive. A method including infiltrating a porous metal organic framework (MOF) including an open metal site with a guest species that is capable of charge transfer; and coordinating the guest species to the open metal site to form a composition including an electrical conductivity greater than an electrical conductivity of the MOF.

  18. Organically complexed iron enhances bioavailability of antimony to maize (Zea mays) seedlings in organic soils.

    PubMed

    Ptak, Corey; McBride, Murray

    2015-12-01

    Antimony (Sb) is a metalloid belonging to group 15 of the periodic table. Chemical similarities between arsenic (As) and Sb produce concerns about potential health effects of Sb and enrichment in the environment. Antimony is found in oxic environments predominately as an oxyanionic species, antimonite (Sb[OH](6-)). As a result of its net negative charge, Sb[OH](6-) was not initially predicted to have strong interactions with natural organic matter. Oxyanionic species could bind the negatively charged organic matter via a ternary complexation mechanism, in which cationic metals mediate the strong association between organic matter functional groups and oxyanions. However, these interactions are poorly understood in how they influence the bioavailability of oxyanionic contaminants to plants. Iron (Fe) additions to organic soils have been found to increase the number of organically complexed Fe sites suitable for Sb exchange, resulting in a reduced bioavailable fraction of Sb. The bioavailability of Sb to maize seedlings as a function of organically complexed Fe was examined using a greenhouse study. A significant increase in plant tissue Sb was observed as organically complexed Fe increased, which was not predicted by methods commonly used to assess bioavailable Sb. Extraction of soils with organic acids common to the maize rhizosphere suggested that organic acid exudation can readily mobilize Sb bound by organic Fe complexes.

  19. Selective degradation of organic dyes by a resin modified Fe-based metal-organic framework under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Araya, Tirusew; Chen, Chun-cheng; Jia, Man-ke; Johnson, David; Li, Ruiping; Huang, Ying-ping

    2017-02-01

    Metal organic frameworks (MOFs), a new class of porous crystalline materials have attracted attention because of potential applications in environmental remediation. In this work, an Fe-based MOF, FeBTC (BTC = 1,3,5-tricarboxylic acid), was successfully modified with Amberlite IRA-200 resin to yield a novel heterogeneous photocatalyst, A@FeBTC. The modification resulted in higher photocatalytic activity than FeBTC under the same conditions. After 60 min of visible light illumination (λ ≥ 420 nm) 99% of rhodamine B was degraded. The modification lowers the zeta potential, enhancing charge-based selective adsorption and subsequent photocatalytic degradation of cationic dye pollutants. The composite also improved catalyst stability and recyclability by significantly reducing loss of iron leaching. Photoluminescence studies show that introduction of the resin reduces the recombination rate of photogenerated charge carriers thereby improving the photocatalytic activity of the composite. Finally, a plausible photocatalytic reaction mechanism is proposed.

  20. Nanosizing a Metal-Organic Framework Enzyme Carrier for Accelerating Nerve Agent Hydrolysis

    DTIC Science & Technology

    2016-10-05

    Chem. Soc. 2016, 138 (26), 8052− 8055. (12) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal- Organic ...Y.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C. Zr-Based Metal- Organic Frameworks: Design, Synthesis, Structure, and Applications . Chem. Soc... Application of Consistency Criteria to Calculate Bet Areas of Micro- and Mesoporous Metal- Organic Frameworks. J. Am. Chem. Soc. 2016, 138 (1), 215−224. (64

  1. Enhanced Electron-Phonon Coupling at Metal Surfaces

    SciTech Connect

    Plummer, Ward E.

    2010-08-04

    The Born-Oppenheimer approximation (BOA) decouples electronic from nuclear motion, providing a focal point for most quantum mechanics textbooks. However, a multitude of important chemical, physical and biological phenomena are driven by violations of this approximation. Vibronic interactions are a necessary ingredient in any process that makes or breaks a covalent bond, for example, conventional catalysis or enzymatically delivered biological reactions. Metastable phenomena associated with defects and dopants in semiconductors, oxides, and glasses entail violation of the BOA. Charge exchange in inorganic polymers, organic slats and biological systems involves charge- induced distortions of the local structure. A classic example is conventional superconductivity, which is driven by the electron-lattice interaction. High-resolution angle-resolved photoemission experiments are yielding new insight into the microscopic origin of electron-phonon coupling (EPC) in anisotropic two-dimensional systems. Our recent surface phonon measurement on the surface of a high-Tc material clearly indicates an important momentum dependent EPC in these materials. In the last few years we have shifted our research focus from solely looking at electron phonon coupling to examining the structure/functionality relationship at the surface of complex transition metal compounds. The investigation on electron phonon coupling has allowed us to move to systems where there is coupling between the lattice, the electrons and the spin.

  2. Metal-organic-framework-derived bi-metallic sulfide on N, S-codoped porous carbon nanocomposites as multifunctional electrocatalysts

    NASA Astrophysics Data System (ADS)

    Chen, Binling; Ma, Guiping; Zhu, Yanqiu; Wang, Jinbo; Xiong, Wei; Xia, Yongde

    2016-12-01

    A novel type of composite, consisting of a bi-metallic sulfide/carbon nanocomposite system, was developed as a multifunctional electrocatalyst. The nanocomposite system was facilely generated via a one-step simultaneous carbonization and sulfurization of a selected metal-organic framework. Sample Ni1Co4S@C-1000 is one of the most efficient electrocatalysts and exhibited superior activity and stability in oxygen evolution reaction (OER) due to the Ni substitution, the high porosity, the homogeneous dispersion of active components and the effect of N, S-codoping. This novel material showed a low onset potential of 1.43 V (vs reversible hydrogen electrode) and a stable current density of 10 mA cm-2 at 1.51 V in a 0.1 M KOH alkaline solution over a long-term operation, which is better than IrO2/C and other composites synthesized under the same conditions. The Ni1Co4S@C-1000 sample can also efficiently catalyse oxygen reduction reaction (ORR), with a four-electron pathway for reversible oxygen evolution and reduction. Furthermore, Ni1Co4S@C-800 showed enhanced electrocatalytic activity for hydrogen evolution reaction (HER) in water splitting. These findings pave a way to develop effective and promising alternative electrocatalysts towards OER, ORR and HER in the next generation of energy storage and conversion technologies.

  3. Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

    PubMed

    Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

    2016-03-09

    Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance.

  4. Production of Metal-Free Composites Composed of Graphite Oxide and Oxidized Carbon Nitride Nanodots and Their Enhanced Photocatalytic Performances.

    PubMed

    Kim, Seung Yeon; Oh, Junghoon; Park, Sunghee; Shim, Yeonjun; Park, Sungjin

    2016-04-04

    A novel metal-free composite (GN) composed of two types of carbon-based nanomaterials, graphite oxide (GO) and 2D oxidized carbon nitride (OCN) nanodots was produced. Chemical and morphological characterizations reveal that GN contains a main component of GO with well-dispersed 2D OCN nanodots. GN shows enhanced photocatalytic performance for degrading an organic pollutant, Rhodamine B, under visible light.

  5. Low-frequency noise properties of metal-organic-metal ultraviolet sensors

    NASA Astrophysics Data System (ADS)

    Su, Peng-Yin; Chuang, Ricky-Wenkuei; Chen, Chin-Hsiang; Kao, Tsung-Hsien

    2015-04-01

    For this study, the metal-organic-metal (MOM) ultraviolet (UV) sensors with organic 4,4‧,4‧‧-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) thin films of various thicknesses were fabricated successfully, and their low-frequency noise (LFN) characteristics were also analyzed. The findings revealed that the UV-to-visible rejection ratio of the fabricated 80-nm-thick m-MTDATA UV sensor was approximately 7.81 when biased at 5 V, with a cutoff at 220 nm. With an incident light wavelength of 220 nm and an applied bias of 5 V, the measured responsivity of the 80-nm-thick m-MTDATA UV sensor was found to be 2.84 × 10-4 A/W. Furthermore, a noise-equivalent power (NEP) of 9.8 × 10-11 W and a detectivity (D*) of 8.3 × 108 cm Hz0.5 W-1 can be achieved using the fabricated 80-nm-thick m-MTDATA UV sensor.

  6. Metal-organic organopolymeric hybrid framework by reversible [2+2] cycloaddition reaction.

    PubMed

    Park, In-Hyeok; Chanthapally, Anjana; Zhang, Zhenjie; Lee, Shim Sung; Zaworotko, Michael J; Vittal, Jagadese J

    2014-01-07

    Organic polymers are usually amorphous or possess very low crystallinity. The metal complexes of organic polymeric ligands are also difficult to crystallize by traditional methods because of their poor solubilities and their 3D structures can not be determined by single-crystal X-ray crystallography owing to a lack of single crystals. Herein, we report the crystal structure of a 1D Zn(II) coordination polymer fused with an organic polymer ligand made in situ by a [2+2] cycloaddition reaction of a six-fold interpenetrated metal-organic framework. It is also shown that this organic polymer ligand can be depolymerized in a single-crystal-to-single-crystal (SCSC) fashion by heating. This strategy could potentially be extended to make a range of monocrystalline metal organopolymeric complexes and metal-organic organopolymeric hybrid materials. Such monocrystalline metal complexes of organic polymers have hitherto been inaccessible for materials researchers.

  7. Plasmonic electrodes for organic photovoltaics: polarization-independent absorption enhancement

    NASA Astrophysics Data System (ADS)

    Zeng, Beibei; Kafafi, Zakya H.; Bartoli, Filbert J.

    2014-10-01

    We systematically investigate the optical and electrical properties of ultrathin two-dimensional (2D) Ag nanogratings (NGs), and explore their use as plasmonic transparent conducting electrodes in molecular organic photovoltaics (OPVs). A large broadband and polarization-insensitive optical absorption enhancement in the CuPc (copper phthalocyanine): PTCBI (perylene tetracarboxylic bisbenzimidazole) active light-harvesting layers is demonstrated using ultrathin 2D Ag NGs, and is attributed to the excitation of surface plasmon resonances and plasmonic cavity modes.

  8. THE MOST METAL-POOR STARS. III. THE METALLICITY DISTRIBUTION FUNCTION AND CARBON-ENHANCED METAL-POOR FRACTION , ,

    SciTech Connect

    Yong, David; Norris, John E.; Bessell, M. S.; Asplund, M.; Christlieb, N.; Beers, Timothy C.; Barklem, P. S.; Frebel, Anna; Ryan, S. G. E-mail: jen@mso.anu.edu.au E-mail: martin@mso.anu.edu.au E-mail: beers@pa.msu.edu E-mail: afrebel@mit.edu

    2013-01-01

    We examine the metallicity distribution function (MDF) and fraction of carbon-enhanced metal-poor (CEMP) stars in a sample that includes 86 stars with [Fe/H] {<=} -3.0, based on high-resolution, high signal-to-noise spectroscopy, of which some 32 objects lie below [Fe/H] = -3.5. After accounting for the completeness function, the 'corrected' MDF does not exhibit the sudden drop at [Fe/H] = -3.6 that was found in recent samples of dwarfs and giants from the Hamburg/ESO survey. Rather, the MDF decreases smoothly down to [Fe/H] = -4.1. Similar results are obtained from the 'raw' MDF. We find that the fraction of CEMP objects below [Fe/H] = -3.0 is 23% {+-} 6% and 32% {+-} 8% when adopting the Beers and Christlieb and Aoki et al. CEMP definitions, respectively. The former value is in fair agreement with some previous measurements, which adopt the Beers and Christlieb criterion.

  9. A multifunctional metal-organic framework based tumor targeting drug delivery system for cancer therapy

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Dong, Zhi-Yue; Cheng, Hong; Wan, Shuang-Shuang; Chen, Wei-Hai; Zou, Mei-Zhen; Huo, Jia-Wei; Deng, He-Xiang; Zhang, Xian-Zheng

    2015-09-01

    Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects.Drug delivery systems (DDSs) with biocompatibility and precise drug delivery are eagerly needed to overcome the paradox in chemotherapy that high drug doses are required to compensate for the poor biodistribution of drugs with frequent dose-related side effects. In this work, we reported a metal-organic framework (MOF) based tumor targeting DDS developed by a one-pot, and organic solvent-free ``green'' post-synthetic surface modification procedure, starting from the nanoscale MOF MIL-101. Owing to the multifunctional surface coating, premature drug release from this DDS was prevented. Due to the pH responsive benzoic imine bond and the redox responsive disulfide bond at the modified surface, this DDS exhibited tumor acid environment enhanced cellular uptake and intracellular reducing environment triggered drug release. In vitro and in vivo results showed that DOX loaded into this DDS exhibited effective cancer cell inhibition with much reduced side effects. Electronic supplementary information (ESI) available

  10. New metal-organic nanomaterials synthesized by laser irradiation of organic liquids

    SciTech Connect

    Kuzmin, Stanislav L.; Wesolowski, Michal J.; Duley, Walter W.

    2014-03-31

    A new type of metal-organic composition consisting of clusters of nanoparticles has been synthesised by laser irradiation of metallocene/benzene solutions. The metallocene molecules in this reaction become the source of the metal. Exposure to high-energy femtosecond laser pulses dehydrogenate benzene molecules and initiate the high-temperature high-pressure conditions that results in the synthesis of new materials. Irradiation experiments have been carried out on ferrocene/benzene and on other solutions. With ferrocene the synthesis of a new compound has been confirmed by X-ray powder diffraction as the peaks detected do not correspond to any known substance in the Crystallography Open Database. Theoretical simulation of the periodic structure of this new carbide predicts that it has hexagonal symmetry and a unit cell with a = 3.2A and c =2.8A. The exact structure is still uncertain but may be determined from scanning tunneling microscope (STM) studies.

  11. Stimuli-Responsive Metal Organic Frameworks: Stimuli-Responsive Metal Organic Frameworks for Energy-Efficient Post Combustion Capture

    SciTech Connect

    2010-07-01

    IMPACCT Project: A team led by three professors at Texas A&M is developing a subset of metal organic frameworks that respond to stimuli such as small changes in temperature to trap CO2 and then release it for storage. These frameworks are a promising class of materials for carbon capture applications because their structure and chemistry can be controlled with great precision. Because the changes in temperature required to trap and release CO2 in Texas A&M’s frameworks are much smaller than in other carbon capture approaches, the amount of energy or stimulus that has to be diverted from coal-fired power plants to accomplish this is greatly reduced. The team is working to alter the materials so they bind only with CO2, and are stable enough to withstand the high temperatures found in the chimneys of coal-fired power plants.

  12. Structural alteration of the metal-organic pyrogallol[4]arene nano-capsule motif by incorporation of large metal centres.

    PubMed

    Jin, Ping; Kumari, Harshita; Kennedy, Stuart; Barnes, Charles L; Teat, Simon J; Dalgarno, Scott J; Atwood, Jerry L

    2014-05-04

    Addition of cadmium(II) nitrate to gallium-coordinated metal-organic C-alkylpyrogallol[4]arene nano-capsules affords a variation of the near spherical hexamer motif, structural changes in which are induced by the markedly different nature of the secondary incorporated metal.

  13. Computational Investigations of Potential Energy Function Development for Metal--Organic Framework Simulations, Metal Carbenes, and Chemical Warfare Agents

    NASA Astrophysics Data System (ADS)

    Cioce, Christian R.

    Metal-Organic Frameworks (MOFs) are three-dimensional porous nanomaterials with a variety of applications, including catalysis, gas storage and separation, and sustainable energy. Their potential as air filtration systems is of interest for designer carbon capture materials. The chemical constituents (i.e. organic ligands) can be functionalized to create rationally designed CO2 sequestration platforms, for example. Hardware and software alike at the bleeding edge of supercomputing are utilized for designing first principles-based molecular models for the simulation of gas sorption in these frameworks. The classical potentials developed herein are named PHAST --- Potentials with High Accuracy, Speed, and Transferability, and thus are designed via a "bottom-up" approach. Specifically, models for N2 and CH4 are constructed and presented. Extensive verification and validation leads to insights and range of applicability. Through this experience, the PHAST models are improved upon further to be more applicable in heterogeneous environments. Given this, the models are applied to reproducing high level ab initio energies for gas sorption trajectories of helium atoms in a variety of rare-gas clusters, the geometries of which being representative of sorption-like environments commonly encountered in a porous nanomaterial. This work seeks to push forward the state of classical and first principles materials modeling. Additionally, the characterization of a new type of tunable radical metal---carbene is presented. Here, a cobalt(II)---porphyrin complex, [Co(Por)], was investigated to understand its role as an effective catalyst in stereoselective cyclopropanation of a diazoacetate reagent. Density functional theory along with natural bond order analysis and charge decomposition analysis gave insight into the electronics of the catalytic intermediate. The bonding pattern unveiled a new class of radical metal---carbene complex, with a doublet cobalt into which a triplet carbene

  14. Residual organic matter and microbial respiration in bottom ash: Effects on metal leaching and eco-toxicity.

    PubMed

    Ilyas, A; Persson, K M; Persson, M

    2015-09-01

    A common assumption regarding the residual organic matter, in bottom ash, is that it does not represent a significant pool of organic carbon and, beyond metal-ion complexation process, it is of little consequence to evolution of ash/leachate chemistry. This article evaluates the effect of residual organic matter and associated microbial respiratory processes on leaching of toxic metals (i.e. arsenic, copper, chromium, molybdenum, nickel, lead, antimony and zinc), eco-toxicity of ash leachates. Microbial respiration was quantified with help of a respirometric test equipment OXITOP control system. The effect of microbial respiration on metal/residual organic matter leaching and eco-toxicity was quantified with the help of batch leaching tests and an eco-toxicity assay - Daphnia magna. In general, the microbial respiration process decreased the leachate pH and eco-toxicity, indicating modification of bioavailability of metal species. Furthermore, the leaching of critical metals, such as copper and chromium, decreased after the respiration in both ash types (fresh and weathered). It was concluded that microbial respiration, if harnessed properly, could enhance the stability of fresh bottom ash and may promote its reuse.

  15. Biodistribution of inhaled metal oxide nanoparticles mimicking occupational exposure: a preliminary investigation using enhanced darkfield microscopy.

    PubMed

    Guttenberg, Marissa; Bezerra, Leonardo; Neu-Baker, Nicole M; Del Pilar Sosa Idelchik, María; Elder, Alison; Oberdörster, Günter; Brenner, Sara A

    2016-10-01

    Inhalation exposure to engineered nanomaterials (ENMs) may result in adverse pulmonary and/or systemic health effects. In this study, enhanced darkfield microscopy (EDFM) was used as a novel approach to visualizing industrial metal oxide nanoparticles (NPs) (silica, ceria, or alumina) in multiple tissue types following inhalation in rats mimicking occupational exposures. Advantages of EDFM over electron microscopy (EM) include reduced cost, time, and ease of sample preparation and operation. Following 4-6 hour inhalation exposures at three concentrations (3.5-34.0 mg/m(3) ), lungs and secondary organs were harvested at 24 hours or 7 days post-exposure and prepared for brightfield (BF) microscopy and EDFM. NPs were visualized within the lung and associated lymphatic tissues and in major organs of excretion (liver, spleen, kidney). EDFM also revealed NPs within pulmonary blood vessels and localization within specific regions of toxicological relevance in liver and kidney, indicating pathways of excretion. Results demonstrate the utility of EDFM for rapid direct visualization of NPs in various tissue types and suggest the potential for metal oxide NPs to distribute to secondary tissues following inhalation exposure. Confirmation of the composition, distribution, and relative abundance of inhaled NPs will be pursued by combining EDFM with hyperspectral imaging (HSI) and mapping.

  16. Enhanced Antimicrobial Activity Of Antibiotics Mixed With Metal Nanoparticles

    NASA Astrophysics Data System (ADS)

    Kumar, Sandeep; Kumar, Neeraj; Bhanjana, Gaurav; Thakur, Rajesh; Dilbaghi, Neeraj

    2011-12-01

    Current producers of antimicrobial technology have a long lasting, environmentally safe, non-leaching, water soluble solution that will eventually replace all poisons and heavy metals. The transition metal ions inevitably exist as metal complexes in biological systems by interaction with the numerous molecules possessing groupings capable of complexation or chelation. Nanoparticles of metal oxides offer a wide variety of potential applications in medicine due to the unprecedented advances in nanobiotechnology research. the bacterial action of antibiotics like penicillin, erythryomycin, ampicillin, streptomycin, kanamycin etc. and that of a mixture of antibiotics and metal and metal oxide nanoparticles like zinc oxide, zirconium, silver and gold on microbes was examined by the agar-well-diffusion method, enumeration of colony-forming units (CFU) and turbidimetry.

  17. Chemical Raman Enhancement of Organic Adsorbates on Metal Surfaces

    DTIC Science & Technology

    2011-02-25

    system with an ordered monolayer of about one BTmolecule per nm2 bonded to a flat periodic Au(111) slab. A 400 eV plane-wave cutoff and 2 2 1 Monkhorst...cm 1 width. (B) Binding geometries. Our supercell consists of 5 atomic layers of Au stacked along [111] with 16 atoms per layer, with 30 Å of vacuum... 1 ] M. Fleischman, P. J. Hendra, and A. McQuillan, Chem. Phys. Lett. 26, 163 (1974). [2] D. L. Jeanmaire and R. P. V . Duyne, J. Electroanal. Chem. 84

  18. Enhancing phytoextraction: the effect of chemical soil manipulation on mobility, plant accumulation, and leaching of heavy metals.

    PubMed

    Schmidt, Ulrich

    2003-01-01

    For heavy metal-contaminated agricultural land, low-cost, plant-based phytoextraction measures can be a key element for a new land management strategy. When agents are applied into the soil, the solubility of heavy metals and their subsequent accumulation by plants can be increased, and, therefore, phytoextraction enhanced. An overview is given of the state of the art of enhancing heavy metal solubility in soils, increasing the heavy metal accumulation of several high-biomass-yielding and metal-tolerant plants, and the effect of these measures on the risk of heavy metal leaching. Several organic as well as inorganic agents can effectively and specifically increase solubility and, therefore, accumulation of heavy metals by several plant species. Crops like willow (Salix viminalis L.), Indian mustard [Brassica juncea (L.) Czern.], corn (Zea mays L.), and sunflower (Helianthus annuus L.) show high tolerance to heavy metals and are, therefore, to a certain extent able to use the surpluses that originate from soil manipulation. More than 100-fold increases of lead concentrations in the biomass of crops were reported, when ethylenediaminetetraacetic acid (EDTA) was applied to contaminated soils. Uranium concentrations could be strongly increased when citric acid was applied. Cadmium and zinc concentrations could be enhanced by inorganic agents like elemental sulfur or ammonium sulfate. However, leaching of heavy metals due to increased mobility in soils cannot be excluded. Thus, implementation on the field scale must consider measures to minimize leaching. So, the application of more than 1 g EDTA kg(-1) becomes inefficient as lead concentration in crops is not enhanced and leaching rate increases. Moreover, for large-scale applications, agricultural measures as placement of agents, dosage splitting, the kind and amount of agents applied, and the soil properties are important factors governing plant growth, heavy metal concentrations, and leaching rates. Effective

  19. Role of hydrocarbons in pore expansion and contraction of a flexible metal-organic framework

    SciTech Connect

    Motkuri, Radha K.; Thallapally, Praveen K.; Nune, Satish K.; Fernandez, Carlos A.; McGrail, B. Peter; Atwood, Jerry L.

    2011-05-06

    A flexible metal organic framework obtained from a flexible organic linker shows a breathing phenomenon upon adsorption of polar protic and non-polar solvents. Sorption profiles indicate favorable interactions with non-polar solvents over polar solvents.

  20. Probing buried organic-organic and metal-organic heterointerfaces by hard x-ray photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Shibuta, Masahiro; Eguchi, Toyoaki; Watanabe, Yoshio; Son, Jin-Young; Oji, Hiroshi; Nakajima, Atsushi

    2012-11-01

    We present a nondestructive characterization method for buried hetero-interfaces for organic/organic and metal/organic systems using hard x-ray photoelectron spectroscopy (HAXPES) which can probe electronic states at depths deeper than ˜10 nm. A significant interface-derived signal showing a strong chemical interaction is observed for Au deposited onto a C60 film, while there is no such additional feature for copper phthalocyanine deposited onto a C60 film reflecting the weak interaction between the molecules in the latter case. A depth analysis with HAXPES reveals that a Au-C60 intermixed layer with a thickness of 5.1 nm is formed at the interface.

  1. Reaction Engineering with Metal-Organic Framework Catalysts

    NASA Astrophysics Data System (ADS)

    Melkonian, Arek Viken

    To date, there has been no comprehensive attempt to perform and/or describe catalytic reactions in the gas phase that utilize metal-organic frameworks (MOFs) as catalysts. In addition, there has been no attempt to reaction engineer these MOF catalysts in order to determine their regimes of optimal catalytic activity and possible limitations to their use. A zinc-based MOF that has been post-synthetically modified with a homogeneous palladium catalyst, Pd(CH 3CN)2Cl2, is used to catalyze the hydrogenation of propylene. The catalyst is assembled in a packed-bed reactor under a continuous flow of reactants. The reaction is optimized with respect to isoreticular metalation, reactant flow rate, and reactor temperature. Maximum catalytic conversion is found at intermediate metalations of 40% and 60%, high hydrogen flow of 50 ccm, and intermediate reactor temperatures of 100 °C and 150 °C. The MOF-60 catalyst is exposed to a traditional catalyst poison, carbon monoxide (CO). It is found that the MOF is reversibly poisoned upon introduction of CO. Upon poisoning, catalytic conversions rates of 90%-100% are dramatically reduced to less than 10%-30%, depending on the CO flow rate and the reactor temperature. The CO poisoning is shown to be reversible, a similar effect as found with palladium on carbon (Pd/C). The time scale of poisoning and recovery is very fast for both the MOF catalyst and Pd/C (approximately 10-30 seconds). Other effects of temperature on the MOF-40 are also investigated. At fixed reactant flow, the temperature grid is partitioned into finer steps of 10 °C to determine the temperature that yields the highest catalytic conversion. It is found that conversion is nearly uniform in the range between the highest conversions, i.e., conversion plateaus between the optimum temperatures. The catalyst also exhibits a weak thermal hysteresis. There is no significant improvement in conversion with thermal cycling after alternating the reactor temperature between

  2. Transmission enhancement based on strong interference in metal-semiconductor layered film for energy harvesting.

    PubMed

    Li, Qiang; Du, Kaikai; Mao, Kening; Fang, Xu; Zhao, Ding; Ye, Hui; Qiu, Min

    2016-07-12

    A fundamental strategy to enhance optical transmission through a continuous metallic film based on strong interference dominated by interface phase shift is developed. In a metallic film coated with a thin semiconductor film, both transmission and absorption are simultaneously enhanced as a result of dramatically reduced reflection. For a 50-nm-thick Ag film, experimental transmission enhancement factors of 4.5 and 9.5 are realized by exploiting Ag/Si non-symmetric and Si/Ag/Si symmetric geometries, respectively. These planar layered films for transmission enhancement feature ultrathin thickness, broadband and wide-angle operation, and reduced resistance. Considering one of their potential applications as transparent metal electrodes in solar cells, a calculated 182% enhancement in the total transmission efficiency relative to a single metallic film is expected. This strategy relies on no patterned nanostructures and thereby may power up a wide spectrum of energy-harvesting applications such as thin-film photovoltaics and surface photocatalysis.

  3. Transmission enhancement based on strong interference in metal-semiconductor layered film for energy harvesting

    NASA Astrophysics Data System (ADS)

    Li, Qiang; Du, Kaikai; Mao, Kening; Fang, Xu; Zhao, Ding; Ye, Hui; Qiu, Min

    2016-07-01

    A fundamental strategy to enhance optical transmission through a continuous metallic film based on strong interference dominated by interface phase shift is developed. In a metallic film coated with a thin semiconductor film, both transmission and absorption are simultaneously enhanced as a result of dramatically reduced reflection. For a 50-nm-thick Ag film, experimental transmission enhancement factors of 4.5 and 9.5 are realized by exploiting Ag/Si non-symmetric and Si/Ag/Si symmetric geometries, respectively. These planar layered films for transmission enhancement feature ultrathin thickness, broadband and wide-angle operation, and reduced resistance. Considering one of their potential applications as transparent metal electrodes in solar cells, a calculated 182% enhancement in the total transmission efficiency relative to a single metallic film is expected. This strategy relies on no patterned nanostructures and thereby may power up a wide spectrum of energy-harvesting applications such as thin-film photovoltaics and surface photocatalysis.

  4. Detection of Volatile Organic Compounds by Weight-Detectable Sensors coated with Metal-Organic Frameworks

    PubMed Central

    Yamagiwa, Hiroki; Sato, Seiko; Fukawa, Tadashi; Ikehara, Tsuyoshi; Maeda, Ryutaro; Mihara, Takashi; Kimura, Mutsumi

    2014-01-01

    Detection of volatile organic compounds (VOCs) using weight-detectable quartz microbalance and silicon-based microcantilever sensors coated with crystalline metal-organic framework (MOF) thin films is described in this paper. The thin films of two MOFs were grown from COOH-terminated self-assembled monolayers onto the gold electrodes of sensor platforms. The MOF layers worked as the effective concentrators of VOC gases, and the adsorption/desorption processes of the VOCs could be monitored by the frequency changes of weight-detectable sensors. Moreover, the MOF layers provided VOC sensing selectivity to the weight-detectable sensors through the size-selective adsorption of the VOCs within the regulated nanospace of the MOFs. PMID:25175808

  5. A Challenge Beyond Bottom Cells: Top-Illuminated Flexible Organic Solar Cells with Nanostructured Dielectric/Metal/Polymer (DMP) Films.

    PubMed

    Ham, Juyoung; Dong, Wan Jae; Park, Jae Yong; Yoo, Chul Jong; Lee, Illhwan; Lee, Jong-Lam

    2015-07-15

    Top-illuminated flexible organic solar cells with a high power conversion efficiency (≈6.75%) are fabricated using a dielectric/metal/polymer (DMP) electrode. Employing a polymer layer (n = 1.49) makes it possible to show the high transmittance, which is insensitive to film thickness, and the excellent haze induced by well-ordered nanopatterns on the DMP electrode, leading to a 28% of enhancement in efficiency compared to bottom cells.

  6. Shock resistance of metal-organic framework Cu-1,3,5-benzenetricarboxylate with and without ferrocene inclusion

    NASA Astrophysics Data System (ADS)

    Wei, Q.; Xu, H. W.; Yu, X. H.; Shimada, T.; Rearick, M. S.; Hickmott, D. D.; Zhao, Y. S.; Luo, S. N.

    2011-09-01

    A first-of-its-kind study on the shock response of a metal-organic framework (MOF) material to planar impact is reported. MOF Cu-1,3,5-benzenetricarboxylate (Cu-BTC) without and with ferrocene inclusion show anisotropic structural collapse under shock loading. The shock resistance of the Cu-BTC framework is enhanced drastically (by a factor of six) via molecular-level inclusion of ferrocene into the pore structures.

  7. Shock Resistance of Metal-Organic Framework Cu-1,3,5-Benzenetricarboxylate with and without Ferrocene Inclusion

    NASA Astrophysics Data System (ADS)

    Wei, Q.; Xu, H. W.; Luo, S. N.

    2011-06-01

    A first-of-the-kind study on the dynamic response of a metal-organic framework (MOF) material to impulsive shock wave loading is reported. MOF Cu-1,3,5-benzenetricarboxylate (Cu-BTC) without and with ferrocene inclusion show anisotropic structural collapse under shock loading, likely due to the elastic anisotropy of the network structure. The shock resistance of Cu-BTC framework is enhanced drastically (by a factor of six) via including ferrocene into the pore structures.

  8. Adsorption of two gas molecules at a single metal site in a metal–organic framework

    SciTech Connect

    Runčevski, Tomče; Kapelewski, Matthew T.; Torres-Gavosto, Rodolfo M.; Tarver, Jacob D.; Brown, Craig M.; Long, Jeffrey R.

    2016-01-01

    One strategy to markedly increase the gas storage capacity of metal-organic frameworks is to introduce coordinatively-unsaturated metal centers capable of binding multiple gas molecules. Herein, we provide an initial demonstration that a single metal site within a framework can support the terminal coordination of two gas molecules--specifically hydrogen, methane, or carbon dioxide.

  9. Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

    PubMed

    Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

    2013-04-10

    Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

  10. X-ray crystallographic insights into post-synthetic metalation products in a metal-organic framework.

    PubMed

    Huxley, Michael T; Coghlan, Campbell J; Bloch, Witold M; Burgun, Alexandre; Doonan, Christian J; Sumby, Christopher J

    2017-01-13

    Post-synthetic modification of metal-organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as 'metalation', is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1: , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1: prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1: with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1: against equivalent solid- and solution-state species suggests that the void space in 1: does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

  11. Understanding H2- H2 interactions in Metal Organic Frameworks (MOFs) with unsaturated metal centers

    NASA Astrophysics Data System (ADS)

    Nijem, Nour; Veyan, Jean F.; Kong, Lingzhu; Zhao, Yonggang; Li, Jing; Langreth, David; Chabal, Yves J.

    2011-03-01

    Unsaturated Metal Organic Frameworks (MOFs) are particularly interesting due to their high H2 uptakes with relatively large isosteric heats of adsorption (Qst > 8 kJ / mol) . ThisworkexploresH 2 - H 2 interactionsbetweenadsorbedH 2 atthedifferentsitesinMOF - 74 (M 2 (dhtp) , dhtp = 2 , 5 - dihydroxyterephthalate) andcombinesIRspectroscopywithvdW - DFTcalculations . TheadsorptionsitesinMOF - 74 arefromhighesttolowestbindingenergiesthemetal , oxygen , benzeneandpore - centersites . ThefrequencyofadsorbedH 2 atthemetalsitesuffersanadditional ~ - 30 cm -1 redshift (forMgandZn) and ~ - 84 cm -1 (forCo) whentheneighboringoxygensiteisoccupied . ThedipolemomentofadsorbedH 2 isalsoaffected . TheseinteractionsextendtothebenzenesitesforMOF - 74 - Co . AdecreaseindipolemomentofH 2 adsorbedatthemetalsiteisobservedwiththepartialoccupationofthebenzenesites . However , thecompleteoccupationofthebenzenesitesinducesanadditional ~ - 10 cm -1 red shift. DOE Grant No. DE-FG02-08ER46491.

  12. Photoreactivity of Metal-Organic Frameworks in Aqueous Solutions: Metal Dependence of Reactive Oxygen Species Production.

    PubMed

    Liu, Kai; Gao, Yanxin; Liu, Jing; Wen, Yifan; Zhao, Yingcan; Zhang, Kunyang; Yu, Gang

    2016-04-05

    Promising applications of metal-organic frameworks (MOFs) in various fields have raised concern over their environmental fate and safety upon inevitable discharge into aqueous environments. Currently, no information regarding the transformation processes of MOFs is available. Due to the presence of repetitive π-bond structure and semiconductive property, photochemical transformations are an important fate process that affects the performance of MOFs in practical applications. In the current study, the generation of reactive oxygen species (ROS) in isoreticular MIL-53s was studied. Scavengers were employed to probe the production of (1)O2, O2(•-), and •OH, respectively. In general, MIL-53(Cr) and MIL-53(Fe) are dominated by type I and II photosensitization reactions, respectively, and MIL-53(Al) appears to be less photoreactive. The generation of ROS in MIL-53(Fe) may be underestimated due to dismutation. Further investigation of MIL-53(Fe) encapsulated diclofenac transformation revealed that diclofenac can be easily transformed by MIL-53(Fe) generated ROS. However, the cytotoxicity results implied that the ROS generated from MIL-53s have little effect on the viability of the human hepatocyte (HepG2) cell line. These results suggest that the photogeneration of ROS by MOFs may be metal-node dependent, and the application of MIL-53s as drug carriers needs to be carefully considered due to their high photoreactivity.

  13. Introduction of functionalized mesopores to metal-organic frameworks via metal-ligand-fragment coassembly.

    PubMed

    Park, Jinhee; Wang, Zhiyong U; Sun, Lin-Bing; Chen, Ying-Pin; Zhou, Hong-Cai

    2012-12-12

    Introduction of functionalized mesopores into microporous metal-organic frameworks (MOFs) can endow them with suitable properties for applications in gas storage, separation, catalysis, and drug delivery. However, common methods for functionalization (including pre- and post-synthetic modifications) of the internal surface of a MOF reduce the pore size of the MOF because the additional functional groups fill up the pores. We present a metal-ligand-fragment coassembly strategy for the introduction of (meso)pores functionalized with various substituent groups on the ligand fragments. Astonishingly, this new functionalization strategy increases the pore volume of a MOF instead of reducing it. Since the ligand fragments are often readily available or easily prepared, the new procedure for synthesis of the modified MOFs becomes much easier and more applicable than existing approaches. Remarkably, mesopores can be generated conveniently and controllably by the coassembly of a ligand and its fragment containing the desired functional groups. The fragment/ligand ratio has been optimized to preserve the parent structure and to promote maximum mesopore introduction, which has led to a systematic evaluation of the effectiveness of a series of functional groups for the adsorption of guest molecules.

  14. Metal Insertion in a Microporous Metal-Organic Framework Lined with 2,2'-Bipyridine

    SciTech Connect

    Bloch, Eric D.; Britt, David; Lee, Chain; Doonan, Christian J.; Uribe-Romo, Fernando J.; Furukawa, Hiroyasu; Long, Jeffrey R.; Yaghi, Omar M.

    2010-10-20

    Reaction of AlCl3·6H2O with 2,2'-bipyridine-5,5'-dicarboxylic acid (H2bpydc) affords Al(OH)(bpydc) (1, MOF-253), the first metal-organic framework with open 2,2'-bipyridine (bpy) coordination sites. The material displays a BET surface area of 2160 m2/g and readily complexes metals to afford, for example, 1·xPdCl2 (x = 0.08, 0.83) and 1·0.97Cu(BF4)2. EXAFS spectroscopy performed on 1·0.83PdCl2 reveals the expected square planar coordination geometry, matching the structure of the model complex (bpy)PdCl2. Finally, significantly, the selectivity factor for binding CO2 over N2 under typical flue gas conditions is observed to increase from 2.8 in 1 to 12 in 1·0.97Cu(BF4)2.

  15. Porous, rigid metal(III)-carboxylate metal-organic frameworks for the delivery of nitric oxide

    NASA Astrophysics Data System (ADS)

    Eubank, Jarrod F.; Wheatley, Paul S.; Lebars, Gaëlle; McKinlay, Alistair C.; Leclerc, Hervé; Horcajada, Patricia; Daturi, Marco; Vimont, Alexandre; Morris, Russell E.; Serre, Christian

    2014-12-01

    The room temperature sorption properties of the biological gas nitric oxide (NO) have been investigated on the highly porous and rigid iron or chromium carboxylate based metal-organic frameworks Material Institut Lavoisier (MIL)-100(Fe or Cr) and MIL-127(Fe). In all cases, a significant amount of NO is chemisorbed at 298 K with a loading capacity that depends both on the nature of the metal cation, the structure and the presence of additional iron(II) Lewis acid sites. In a second step, the release of NO triggered by wet nitrogen gas has been studied by chemiluminescence and indicates that only a partial release of NO occurs as well as a prolonged delivery at the biological level. Finally, an in situ infrared spectroscopy study confirms not only the coordination of NO over the Lewis acid sites and the stronger binding of NO on the additional iron(II) sites, providing further insights over the partial release of NO only in the presence of water at room temperature.

  16. Three-dimensional metal-intercalated covalent organic frameworks for near-ambient energy storage

    NASA Astrophysics Data System (ADS)

    Gao, Fei; Ding, Zijing; Meng, Sheng

    2013-05-01

    A new form of nanoporous material, metal intercalated covalent organic framework (MCOF) is proposed and its energy storage property revealed. Employing density functional and thermodynamical analysis, we find that stable, chemically active, porous materials could form by stacking covalent organic framework (COF) layers with metals as a gluing agent. Metal acts as active sites, while its aggregation is suppressed by a binding energy significantly larger than the corresponding cohesive energy of bulk metals. Two important parameters, metal binding and metal-metal separation, are tuned by selecting suitable building blocks and linkers when constructing COF layers. Systematic searches among a variety of elements and organic molecules identify Ca-intercalated COF with diphenylethyne units as optimal material for H2 storage, reaching a striking gravimetric density ~ 5 wt% at near-ambient conditions (300 K, 20 bar), in comparison to < 0.1 wt% for bare COF-1 under the same condition.

  17. Performance enhancement of top contact pentacene-based organic thin-film transistor (OTFT) using perylene interlayer between organic/electrode interface

    NASA Astrophysics Data System (ADS)

    Borthakur, Tribeni; Sarma, Ranjit

    2017-03-01

    We have investigated the effect of perylene interlayer between the organic/electrode interface on the electrical performance of a top contact pentacene-based OTFT. We have found the performance enhancement of the OTFT device. The OTFT devices with perylene layer show better field effect mobility and on-off ratio than that of having only metal electrodes. It also lowers the subthreshold slope and threshold voltage compared to single-layered OTFT devices.

  18. Seebeck coefficient in correlated low-dimensional organic metals

    NASA Astrophysics Data System (ADS)

    Shahbazi, M.; Bourbonnais, C.

    2016-11-01

    We study the influence of inelastic electron-electron scattering on the temperature variation of the Seebeck coefficient in the normal phase of quasi-one-dimensional organic superconductors. The theory is based on the numerical solution of the semiclassical Boltzmann equation for which the collision integral equation is solved with the aid of the renormalization-group method for the electronic umklapp scattering vertex. We show that the one-loop renormalization-group flow of momentum and temperature-dependent umklapp scattering, in the presence of nesting alterations of the Fermi surface, introduce electron-hole asymmetry in the energy dependence of the anisotropic scattering time. This is responsible for the enhancement of the Seebeck coefficient with respect to the band T -linear prediction and even its sign reversal around the quantum critical point of the phase diagram, namely, where the interplay between antiferromagnetism and superconductivity and also the strength of spin fluctuations are the strongest. A comparison of the results with available data on low-dimensional organic superconductors is presented and critically discussed.

  19. Enhanced anaerobic digestion of food waste by trace metal elements supplementation and reduced metals dosage by green chelating agent [S, S]-EDDS via improving metals bioavailability.

    PubMed

    Zhang, Wanli; Zhang, Lei; Li, Aimin

    2015-11-01

    This study aimed at investigating the effects of trace metals on methane production from food waste and examining the feasibility of reducing metals dosage by ethylenediamine-N,N'-disuccinic acid (EDDS) via improving metals bioavailability. The results indicated that the effects of metal elements highly depended on the supplemental concentrations. Trace metals supplemented under moderate concentrations greatly enhanced the methane yield. However, the excessive supplementation of Fe (1000 mg/L) and Ni (50 mg/L) exhibited the obvious toxicity to methanogens. The combinations of trace metals exhibited remarkable synergistic effects. The supplementation of Fe (100 mg/L) + Co (1 mg/L) + Mo (5 mg/L) + Ni (5 mg/L) obtained the greatest methane yield of 504 mL/g VSadded and the highest increment of 35.5% compared to the reactor without metals supplementation (372 mL/g VSadded). The changes of metals speciation showed the reduction of metals bioavailability during anaerobic digestion, which might weaken the stimulative effects of trace metals. However, the addition of EDDS improved metals bioavailability for microbial uptake and stimulated the activity of methanogens, and therefore, strengthened the stimulative effects of metals on anaerobic digestion of food waste. The batch and semi-continuous experiments confirmed that the addition of EDDS (20 mg/L) bonded to trace metals prior to their supplementation could obtain a 50% reduction of optimal metals dosage. This study provided a feasible method to reduce trace metals dosage without the degeneration of process performance of anaerobic digestion.

  20. Synthesis and Characterization of Functionalized Metal-organic Frameworks

    PubMed Central

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A.; Hupp, Joseph T.; Farha, Omar K.

    2014-01-01

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy. PMID:25225784

  1. Synthesis and characterization of functionalized metal-organic frameworks.

    PubMed

    Karagiaridi, Olga; Bury, Wojciech; Sarjeant, Amy A; Hupp, Joseph T; Farha, Omar K

    2014-09-05

    Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

  2. Metal-organic frameworks for lithium ion batteries and supercapacitors

    SciTech Connect

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  3. Redox-Active Metal-Organic Composites for Highly Selective Oxygen Separation Applications

    SciTech Connect

    Zhang, Wen; Banerjee, Debasis; Liu, Jian; Schaef, Herbert T.; Crum, Jarrod V.; Fernandez, Carlos A.; Kukkadapu, Ravi K.; Nie, Zimin; Nune, Satish K.; Motkuri, Radha K.; Chapman, Karena W.; Engelhard, Mark H.; Hayes, James C.; Silvers, Kurt L.; Krishna, Rajamani; McGrail, B. Peter; Liu, Jun; Thallapally, Praveen K.

    2016-03-08

    A redox-active metal-organic composite material shows improved and selective O-2 adsorption over N-2 with respect to individual components (MIL-101 and ferrocene). The O-2 sensitivity of the composite material arises due to the formation of maghemite nanoparticles with the pore of the metal-organic framework material.

  4. Capturing neon - the first experimental structure of neon trapped within a metal-organic environment.

    PubMed

    Wood, Peter A; Sarjeant, Amy A; Yakovenko, Andrey A; Ward, Suzanna C; Groom, Colin R

    2016-08-21

    Despite being the fifth most abundant element in the atmosphere, neon has never been observed in an organic or metal-organic environment. This study shows the adsorption of this highly unreactive element within such an environment and reveals the first crystallographic observation of an interaction between neon and a transition metal.

  5. Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

    NASA Technical Reports Server (NTRS)

    Sinha, Mahadeva P. (Inventor)

    1996-01-01

    Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

  6. Enhancing thermoelectric properties of organic composites through hierarchical nanostructures

    PubMed Central

    Zhang, Kun; Zhang, Yue; Wang, Shiren

    2013-01-01

    Organic thermoelectric (TE) materials are very attractive due to easy processing, material abundance, and environmentally-benign characteristics, but their potential is significantly restricted by the inferior thermoelectric properties. In this work, noncovalently functionalized graphene with fullerene by π-π stacking in a liquid-liquid interface was integrated into poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate). Graphene helps to improve electrical conductivity while fullerene enhances the Seebeck coefficient and hinders thermal conductivity, resulting in the synergistic effect on enhancing thermoelectric properties. With the integration of nanohybrids, the electrical conductivity increased from ~10000 to ~70000 S/m, the thermal conductivity changed from 0.2 to 2 W·K−1m−1 while the Seebeck coefficient was enhanced by around 4-fold. As a result, nanohybrids-based polymer composites demonstrated the figure of merit (ZT) as high as 6.7 × 10−2, indicating an enhancement of more than one order of magnitude in comparison to single-phase filler-based polymer composites with ZT at the level of 10−3. PMID:24336319

  7. Alternate metal framework designs for the metal ceramic prosthesis to enhance the esthetics

    PubMed Central

    Vernekar, Naina Vilas; Jagadish, Prithviraj Kallahalla; Diwakar, Srinivasan; Nadgir, Ramesh

    2011-01-01

    PURPOSE The objective of the present study was to evaluate the effect of five different metal framework designs on the fracture resistance of the metal-ceramic restorations. MATERIALS AND METHODS For the purpose of this study, the central incisor tooth was prepared, and the metal analogue of it and a master die were fabricated. The counter die with the 0.5 mm clearance was used for fabricating the wax patterns for the metal copings. The metal copings with five different metal framework designs were designed from Group 1 to 5. Group 1 with the metal collar, Group 2, 3, 4 and 5 with 0 mm, 0.5 mm, 1 mm and 1.5 mm cervical metal reduction respectively were fabricated. Total of fifty metal ceramic crown samples were fabricated. The fracture resistance was evaluated with the Universal Testing Machine (Instron model No 1011, UK). The basic data was subjected to statistical analysis by ANOVA and Student's t-test. RESULTS Results revealed that the fracture resistance ranged from 651.2 to 993.6 N/m2. Group 1 showed the maximum and Group 5 showed the least value. CONCLUSION The maximum load required to fracture the test specimens even in the groups without the metal collar was found to be exceeding the occlusal forces. Therefore, the metal frameworks with 0.5 mm and 1 mm short of the finish line are recommended for anterior metal ceramic restoration having adequate fracture resistance. PMID:22053240

  8. Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

    NASA Astrophysics Data System (ADS)

    Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; Mattson, Eric C.; Veyan, Jean-François; Wang, Hao; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

    2016-12-01

    The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk--as is typically done to enhance adsorption--here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO2, SO2, C2H4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. These findings may provide alternative strategies for gas storage, delivery and separation.

  9. Trapping gases in metal-organic frameworks with a selective surface molecular barrier layer

    PubMed Central

    Tan, Kui; Zuluaga, Sebastian; Fuentes, Erika; Mattson, Eric C.; Veyan, Jean-François; Wang, Hao; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

    2016-01-01

    The main challenge for gas storage and separation in nanoporous materials is that many molecules of interest adsorb too weakly to be effectively retained. Instead of synthetically modifying the internal surface structure of the entire bulk—as is typically done to enhance adsorption—here we show that post exposure of a prototypical porous metal-organic framework to ethylenediamine can effectively retain a variety of weakly adsorbing molecules (for example, CO, CO2, SO2, C2H4, NO) inside the materials by forming a monolayer-thick cap at the external surface of microcrystals. Furthermore, this capping mechanism, based on hydrogen bonding as explained by ab initio modelling, opens the door for potential selectivity. For example, water molecules are shown to disrupt the hydrogen-bonded amine network and diffuse through the cap without hindrance and fully displace/release the retained small molecules out of the metal-organic framework at room temperature. These findings may provide alternative strategies for gas storage, delivery and separation. PMID:27958274

  10. Incorporation of Molecular Catalysts in Metal-Organic Frameworks for Highly Efficient Heterogeneous Catalysis.

    PubMed

    Wu, Chuan-De; Zhao, Min

    2017-03-03

    Porous metal-organic frameworks (MOFs) are built from periodically alternate organic moieties and metal ions/clusters. The unique features of the open framework structures, the high surface areas, the permanent porosity, and the appropriate hydrophilic and hydrophobic pore nature mean that MOF materials are a class of ideal host matrices for immobilization of molecular catalysts. The emerging porous materials can not only retain but are also able to enhance the catalytic functions of the single individuals. MOF catalysts have the following super characters: i) uniformly dispersed catalytic sites on the pore surfaces to improve the utility, ii) appropriate hydrophilic and hydrophobic pore nature to facilitate the recognition and transportation of reactant and product molecules, iii) a collaborative microenvironment to realize synergistic catalysis, and iv) simple separation and recovery for long-term usage. Accompanying the development of the synthetic strategies and the technologies for the characterization of MOF materials, MOF catalysis has undergone an upsurge, which has transcended the stage of opportunism. Here, the rational design and synthesis of MOF catalysts are discussed, along with the key factors of active sites, microenvironments, and transmission channels that lead to the distinct catalytic properties of MOF catalysts.

  11. Diagenesis of Metals Chemically Complexed to Bacteria: Laboratory Formation of Metal Phosphates, Sulfides, and Organic Condensates in Artificial Sediments

    PubMed Central

    Beveridge, T. J.; Meloche, J. D.; Fyfe, W. S.; Murray, R. G. E.

    1983-01-01

    Cells of Bacillus subtilis, when suspended in a 5mM metal solution, bind metals tenaciously to their cell walls. These metal-loaded cells, when mixed with a synthetic sediment and put under laboratory conditions to simulate low-temperature sediment diagenesis, nucleate the formation of a mixed assemblage of crystalline metal phosphates, metal sulfides, and polymeric, metal-complexed, organic residues. The sequential series of diagenetic events leading to the formation of authigenic mineral phases was followed by transmission electron microscopy and energy-dispersive X-ray analysis. The minerals quartz (SiO2) and calcite (CaCO3) were employed in the synthetic sediment. Crystalline magnetite (Fe2O3) and elemental sulfur were added as redox buffering agents to ensure anoxic conditions. Quartz and magnetite appeared unreactive throughout the experimental conditions. Elemental sulfur interacted with the metal-loaded cells, affected both the eventual chemistry and crystal habit of the metal phosphates, and formed a variety of crystalline metal sulfides. Calcite raised the pH of the fluid phase of the sediment, which influenced phosphate mineralization and inhibited metal sulfide genesis. Images PMID:16346230

  12. Enhanced chlorine dioxide decay in the presence of metal oxides: relevance to drinking water distribution systems.

    PubMed

    Liu, Chao; von Gunten, Urs; Croué, Jean-Philippe

    2013-08-06

    Chlorine dioxide (ClO2) decay in the presence of typical metal oxides occurring in distribution systems was investigated. Metal oxides generally enhanced ClO2 decay in a second-order process via three pathways: (1) catalytic disproportionation with equimolar formation of chlorite and chlorate, (2) reaction to chlorite and oxygen, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly stronger abilities than goethite (α-FeOOH) to catalyze the ClO2 disproportionation (pathway 1), which predominated at higher initial ClO2 concentrations (56-81 μM). At lower initial ClO2 concentrations (13-31 μM), pathway 2 also contributed. The CuO-enhanced ClO2 decay is a base-assisted reaction with a third-order rate constant of 1.5 × 10(6) M(-2) s(-1) in the presence of 0.1 g L(-1) CuO at 21 ± 1 °C, which is 4-5 orders of magnitude higher than in the absence of CuO. The presence of natural organic matter (NOM) significantly enhanced the formation of chlorite and decreased the ClO2 disproportionation in the CuO-ClO2 system, probably because of a higher reactivity of CuO-activated ClO2 with NOM. Furthermore, a kinetic model was developed to simulate CuO-enhanced ClO2 decay at various pH values. Model simulations that agree well with the experimental data include a pre-equilibrium step with the rapid formation of a complex, namely, CuO-activated Cl2O4. The reaction of this complex with OH(-) is the rate-limiting and pH-dependent step for the overall reaction, producing chlorite and an intermediate that further forms chlorate and oxygen in parallel. These novel findings suggest that the possible ClO2 loss and the formation of chlorite/chlorate should be carefully considered in drinking water distribution systems containing copper pipes.

  13. Metal-organic frameworks based on uranyl and phosphonate ligands.

    PubMed

    Monteiro, Bernardo; Fernandes, José A; Pereira, Cláudia C L; Vilela, Sérgio M F; Tomé, João P C; Marçalo, Joaquim; Almeida Paz, Filipe A

    2014-02-01

    Three new crystalline metal-organic frameworks have been prepared from the reaction of uranyl nitrate with nitrilotris(methylphosphonic acid) [H6nmp, N(CH2PO3H2)3], 1,4-phenylenebis(methylene)diphosphonic acid [H4pmd, C6H4(PO3H2)2], and (benzene-1,3,5-triyltris(methylene))triphosphonic acid [H6bmt, C6H3(PO3H2)3]. Compound [(UO2)2F(H3nmp)(H2O)]·4H2O (I) crystallizes in space group C2/c, showing two crystallographically independent uranyl centres with pentagonal bipyramidal coordination geometries. While one metal centre is composed of a {(UO2)O3(μ-F)}2 dimer, the other comprises an isolated {(UO2)O5} polyhedron. Compound [(UO2)(H2pmd)] (II) crystallizes in space group P21/c, showing a centrosymmetric uranyl centre with an octahedral {(UO2)O4} coordination geometry. Compound [(UO2)3(H3bmt)2(H2O)2]·14H2O (III) crystallizes in space group P\\bar 1, showing two crystallographically independent uranyl centres. One uranyl centre is a {(UO2)O5} pentagonal bipyramid similar to that in (I), while the other is a {(UO2)O4} centrosymmetric octahedron similar to that in (II). Compounds (I) and (III) contain solvent-accessible volumes accounting for ca 23.6 and 26.9% of their unit-cell volume, respectively. In (I) the cavity has a columnar shape and is occupied by disordered water molecules, while in (III) the cavity is a two-dimensional layer with more ordered water molecules. All compounds have been studied in the solid state using FT-IR spectroscopy. Topological studies show that compounds (I) and (III) are trinodal, with 3,6,6- and 4,4,6-connected networks, respectively. Compound (II) is instead a 4-connected uninodal network of the type cds.

  14. Metal enhanced fluorescence in rare earth doped plasmonic core-shell nanoparticles.

    PubMed

    Derom, S; Berthelot, A; Pillonnet, A; Benamara, O; Jurdyc, A M; Girard, C; Colas des Francs, G

    2013-12-13

    We theoretically and numerically investigate metal enhanced fluorescence of plasmonic core-shell nanoparticles doped with rare earth (RE) ions. Particle shape and size are engineered to maximize the average enhancement factor (AEF) of the overall doped shell. We show that the highest enhancement (11 in the visible and 7 in the near-infrared) is achieved by tuning either the dipolar or the quadrupolar particle resonance to the rare earth ion's excitation wavelength. Additionally, the calculated AEFs are compared to experimental data reported in the literature, obtained in similar conditions (plasmon mediated enhancement) or when a metal-RE energy transfer mechanism is involved.

  15. Organic acid compounds in root exudation of Moso Bamboo (Phyllostachys pubescens) and its bioactivity as affected by heavy metals.

    PubMed

    Chen, Junren; Shafi, Mohammad; Wang, Ying; Wu, Jiasen; Ye, Zhengqian; Liu, Chen; Zhong, Bin; Guo, Hua; He, Lizhi; Liu, Dan

    2016-10-01

    Moso bamboo (Phyllostachys pubescens) has great potential as phytoremediation material in soil contaminated by heavy metals. A hydroponics experiment was conducted to determine organic acid compounds of root exudates of lead- (Pb), zinc- (Zn), copper- (Cu), and cadmium (Cd)-tolerant of Moso bamboo. Plants were grown in nutrients solution which included Pb, Zn, Cu, and Cd applied as Pb(NO3)2 (200 μM), ZnSO4·7H2O (100 μM), CuSO4·5H2O (25 μM), and CdCl2 (10 μM), respectively. Oxalic acid and malic acid were detected in all treatments. Lactic acid was observed in Cu, Cd, and control treatments. The oxalic was the main organic acid exudated by Moso bamboo. In the sand culture experiment, the Moso bamboo significantly activated carbonate heavy metals under activation of roots. The concentration of water-soluble metals (except Pb) in sand were significantly increased as compared with control. Organic acids (1 mM mixed) were used due to its effect on the soil adsorption of heavy metals. After adding mixed organic acids, the Cu and Zn sorption capacity in soils was decreased markedly compared with enhanced Pb and Cd sorption capacity in soils. The sorption was analyzed using Langmuir and Freundlich equations with R (2) values that ranged from 0.956 to 0.999 and 0.919 to 0.997, respectively.

  16. ENHANCED BIOACCUMULATION OF HEAVY METAL BY BACTERIA CELLS DISPLAYING SYNTHETIC PHYTOCHELATINS. (R827227)

    EPA Science Inventory

    A novel strategy using synthetic phytochelatins is described for the purpose of developing microbial agents for enhanced bioaccumulation of toxic metals. Synthetic genes encoding for several metal-chelating phytochelatin analogs (Glu-Cys)nGly (EC8 (n = 8), EC11 (n = 11...

  17. Enhancement of spontaneous emission in metal-dielectric multilayer structures accounting losses

    NASA Astrophysics Data System (ADS)

    Gubaydullin, A. R.; Kaliteevski, M. A.

    2015-11-01

    We study the emission rate enhancement of the dipole emitter centred in the stratified metal-dielectric metamaterial, characterized by the hyperbolic isofrequency surface. We find out a limited enhancement of the Purcell factor in the layered metamaterial. We demonstrate that the radiative decay rate is strongly depends on a ratio of the thickness of layers and is affected by the level of losses in metal.

  18. Pore Space Partition in Metal-Organic Frameworks.

    PubMed

    Zhai, Quan-Guo; Bu, Xianhui; Zhao, Xiang; Li, Dong-Sheng; Feng, Pingyun

    2017-02-21

    Metal-organic framework (MOF) materials have emerged as one of the favorite crystalline porous materials (CPM) because of their compositional and geometric tunability and many possible applications. In efforts to develop better MOFs for gas storage and separation, a number of strategies including creation of open metal sites and implantation of Lewis base sites have been used to tune host-guest interactions. In addition to these chemical factors, the geometric features such as pore size and shape, surface area, and pore volume also play important roles in sorption energetics and uptake capacity. For efficient capture of small gas molecules such as carbon dioxide under ambient conditions, large surface area or high pore volume are often not needed. Instead, maximizing host-guest interactions or the density of binding sites by encaging gas molecules in snug pockets of pore space can be a fruitful approach. To put this concept into practice, the pore space partition (PSP) concept has been proposed and has achieved a great experimental success. In this account, we will highlight many efforts to implement PSP in MOFs and impact of PSP on gas uptake performance. In the synthetic design of PSP, it is helpful to distinguish between factors that contribute to the framework formation and factors that serve the purpose of PSP. Because of the need for complementary structural roles, the synthesis of MOFs with PSP often involves multicomponent systems including mixed ligands, mixed inorganic nodes, or both. It is possible to accomplish both framework formation and PSP with a single type of polyfunctional ligands that use some functional groups (called framework-forming group) for framework formation and the remaining functional groups (called pore-partition group) for PSP. Alternatively, framework formation and PSP can be shouldered by different chemical species. For example, in a mixed-ligand system, one ligand (called framework-forming agent) can play the role of the

  19. Metal organic frameworks for enzyme immobilization in biofuel cells

    NASA Astrophysics Data System (ADS)

    Bodell, JaDee

    Interest in biofuel cells has been rapidly expanding as an ever-growing segment of the population gains access to electronic devices. The largest areas of growth for new populations using electronic devices are often in communities without electrical infrastructure. This lack of infrastructure in remote environments is one of the key driving factors behind the development of biofuel cells. Biofuel cells employ biological catalysts such as enzymes to catalyze oxidation and reduction reactions of select fuels to generate power. There are several benefits to using enzymes to catalyze reactions as compared to traditional fuel cells which use metal catalysts. First, enzymes are able to catalyze reactions at or near room temperature, whereas traditional metal catalysts are only efficient at very high temperatures. Second, biofuel cells can operate under mild pH conditions which is important for the eventual design of safe, commercially viable devices. Also, biofuel cells allow for implantable and flexible technologies. Finally, enzymes exhibit high selectivity and can be combined to fully oxidize or reduce the fuel which can generate several electrons from a single molecule of fuel, increasing the overall device efficiency. One of the main challenges which persist in biofuel cells is the instability of enzymes over time which tend to denature after hours or days. For a viable commercial biofuel cell to be produced, the stability of enzymes must be extended to months or years. Enzymes have been shown to have improved stability after being immobilized. The focus of this research was to find a metal organic framework (MOF) structure which could successfully immobilize enzymes while still allowing for electron transport to occur between the catalytic center of the enzyme and the electrode surface within a biofuel cell for power generation. Four MOF structures were successfully synthesized and were subsequently tested to determine the MOF's ability to immobilize the following

  20. Mechanistic Studies of Charge Injection from Metallic Electrodes into Organic Semiconductors Mediated by Ionic Functionalities: Final Report

    SciTech Connect

    Nguyen, Thuc-Quyen; Bazan, Guillermo; Mikhailovsky, Alexander

    2014-04-15

    cost. During the execution of the project, main efforts were focused on the synthesis of new charge-bearing organic materials, such as CPEs and COEs, and block copolymers with neutral and ionic segments, studies of mechanisms responsible for the charge injection modulation in devices with ionic interlayers, and use of naturally occurring charged molecules for creation of enhanced devices. The studies allowed PIs to demonstrate the usefulness of the proposed approach for the improvement of operational parameters in model OLED and FET systems resulting in increased efficiency, decreased contact resistance, and possibility to use stable metals for fabrication of device electrodes. The successful proof-of-the-principle results potentially promise development of light-weight, low fabrication cost devices which can be used in consumer applications such as displays, solar cells, and printed electronic devices. Fundamental mechanisms responsible for the phenomena observed have been identified thus advancing the fundamental knowledgebase.

  1. Dramatic enhancement of enzymatic activity in organic solvents by lyoprotectants

    SciTech Connect

    Dabulis, K.; Klibanov, A.M. )

    1993-03-05

    When seven different hydrolytic enzymes (four proteases and three lipases) were lyophilized from aqueous solution containing a ligand, N-Ac-L-Phe-NH[sub 2], their catalytic activity in anhydrous solvents was far greater (one to two orders of magnitude) than that of the enzymes lyophilized without the ligand. This ligand-induced activation was expressed regardless of whether the substrate employed in organic solvents structurally resembled the ligand. Furthermore, nonligand lyoprotectants [sorbitol, other sugars, and poly(ethylene glycol)] also dramatically enhanced enzymatic activity in anhydrous solvents when present in enzyme aqueous solution prior to lyophilization. The effects of the ligand and of the lyoprotectants were nonadditive, suggesting the same mechanism of action. Excipient-activated and nonactivated enzymes exhibited identical activities in water. Also, addition of the excipients directly to suspensions of nonactivated enzymes in organic solvents had no appreciable effect on catalytic activity. These observations indicate that the mechanism of the excipient-induced activation is based on the ability of the excipients to alleviate reversible denaturation of enzymes upon lyophilization. Activity enhancement induced by the excipients is displayed even after their removal by washing enzymes with anhydrous solvents. Subtilisin Carlsberg, lyophilized with sorbitol, was found to be a much more efficient practical catalyst than its regular' counterpart.

  2. Flexible organic solar cells including efficiency enhancing grating structures.

    PubMed

    de Oliveira Hansen, Roana Melina; Liu, Yinghui; Madsen, Morten; Rubahn, Horst-Günter

    2013-04-12

    In this work, a new method for the fabrication of organic solar cells containing functional light-trapping nanostructures on flexible substrates is presented. Polyimide is spin-coated on silicon support substrates, enabling standard micro- and nanotechnology fabrication techniques, such as photolithography and electron-beam lithography, besides the steps required for the bulk-heterojunction organic solar cell fabrication. After the production steps, the solar cells on polyimide are peeled off the silicon support substrates, resulting in flexible devices containing nanostructures for light absorption enhancement. Since the solar cells avoid using brittle electrodes, the performance of the flexible devices is not affected by the peeling process. We have investigated three different nanostructured grating designs and conclude that gratings with a 500 nm pitch distance have the highest light-trapping efficiency for the selected active layer material (P3HT:PCBM), resulting in an enhancement of about 34% on the solar cell efficiency. The presented method can be applied to a large variety of flexible nanostructured devices in future applications.

  3. Flexible organic solar cells including efficiency enhancing grating structures

    NASA Astrophysics Data System (ADS)

    Melina de Oliveira Hansen, Roana; Liu, Yinghui; Madsen, Morten; Rubahn, Horst-Günter

    2013-04-01

    In this work, a new method for the fabrication of organic solar cells containing functional light-trapping nanostructures on flexible substrates is presented. Polyimide is spin-coated on silicon support substrates, enabling standard micro- and nanotechnology fabrication techniques, such as photolithography and electron-beam lithography, besides the steps required for the bulk-heterojunction organic solar cell fabrication. After the production steps, the solar cells on polyimide are peeled off the silicon support substrates, resulting in flexible devices containing nanostructures for light absorption enhancement. Since the solar cells avoid using brittle electrodes, the performance of the flexible devices is not affected by the peeling process. We have investigated three different nanostructured grating designs and conclude that gratings with a 500 nm pitch distance have the highest light-trapping efficiency for the selected active layer material (P3HT:PCBM), resulting in an enhancement of about 34% on the solar cell efficiency. The presented method can be applied to a large variety of flexible nanostructured devices in future applications.

  4. Reduced quenching effects of organic gain media with metallic electrodes via introducing a conjugated macroelectrolyte interlayer

    NASA Astrophysics Data System (ADS)

    Yi, Jianpeng; Huang, Jinjin; Liu, Chengfang; Lai, Wen-Yong; Huang, Wei

    2017-01-01

    We have demonstrated amplified spontaneous emission (ASE) restoration and threshold reduction by introducing a novel water/alcohol soluble conjugated macroelectrolyte, tris(4-(7-(9,9-di(hexyl-1-N,N-diethanolamino)-9H-fluoren-2-yl)-9,9-di(hexyl-1-N,N-diethanolamino)-9H-fluoren-2-yl)phenyl)amine (TPAOH), serving as an interfacial layer between the gain media layer, dioctyl substituted polyfluorene (PFO), and the Ag electrode layer. By optimizing the film thickness of TPAOH, enhanced ASE performance has been achieved with the lowest threshold of 21 μJ/cm2, demonstrating 3.5-fold reduction from 74 μJ/cm2. Atomic force microscopy results showed good compatibility between the TPAOH film and the PFO layer. The results suggest a facile and low-cost solution-processing interfacial technique to construct efficient organic semiconductor lasers in the presence of metallic electrodes.

  5. Lithium inclusion in indium metal-organic frameworks showing increased surface area and hydrogen adsorption

    SciTech Connect

    Bosch, Mathieu; Zhang, Muwei; Feng, Dawei; Yuan, Shuai; Wang, Xuan; Chen, Ying-Pin; Zhou, Hong-Cai

    2014-12-01

    Investigation of counterion exchange in two anionic In-Metal-Organic Frameworks (In-MOFs) showed that partial replacement of disordered ammonium cations was achieved through the pre-synthetic addition of LiOH to the reaction mixture. This resulted in a surface area increase of over 1600% in (Li [In(1,3 − BDC){sub 2}]){sub n} and enhancement of the H{sub 2} uptake of approximately 275% at 80 000 Pa at 77 K. This method resulted in frameworks with permanent lithium content after repeated solvent exchange as confirmed by inductively coupled plasma mass spectrometry. Lithium counterion replacement appears to increase porosity after activation through replacement of bulkier, softer counterions and demonstrates tuning of pore size and properties in MOFs.

  6. Urea Metal-Organic Frameworks for Nitro-Substituted Compounds Sensing.

    PubMed

    Azhdari Tehrani, Alireza; Esrafili, Leili; Abedi, Sedigheh; Morsali, Ali; Carlucci, Lucia; Proserpio, Davide M; Wang, Jun; Junk, Peter C; Liu, Tianfu

    2017-02-06

    Urea groups are known to form strong hydrogen bonds with molecules containing atom(s) that can act as hydrogen bond acceptor(s). Thus, urea is a particularly interesting building block for designing receptors for neutral or charged guests. In the quest for new sensors with enhanced performance for the detection of nitro-substituted compounds, two pillared metal-organic frameworks containing urea functional groups were synthesized and structurally characterized. The sensing properties of these frameworks toward nitro-analytes were investigated and compared to each other. The study clearly reveals the importance of urea groups orientation inside the pore cavity of MOFs, as well as the supramolecular interactions between the interpenetrated networks. This work is interesting as it represents the first example of urea-functionalized MOFs for nitro-analytes recognition.

  7. Metal-organic framework nanoparticles decorated with graphene: A high-performance electromagnetic wave absorber

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Zhang, Wenzhi; Wu, Xinming; Luo, Chunyan; Liang, Tan; Yan, Gang

    2016-10-01

    A novel metal organic framework (MOF) coated RGO was fabricated by a one-step method. The morphology and microstructure of MOF-53(Fe)/RGO composite were characterized by XRD and TEM. The electromagnetic parameters indicate that MOF-53(Fe)/RGO composite shows enhanced electromagnetic absorption properties compared with MOF-53(Fe). The maximum RL can reach -25.8 dB at 15.4 GHz and the absorption bandwidth with the reflection loss exceeding -10 dB is 5.9 GHz (from 12.1 to 18 GHz) with the thickness of 2 mm. The possible absorption mechanism was also investigated in detail. Our results indicate the potential application of MOF/RGO composite as a more efficient microwave absorber.

  8. Quantum Chemistry in Nanoscale Environments: Insights on Surface-Enhanced Raman Scattering and Organic Photovoltaics

    NASA Astrophysics Data System (ADS)

    Olivares-Amaya, Roberto

    The understanding of molecular effects in nanoscale environments is becoming increasingly relevant for various emerging fields. These include spectroscopy for molecular identification as well as in finding molecules for energy harvesting. Theoretical quantum chemistry has been increasingly useful to address these phenomena to yield an understanding of these effects. In the first part of this dissertation, we study the chemical effect of surface-enhanced Raman scattering (SERS). We use quantum chemistry simulations to study the metal-molecule interactions present in these systems. We find that the excitations that provide a chemical enhancement contain a mixed contribution from the metal and the molecule. Moreover, using atomistic studies we propose an additional source of enhancement, where a transition metal dopant surface could provide an additional enhancement. We also develop methods to study the electrostatic effects of molecules in metallic environments. We study the importance of image-charge effects, as well as field-bias to molecules interacting with perfect conductors. The atomistic modeling and the electrostatic approximation enable us to study the effects of the metal interacting with the molecule in a complementary fashion, which provides a better understanding of the complex effects present in SERS. In the second part of this dissertation, we present the Harvard Clean Energy Project, a high-throughput approach for a large-scale computational screening and design of organic photovoltaic materials. We create molecular libraries to search for candidates structures and use quantum chemistry, machine learning and cheminformatics methods to characterize these systems and find structure-property relations. The scale of this study requires an equally large computational resource. We rely on distributed volunteer computing to obtain these properties. In the third part of this dissertation we present our work related to the acceleration of electronic structure

  9. Anisotropic thermal expansion in a metal-organic framework.

    PubMed

    Madsen, Solveig Røgild; Lock, Nina; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-06-01

    Ionothermal reaction between Mn(II)(acetate)2·4H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) in either of the two ionic liquids 1-ethyl-3-methylimidazolium bromide (EMIMBr) and 1-ethyl-3-methylimidazolium tosylate (EMIMOTs) resulted in the formation of the new metal-organic framework (MOF) EMIM[Mn(II)BTC] (BTC = 1,3,5-benzenetricarboxylate). The compound crystallizes in the orthorhombic space group Pbca with unit-cell parameters of a = 14.66658 (12), b = 12.39497 (9), c = 16.63509 (14) Å at 100 K. Multi-temperature single-crystal (15-340 K) and powder X-ray diffraction studies (100-400 K) reveal strongly anisotropic thermal expansion properties. The linear thermal expansion coefficients, αL(l), attain maximum values at 400 K along the a- and b-axis, with αL(a) = 115 × 10(-6) K(-1) and αL(b) = 75 × 10(-6) K(-1). At 400 K a negative thermal expansion coefficient of -40 × 10(-6) K(-1) is observed along the c-axis. The thermal expansion is coupled to a continuous deformation of the framework, which causes the structure to expand in two directions. Due to the rigidity of the linker, the expansion in the ab plane causes the network to contract along the c-axis. Hirshfeld surface analysis has been used to describe the interaction between the framework structure and the EMIM cation that resides within the channel. This reveals a number of rather weak interactions and one governing hydrogen-bonding interactions.

  10. The Importance of Polymorphism in Metal-Organic Framework Studies.

    PubMed

    Aulakh, Darpandeep; Varghese, Juby R; Wriedt, Mario

    2015-09-08

    Polymorphic phase transitions remain frequently undetected in routine metal-organic framework (MOF) studies; however, their discovery is of major importance in interpreting structure-property relationships. We herein report a reversible enantiotropic single-crystal to single-crystal polymorphic phase transition of a new microporous MOF [Eu(BDC)(NO3)(DMF)2]n (H2BDC = 1,4-benzenedicarboxylic acid; DMF = dimethylformamide). While modification 1LT at 170 K crystallizes in the monoclinic space group P21/c with unit cell dimensions of a = 17.673(2) Å, b = 20.023(2) Å, c = 10.555(9) Å, β = 90.129(4)°, modification 1HT at 290 K crystallizes in higher symmetry space group C2/c with unit cell dimensions of a = 17.200(7) Å, b = 10.737(4) Å, c = 10.684(4) Å, β = 90.136(2)°. This temperature-induced phase transition is accompanied by a small change in the solvent-accessible voids from 46.8 in 1LT to 49.8% in 1HT, which triggers a significant change in the adsorption properties as compared to a reported isostructural compound. Detailed investigations on the phase transition were studied with variable-temperature single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction, and differential scanning calorimetry measurements. The herein-presented investigations emphasize the importance of polymorphic phase transitions in routine MOF studies originating from low-temperature SCXRD data and high-temperature physical property characterizations in avoiding the use of a wrong structure in interpreting structure-property relationships.

  11. Thermodynamics of impurity-enhanced vacancy formation in metals

    NASA Astrophysics Data System (ADS)

    Bukonte, Laura; Ahlgren, Tommy; Heinola, Kalle

    2017-01-01

    Hydrogen induced vacancy formation in metals and metal alloys has been of great interest during the past couple of decades. The main reason for this phenomenon, often referred to as the superabundant vacancy formation, is the lowering of vacancy formation energy due to the trapping of hydrogen. By means of thermodynamics, we study the equilibrium vacancy formation in fcc metals (Pd, Ni, Co, and Fe) in correlation with the H amounts. The results of this study are compared and found to be in good agreement with experiments. For the accurate description of the total energy of the metal-hydrogen system, we take into account the binding energies of each trapped impurity, the vibrational entropy of defects, and the thermodynamics of divacancy formation. We demonstrate the effect of vacancy formation energy, the hydrogen binding, and the divacancy binding energy on the total equilibrium vacancy concentration. We show that the divacancy fraction gives the major contribution to the total vacancy fraction at high H fractions and cannot be neglected when studying superabundant vacancies. Our results lead to a novel conclusion that at high hydrogen fractions, superabundant vacancy formation takes place regardless of the binding energy between vacancies and hydrogen. We also propose the reason of superabundant vacancy formation mainly in the fcc phase. The equations obtained within this work can be used for any metal-impurity system, if the impurity occupies an interstitial site in the lattice.

  12. Surface plasmon coupling enhanced dielectric environment sensitivity in a quasi-three-dimensional metallic nanohole array.

    PubMed

    Li, Yuanyuan; Pan, Jian; Zhan, Peng; Zhu, Shining; Ming, Naiben; Wang, Zhenlin; Han, Wenda; Jiang, Xunya; Zi, Jian

    2010-02-15

    An enhanced dielectric environment response is observed in a kind of metallic nanohole arrays which are prepared by metal deposition on a sacrificial two dimensional colloidal crystal template. The periodic metallic structures are composed of interlinked metallic half-shells supported on a planar dielectric substrate. When putting in dielectric matrix of different refractive index, the measured sensitivity of the quasi-three-dimensional metallic nanohole array can reach a value of 1192 nm per refractive index unit which shows a five-fold increase as compared with the metallic structures supported on the template. The observed boost in sensitivity is found to originate from a substantially reduced substrate effect, resulting in a pronounced surface plasmon coupling of which its strength is independent of the dielectric environment, a characteristics absent in conventional planar metallic subwavelength hole arrays. These findings are analyzed theoretically and confirmed by numerical simulations.

  13. Metal-organic frameworks as functional, porous materials

    NASA Astrophysics Data System (ADS)

    Rood, Jeffrey A.

    The research presented in this thesis investigates the use of metal carboxylates as permanently porous materials called metal-organic frameworks (MOFs). The project has focused on three broad areas of study, each which strives to develop a further understanding of this class of materials. The first topic is concerned with the synthesis and structural characterization of MOFs. Our group and others have found that the reaction of metal salts with carboxylic acids in polar solvents at elevated temperatures often leads the formation of crystalline MOF materials that can be examined by single crystal X-ray diffraction. Specifically, Chapter 2 reports on some of the first examples of magnesium MOFs, constructed from formate or aryldicarboxylate ligands. The magnesium formate MOF, [Mg3(O2CH) 6] was found to be a permanently porous 3-D material capable of selective uptake and exchange of small molecules. Once the synthesis and structures of some of these materials was known, their physical properties were studied. The magnesium formate MOF, [Mg 3(O2CH)6], was found to be permanently porous and able to reversibly adsorb both N2 and H2 gas. Furthermore, the material was also capable of taking up a variety of organic molecules to form new inclusion compounds that were characterized by XRD studies. Size exclusion was shown for cyclohexane and larger molecules. Chapters 3, 5, and 6 attempt to build off of the synthetic findings reported in Chapter 2. Specifically, the ability of these materials to take up guest molecules is expanded by the attempted synthesis of porous, homochiral MOFs using enantiopure carboxylic acids in the synthesis. It was found that under the appropriate synthetic conditions, both L-tartaric acid and (+)-camphoric acid were robust linkers for the formation of homochiral MOFs. Of the compounds synthesized, the most interesting were the set of compounds, [Zn2(Cam) 2(bipy)⊃3DMF] and [Zn2(Cam)2(apyr)⊃2DMF]. These compounds formed isoreticular cubic

  14. Computational study of hydrocarbon adsorption in metal-organic framework Ni2(dhtp).

    PubMed

    Sun, Xiuquan; Wick, Collin D; Thallapally, Praveen K; McGrail, B Peter; Dang, Liem X

    2011-03-31

    Enhancing the efficiency of the Rankine cycle, which is utilized for multiple renewable energy sources, requires the use of a working fluid with a high latent heat of vaporization. To further enhance its latent heat, a working fluid can be placed in a metal organic heat carrier (MOHC) with a high heat of adsorption. One such material is Ni\\DOBDC, in which linear alkanes have a higher heat of adsorption than cyclic alkanes. We carried out molecular dynamics simulations to investigate the structural, diffusive, and adsorption properties of n-hexane and cyclohexane in Ni\\DOBDC. The strong binding for both n-hexane and cyclohexane with Ni\\DOBDC is attributed to the increase of the heat of adsorption observed in experiments. Our structural results indicate the organic linkers in Ni\\DOBDC are the primary binding sites for both n-hexane and cyclohexane molecules. However, at all temperatures and loadings examined in present work, n-hexane clearly showed stronger binding with Ni\\DOBDC than cyclohexane. This was found to be the result of the ability of n-hexane to reconfigure its structure to a greater degree than cyclohexane to gain more contacts between adsorbates and adsorbents. The geometry and flexibility of guest molecules were also related to their diffusivity in Ni\\DOBDC, with higher diffusion for flexible molecules. Because of the large pore sizes in Ni\\DOBDC, energetic effects were the dominant force for alkane adsorption and selectivity.

  15. Template-Directed Approach Towards the Realization of Ordered Heterogeneity in Bimetallic Metal-Organic Frameworks.

    PubMed

    Kim, Daeok; Coskun, Ali

    2017-03-29

    Controlling the arrangement of different metal ions to achieve ordered heterogeneity in metal-organic frameworks (MOFs) has been a great challenge. Herein, we introduce a template-directed approach, in which a 1D metal-organic polymer incorporating well-defined binding pockets for the secondary metal ions used as a structural template and starting material for the preparation of well-ordered bimetallic MOF-74s under heterogeneous-phase hydrothermal reaction conditions in the presence of secondary metal ions such as Ni(2+) and Mg(2+) in 3 h. The resulting bimetallic MOF-74s were found to possess a nearly 1:1 metal ratio regardless of their initial stoichiometry in the reaction mixture, thus demonstrating the possibility of controlling the arrangement of metal ions within the secondary building blocks in MOFs to tune their intrinsic properties such as gas affinity.

  16. Enhancement of the electrical characteristics of metal-free phthalocyanine films using cold isostatic pressing

    SciTech Connect

    Matsushima, Toshinori E-mail: adachi@cstf.kyushu-u.ac.jp; Adachi, Chihaya E-mail: adachi@cstf.kyushu-u.ac.jp; Esaki, Yu

    2014-12-15

    Spatial gaps between grains and other grains, substrates, or electrodes in organic electronic devices are one of the causes of the reduction in the electrical characteristics. In this study, we demonstrate that cold isostatic pressing (CIP) is an effective method to crush the gaps and enhance the electrical characteristics. CIP of metal-free phthalocyanine (H{sub 2}PC) films induced a decrease in the film thickness by 34%–40% because of the gap crush. The connection of smaller grains into a larger grain and planarization of the film surface were also observed in the CIP film. The crystal axes of the H{sub 2}PC crystallites were rearranged from the a-axis to the c-axis of the α-phase crystal structure in a direction perpendicular to the substrate by CIP, indicating favorable hole injection and transport in this direction because of a better overlap of π orbitals. Thermally stimulated current measurements showed that deep hole traps disappeared and the total hole-trap density decreased after CIP. These CIP-induced changes of the film thicknesses, crystal axes and the hole traps lead to a marked increase in the hole mobility of the H{sub 2}PC films from 2.0 × 10{sup −7} to 4.0 × 10{sup −4} cm{sup 2}/V s by 2000 times in the perpendicular direction. We believe that these findings are important for unveiling the underlying carrier injection and transport mechanisms of organic films and for enhancing the performance of future organic electronic devices.

  17. Synthesis and characterization of metal-organic framework-74 containing 2, 4, 6, 8, and 10 different metals.

    PubMed

    Wang, Lisa J; Deng, Hexiang; Furukawa, Hiroyasu; Gándara, Felipe; Cordova, Kyle E; Peri, Dani; Yaghi, Omar M

    2014-06-16

    Metal-organic frameworks (MOFs) containing more than two kinds of metal ions mixed in one secondary building unit are rare because the synthesis often yields mixed MOF phases rather than a pure phase of a mixed-metal MOF (MM-MOF). In this study, we use a one-pot reaction to make microcrystalline MOF-74 [M2(DOT); DOT = dioxidoterephthalate] with 2 (Mg and Co), 4 (Mg, Co, Ni, and Zn), 6 (Mg, Sr, Mn, Co, Ni, and Zn), 8 (Mg, Ca, Sr, Mn, Fe, Co, Ni, and Zn), and 10 (Mg, Ca, Sr, Ba, Mn, Fe, Co, Ni, Zn, and Cd) different kinds of divalent metals. The powder X-ray diffraction patterns of MM-MOF-74 were identical with those of single-metal MOF-74, and no amorphous phases were found by scanning electron microscopy. The successful preparation of guest-free MM-MOF-74 samples was confirmed by N2 adsorption measurements. Elemental analysis data also support the fact that all metal ions used in the MOF synthesis are incorporated within the same MOF-74 structure. Energy-dispersive X-ray spectroscopies indicate that metal ions are heterogeneously distributed within each of the crystalline particles. This approach is also employed to incorporate metal ions (i.e., Ca, Sr, Ba, and Cd) from which the parent MOF structure could not be made as a single-metal-containing MOF.

  18. Novel metal-organic photocatalysts: synthesis, characterization and decomposition of organic dyes.

    PubMed

    Gopal Reddy, N B; Murali Krishna, P; Kottam, Nagaraju

    2015-02-25

    An efficient method for the photocatalytic degradation of methylene blue in an aqueous medium was developed using metal-organic complexes. Two novel complexes were synthesized using, Schiff base ligand, N'-[(E)-(4-ethylphenyl)methylidene]-4-hydroxybenzohydrazide (HL) and Ni(II) (Complex 1)/Co(II) (Complex 2) chloride respectively. These complexes were characterized using microanalysis, various spectral techniques. Spectral studies reveal that the complexes exhibit square planar geometry with ligand coordination through azomethine nitrogen and enolic oxygen. The effects of catalyst dosage, irradiation time and aqueous pH on the photocatalytic activity were studied systematically. The photocatalytic activity was found to be more efficient in the presence of Ni(II) complexes than the Co(II) complex. Possible mechanistic aspects were discussed.

  19. Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks.

    PubMed

    Feng, Dawei; Wang, Kecheng; Wei, Zhangwen; Chen, Ying-Pin; Simon, Cory M; Arvapally, Ravi K; Martin, Richard L; Bosch, Mathieu; Liu, Tian-Fu; Fordham, Stephen; Yuan, Daqiang; Omary, Mohammad A; Haranczyk, Maciej; Smit, Berend; Zhou, Hong-Cai

    2014-12-04

    Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

  20. Using biochar for remediation of soils contaminated with heavy metals and organic pollutants.

    PubMed

    Zhang, Xiaokai; Wang, Hailong; He, Lizhi; Lu, Kouping; Sarmah, Ajit; Li, Jianwu; Bolan, Nanthi S; Pei, Jianchuan; Huang, Huagang

    2013-12-01

    Soil contamination with heavy metals and organic pollutants has increasingly become a serious global environmental issue in recent years. Considerable efforts have been made to remediate contaminated soils. Biochar has a large surface area, and high capacity to adsorb heavy metals and organic pollutants. Biochar can potentially be used to reduce the bioavailability and leachability of heavy metals and organic pollutants in soils through adsorption and other physicochemical reactions. Biochar is typically an alkaline material which can increase soil pH and contribute to stabilization of heavy metals. Application of biochar for remediation of contaminated soils may provide a new solution to the soil pollution problem. This paper provides an overview on the impact of biochar on the environmental fate and mobility of heavy metals and organic pollutants in contaminated soils and its implication for remediation of contaminated soils. Further research directions are identified to ensure a safe and sustainable use of biochar as a soil amendment for remediation of contaminated soils.

  1. Size characterization of dissolved metals and organic matter in source waters to streams in developed landscapes.

    PubMed

    Luan, Hongwei; Vadas, Timothy M

    2015-02-01

    Individual and mixed water samples from wastewater treatment plant effluents, stormwater runoff, streams from developed areas were characterized with respect to organic matter concentration and spectral properties and metal concentration and size distribution. In addition, asymmetric flow-field flow fractionation coupled to inductively coupled plasma mass spectrometry was used to measure concentration, size distribution and association of metals in the colloidal size range. Results reveal that Fe, Cu, Zn and Pb in the colloidal size range were mainly associated with the less than 5 nm, or less than 10 kDa size range. Cu was most strongly associated with organic matter, while Zn and Pb were mixed between Fe and organic matter. Effluent showed higher binding capacity for metals, while stormwater, even with higher organic matter concentrations showed more exchangeable metals. Upon mixing of source waters, colloidal metal concentrations and size distributions were conserved.

  2. Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

    SciTech Connect

    Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

    2016-08-30

    Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.

  3. PH DEPENDENT TOXICITY OF FIVE METALS TO THREE MARINE ORGANISMS

    EPA Science Inventory

    The pH of natural marine systems is relatively stable; this may explain why metal toxicity changes with pH have not been well documented. However, changes in metal toxicity with pH in marine waters are of concern in toxicity testing. During porewater toxicity testing pH can chang...

  4. Nanoscale patterning, macroscopic reconstruction, and enhanced surface stress by organic adsorption on vicinal surfaces

    NASA Astrophysics Data System (ADS)

    Pollinger, Florian; Schmitt, Stefan; Sander, Dirk; Tian, Zhen; Kirschner, Jürgen; Vrdoljak, Pavo; Stadler, Christoph; Maier, Florian; Marchetto, Helder; Schmidt, Thomas; Schöll, Achim; Umbach, Eberhard

    2017-01-01

    Self-organization is a promising method within the framework of bottom-up architectures to generate nanostructures in an efficient way. The present work demonstrates that self-organization on the length scale of a few to several tens of nanometers can be achieved by a proper combination of a large (organic) molecule and a vicinal metal surface if the local bonding of the molecule on steps is significantly stronger than that on low-index surfaces. In this case thermal annealing may lead to large mass transport of the subjacent substrate atoms such that nanometer-wide and micrometer-long molecular stripes or other patterns are being formed on high-index planes. The formation of these patterns can be controlled by the initial surface orientation and adsorbate coverage. The patterns arrange self-organized in regular arrays by repulsive mechanical interactions over long distances accompanied by a significant enhancement of surface stress. We demonstrate this effect using the planar organic molecule PTCDA as adsorbate and Ag(10 8 7) and Ag(775) surfaces as substrate. The patterns are directly observed by STM, the formation of vicinal surfaces is monitored by high-resolution electron diffraction, the microscopic surface morphology changes are followed by spectro-microscopy, and the macroscopic changes of surface stress are measured by a cantilever bending method. The in situ combination of these complementary techniques provides compelling evidence for elastic interaction and a significant stress contribution to long-range order and nanopattern formation.

  5. Metallic Nanomaterials for Sensitivity Enhancement of Fluorescence Detection

    PubMed Central

    Goldys, Ewa M.; Xie, Fang

    2008-01-01

    Utrasensitive detection of trace analytes by fluorescence benefits for fluorescence amplifying substrates. We review here our recent work concerned with understanding of enhancement mechanisms and formation of three such substrates: silver fractals, silver coated gold nanoparticles deposited on glass and fluorescence enhancing gold colloids. PMID:27879741

  6. Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network

    SciTech Connect

    Shi, Fa-Nian; Rosa Silva, Ana; Bian, Liang

    2015-05-15

    A new terminology of metal organic oxide (MOO) was given a definition as a type of coordination polymers which possess the feature of inorganic connectivity between metals and the direct bonded atoms and show 1D, 2D or 3D inorganic sub-networks. One such compound was shown as an example. A 3d-6p (Mn–Bi. Named MOOMnBi) mixed metals coordination network has been synthesized via hydrothermal method. The new compound with the molecular formula of [MnBi{sub 2}O(1,3,5-BTC){sub 2}]{sub n} (1,3,5-BTC stands for benzene-1,3,5-tricarboxylate) was characterized via single crystal X-ray diffraction technique that revealed a very interesting 3-dimensional (3D) framework with Bi{sub 4}O{sub 2}(COO){sub 12} clusters which are further connected to Mn(COO){sub 6} fragments into a 2D MOO. The topology study indicates an unprecedented topological type with the net point group of (4{sup 13}.6{sup 2})(4{sup 13}.6{sup 8})(4{sup 16}.6{sup 5})(4{sup 18}.6{sup 10})(4{sup 22}.6{sup 14})(4{sup 3}) corresponding to 3,6,7,7,8,9-c hexa-nodal net. MOOMnBi shows catalytic activity in the synthesis of (E)-α,β-unsaturated ketones. - Graphical abstract: This metal organic framework (MOF) is the essence of a 2D metal organic oxide (MOO). - Highlights: • New concept of metal organic oxide (MOO) was defined and made difference from metal organic framework. • New MOO of MOOMnBi was synthesized by hydrothermal method. • Crystal structure of MOOMnBi was determined by single crystal X-ray analysis. • The catalytic activity of MOOMnBi was studied showing reusable after 2 cycles.

  7. Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiu-Mei; Li, Peng; Gao, Wei; Liu, Feng; Liu, Jie-Ping

    2016-12-01

    Three lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TZI)(H2O)4]·3H2O (Ln=Gd (1) and Tb (2) and Dy (3), H3TZI=5-(1H-tetrazol-5-yl)isophthalic acid), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction reveals that 1-3 are isostructural and display a 1D double chain based on dinuclear motifs with (μ-COO)2 double bridges. Magnetic studies indicate antiferromagnetic interactions in 1, ferromagnetic interactions in 2 and 3. Furthermore, compound 3 displays a slow relaxation behavior. Compound 2 exhibits intense characteristic green emission of Tb(III) ions in the solid state, which can be observed by the naked eye under UV light. Interestingly, 2 can selectively sense Pb2+ and Fe3+ ions through luminescence enhancement and quenching, respectively. The luminescence quenching mechanisms have been investigated in detail. The study on luminescence Ln-MOFs as a probe for sensing Pb2+ and Fe3+ ions is exceedingly rare example.

  8. Enhanced organic photovoltaic properties via structural modifications in PEDOT:PSS due to graphene oxide doping

    SciTech Connect

    Goutham, Raj P.; Sandhya, Rani V.; Kanwat, Anil; Jang, Jin

    2016-02-15

    Highlights: • Graphene oxide(GO) blended with PEDOT:PSS is used as HTL for PTB7:PCBM BHJ solar cells. • Increase in conductivity due to structural alterations in PEDOT:PSS by GO addition. • The structural alterations are reaveled under Raman spectroscopy, XPS and AFM. • PEDOT:PSS changed to extended coil due to addition of GO to PEDOT:PSS. • Enhanced conductivity after GO addition to PEDOT:PSS resulted in enhanced PCE. - Abstract: Poly(3,4-thylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS is a well-known conductive polymer for hole transport in organic devices, the properties of which can be enhanced by doping. Common dopants are metal oxides and nanoparticles. In this study, addition of graphene oxide (GO) to PEDOT:PSS as a dopant is addressed in organic photovoltaics (OPVs). With GO doping, electrical conductivity and transport properties of PEDOT:PSS increases due to structural alterations in the presence of −COOH and −OH functional groups in GO. These structural alterations have been revealed under detailed study of Raman spectra, X-ray photoelectron spectroscopy (XPS) analysis, Topographical and conductive Atom force microscopy (AFM/C-AFM) mapping. OPVs fabricated using PEDOT:PSS: GO (5:1) as a hole transport layer (HTL) exhibited a power conversion efficiency (PCE) of 7.68%, which was higher than the 7.01% that was obtained for the OPVs using pristine PEDOT:PSS.

  9. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    DOEpatents

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2016-08-02

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  10. Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

    DOEpatents

    McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

    2014-08-05

    Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

  11. Impact of organic pollutants on metal and As uptake by helophyte species and consequences for constructed wetlands design and management.

    PubMed

    Guittonny-Philippe, Anna; Masotti, Véronique; Claeys-Bruno, Magalie; Malleret, Laure; Coulomb, Bruno; Prudent, Pascale; Höhener, Patrick; Petit, Marie-Éléonore; Sergent, Michelle; laffont-Schwob, Isabelle

    2015-01-01

    Various industrial processes and anthropogenic activities in urban areas induce a release of metals, metalloids and organic pollutants. Phytoremediation of co-contaminated waters in constructed wetlands is a promising solution for reducing the impact on natural environments. In order to improve the design and management of constructed wetlands, more knowledge is needed concerning the effect of organic pollutants on plant metal and metalloid uptake. In this study, the effects of a mixture of organic pollutants commonly found in industrial effluents (hydrocarbons, polycyclic aromatic hydrocarbons, anionic detergent) on the uptake of ten metals and metalloids (MM), i.e. Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn, by five helophytes having a wide European distribution were studied. Main effects of plant species and pollutant conditions on metal uptake and interactions between factors were determined by a statistical treatment of a microcosm experiment. Overall, the order of element uptake in plants was Fe > Al > Mn > Cr, Ni, Zn, > Cu > As, Cd, Pb, which was consistent with relative concentrations in the rhizosphere environment of microcosms. Larger amounts of metals were retained in belowground biomass of plants than in aboveground parts. Statistical analysis showed that organic pollutants enhanced the accumulation of Mn in whole plants and the retention of Fe in belowground parts, while they reduced the accumulation of Cd, Ni, and Zn in whole plants and the retention of Cu in belowground parts. For the other MM (Al, As, Cr, Pb), effects were variable, depending on the plant species. Among the five plants tested, Carex cuprina generally removed the highest quantities of MM, which was the result of both a high metal accumulation capacity and high biomass production. Nevertheless, no significant proportion of the MM total loading could be removed in plants' aboveground parts.

  12. Highly mesoporous metal-organic framework assembled in a switchable solvent

    NASA Astrophysics Data System (ADS)

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-01

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  13. Highly mesoporous metal-organic framework assembled in a switchable solvent.

    PubMed

    Peng, Li; Zhang, Jianling; Xue, Zhimin; Han, Buxing; Sang, Xinxin; Liu, Chengcheng; Yang, Guanying

    2014-07-22

    The mesoporous metal-organic frameworks are a family of materials that have pore sizes ranging from 2 to 50 nm, which have shown promising applications in catalysis, adsorption, chemical sensing and so on. The preparation of mesoporous metal-organic frameworks usually needs the supramolecular or cooperative template strategy. Here we report the template-free assembly of mesoporous metal-organic frameworks by using CO2-expanded liquids as switchable solvents. The mesocellular metal-organic frameworks with large mesopores (13-23 nm) are formed, and their porosity properties can be easily adjusted by controlling CO2 pressure. Moreover, the use of CO2 can accelerate the reaction for metal-organic framework formation from metal salt and organic linker due to the viscosity-lowering effect of CO2, and the product can be recovered through CO2 extraction. The as-synthesized mesocellular metal-organic frameworks are highly active in catalysing the aerobic oxidation of benzylic alcohols under mild temperature at atmospheric pressure.

  14. Enhancement of ecosystem services during endophyte-assisted aided phytostabilization of metal contaminated mine soil.

    PubMed

    Burges, Aritz; Epelde, Lur; Benito, Garazi; Artetxe, Unai; Becerril, José M; Garbisu, Carlos

    2016-08-15

    Endophytic plant growth-promoting bacteria (endophytes) were isolated from a variety of (pseudo)metallophytes growing in an abandoned Zn/Pb mine and then characterized according to their plant growth-promoting traits (i.e. ACC deaminase activity, IAA production, siderophore production, phosphate solubilising capacity, metal and salt tolerance and phenotypic characterization). Initially, under growth chamber conditions, an endophyte-assisted aided phytostabilization study was carried out with Festuca rubra plants (native vs. commercial variety) inoculated with a Pseudomonas sp. isolate and cow slurry as organic amendment. The effect of treatments on soil physicochemical and microbial indicators of soil quality, as well as plant physiological parameters and metal concentrations, was assessed. We performed a complementary interpretation of our data through their grouping within a set of ecosystem services. Although the application of cow slurry had the most pronounced effects on soil quality indicators and ecosystem services, the growth of native F. rubra plants reduced soil bioavailability of Cd and Zn by 19 and 22%, respectively, and enhanced several soil microbial parameters. On the other hand, endophyte (Pseudomonas sp.) inoculation improved the physiological status of F. rubra plants by increasing the content of carotenoids, chlorophylls and Fv/Fm by 69, 65 and 37%, respectively, while also increasing the values of several soil microbial parameters. Finally, a consortium of five endophyte isolates was used for an endophyte-assisted aided phytostabilization field experiment, where lower metal concentrations in native excluder plants were found. Nonetheless, the field inoculation of the endophyte consortium had no effect on the biomass of native plants.

  15. Modelling of trace metal uptake by roots taking into account complexation by exogenous organic ligands

    NASA Astrophysics Data System (ADS)

    Jean-Marc, Custos; Christian, Moyne; Sterckeman, Thibault

    2010-05-01

    The context of this study is phytoextraction of soil trace metals such as Cd, Pb or Zn. Trace metal transfer from soil to plant depends on physical and chemical processes such as minerals alteration, transport, adsorption/desorption, reactions in solution and biological processes including the action of plant roots and of associated micro-flora. Complexation of metal ions by organic ligands is considered to play a role on the availability of trace metals for roots in particular in the event that synthetic ligands (EDTA, NTA, etc.) are added to the soil to increase the solubility of the contaminants. As this role is not clearly understood, we wanted to simulate it in order to quantify the effect of organic ligands on root uptake of trace metals and produce a tool which could help in optimizing the conditions of phytoextraction.We studied the effect of an aminocarboxilate ligand on the absorption of the metal ion by roots, both in hydroponic solution and in soil solution, for which we had to formalize the buffer power for the metal. We assumed that the hydrated metal ion is the only form which can be absorbed by the plants. Transport and reaction processes were modelled for a system made up of the metal M, a ligand L and the metal complex ML. The Tinker-Nye-Barber model was adapted to describe the transport of solutes M, L and ML in the soil and absorption of M by the roots. This allowed to represent the interactions between transport, chelating reactions, absorption of the solutes at the root surface, root growth with time, in order to simulate metal uptake by a whole root system.Several assumptions were tested such as i) absorption of the metal by an infinite sink and according to a Michaelis-Menten kinetics, solutes transport by diffusion with and without ii) mass flow and iii) soil buffer power for the ligand L. In hydroponic solution (without soil buffer power), ligands decreased the trace metal flux towards roots, as they reduced the concentration of hydrated

  16. Enhanced selective metal adsorption on optimised agroforestry waste mixtures.

    PubMed

    Rosales, Emilio; Ferreira, Laura; Sanromán, M Ángeles; Tavares, Teresa; Pazos, Marta

    2015-04-01

    The aim of this work is to ascertain the potentials of different agroforestry wastes to be used as biosorbents in the removal of a mixture of heavy metals. Fern (FE), rice husk (RI) and oak leaves (OA) presented the best removal percentages for Cu(II) and Ni(II), Mn(II) and Zn(II) and Cr(VI), respectively. The performance of a mixture of these three biosorbents was evaluated, and an improvement of 10% in the overall removal was obtained (19.25mg/g). The optimum mixture proportions were determined using simplex-centroid mixture design method (FE:OA:RI=50:13.7:36.3). The adsorption kinetics and isotherms of the optimised mixture were fit by the pseudo-first order kinetic model and Langmuir isotherm. The adsorption mechanism was studied, and the effects of the carboxylic, hydroxyl and phenolic groups on metal-biomass binding were demonstrated. Finally, the recoveries of the metals using biomass were investigated, and cationic metal recoveries of 100% were achieved when acidic solutions were used.

  17. Enhancement of Platinum Cathode Catalysis by Addition of Transition Metals

    ERIC Educational Resources Information Center

    Duong, Hung Tuan

    2009-01-01

    The sluggish kinetics of oxygen reduction reaction (ORR) contributes significantly to the loss of cathode overpotential in fuel cells, thus requiring high loadings of platinum (Pt), which is an expensive metal with limited supply. However, Pt and Pt-based alloys are still the best available electrocatalysts for ORR thus far. The research presented…

  18. How surface-enhanced chemiluminescence depends on the distance from a corrugated metal film

    NASA Astrophysics Data System (ADS)

    Lu, Guowei; Shen, Hong; Cheng, Bolin; Chen, Zhenghao; Marquette, Christophe A.; Blum, Loic J.; Tillement, Olivier; Roux, Stéphane; Ledoux, Gilles; Ou, Meigui; Perriat, Pascal

    2006-11-01

    Peroxidase labeled streptavidin was immobilized onto the surface of bulk and clusterlike metal films at a distance controlled by a peptide chain with a length between 1.3 and 7.8nm. Luminol chemiluminescence which occurred at peroxidase vicinity depends on the metal nanostructure. When peroxidase is attached on a bulklike film, chemiluminescence increases monotonously with the distance because of a decrease of the light emission quenching by metal. When peroxidase is attached on a clusterlike film, chemiluminescence undergoes a complex variation with the metal/catalyst distance evidencing a competition between the already mentioned quenching process and a nanostructure-induced catalysis enhancement.

  19. Enhanced light-harvesting capability for silicon single-nanowire solar cells coupled with metallic cavity.

    PubMed

    Gai, Feng; Zhang, Cheng; Zhan, Yaohui; Li, Xiaofeng

    2016-12-26

    Single-nanowire solar cells (SNSCs) are attracting increasing interest due to their unique optical antenna effect beneficial for achieving higher light-trapping capability. However, for conventional circular-cross-sectional SNSCs, the light-trapping performance is still far from the expectation. Here we demonstrate that integrating a silicon single nanowire into a metallic slit can dramatically enhance the absorption efficiency over almost the whole spectral band due to strengthened optical antenna effect. Especially, it is found that by using finite-size metallic blocks to form a nanoscale metallic cavity, the light-trapping performance of the SNSCs can be further improved. Through examining the detailed optical spectral response, electric field distribution, and cavity dispersion characteristics, the metallic-coupled SNSC system is optimized and the underlying physics are provided. Simulation results indicate that the photocurrent density of the SNSCs coupled with the designed metallic cavity can be enhanced by 44.4% than that of the conventional bare SNSCs.

  20. Phase-locked coherent modes in a patterned metal-organic microcavity

    NASA Astrophysics Data System (ADS)

    Brückner, R.; Zakhidov, A. A.; Scholz, R.; Sudzius, M.; Hintschich, S. I.; Fröb, H.; Lyssenko, V. G.; Leo, K.

    2012-05-01

    Organic microcavities offer tantalizing prospects for studying the interactions of light and matter. For electrical excitation of these processes, electrodes must be integrated. However, the large absorption properties of metals are generally considered fatal for optical coherence. With this in mind, we embedded a thin silver grating into an organic microcavity to generate periodic arrays of localized cavity modes and metal-based Tamm plasmon polaritons. These excited states are capable of phase coupling across the grating. At room temperature and under non-resonant pumping, we selectively stimulated coherent emission from in- and out-of-phase locked arrays. We show that an absorptive metal inside an optical cavity is compatible with coherent emission. Most importantly, the inherently low residual absorption of the organic layer enables coherence to spread over macroscopic distances, even at room temperature. Our strategy of embedding metal patterns into an organic microcavity yields a viable route towards electrically driven organic solid-state lasers.