Chemistry Commons^™

Light-Activated Photocurrent Degradation And Self-Healing In Perovskite Solar Cells, Wanyi Nie, Jean-Christophe Blancon, Amanda J. Neukirch, Kannatassen Appavoo, Hsinhan Tsai, Manish Chhowalla, Muhammad A. Alam, Matthew Y. Sfeir, Claudine Katan, Jacky Even, Sergei Tretiak, Jared J. Crochet, Gautam Gupta, Aditya D. Mohite

Publications and Research

Solution-processed organometallic perovskite solar cells have emerged as one of the most promising thin-film photovoltaic technology. However, a key challenge is their lack of stability over prolonged solar irradiation. Few studies have investigated the effect of light soaking on hybrid perovskites and have attributed the degradation in the optoelectronic properties to photochemical or field-assisted ion migration. Here we show that the slow photocurrent degradation in thin-film photovoltaic devices is due to the formation of light-activated meta-stable deep-level trap states. However, the devices can self-heal completely by resting them in the dark for <1 min or the degradation can be completely prevented by operating the devices at 0°C. We investigate several physical mechanisms to explain the microscopic origin for the formation of these trap states, among which the creation of small polaronic states involving localized cooperative lattice strain and molecular orientations emerges as a credible microscopic mechanism requiring further detailed studies.

Direct Band Gap Gallium Antimonide Phosphide (Gasbxp1-X) For Solar Fuels., Harry Benjamin Russell

Electronic Theses and Dissertations

Photoelectrochemical water splitting has been identified as a promising route for achieving sustainable energy future. However, semiconductor materials with the appropriate optical, electrical and electrochemical properties have yet to be discovered. In search of an appropriate semiconductor to fill this gap, GaSbP, a semiconductor never tested for PEC performance is proposed here and investigated. Density functional theory (DFT+U) techniques were utilized to predict band gap and band edge energetics for GaSbP alloys with low amount of antimony. The overall objective of this dissertation is to understand the suitability of GaSb_xP_1-x alloys for photoelectrochemical water splitting application. Specifically, …

Special Issue: Electrocatalyst And Electrocatalysis In Fuel Cells Preface, Zi-Dong Wei

Journal of Electrochemistry

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Recent Progress In Non-Precious Metal Oxygen Reduction Reaction Catalysts With An Encapsulation Structure, Mei-Ling Xiao, Jian-Bing Zhu, Chang-Peng Liu, Jun-Jie Ge, Wei Xing

Journal of Electrochemistry

Platinum-based materials, the state-of-the-art catalysts for fuel cells, suffer from prohibitive costs, limited resources and insufficient durability. Accordingly, tremendous efforts were made in searching for efficient, durable and inexpensive alternatives to precious-metal electrocatalysts for the oxygen reduction reaction (ORR). Transition-metals (Fe, Co)/nitrogen co-doped hybrids, heteroatom (N, P, S, F, et al) doped carbons and composites with transition-metals encapsulated in graphitic layers are reported as the most efficient non-precious metal ORR catalysts. Among the various non-precious metal ORR catalysts, transition-metals encased in graphitic layer catalysts are a novel type of catalysts for ORR with high activity and durability, and thus, the …

Mini-Review: Possible Applications Of Scanning Electrochemical Microscopy (Secm) In Characterizations Of Oxygen Reduction Reaction And Oxygen Evolution Reaction, Xing-Xing Chen

Journal of Electrochemistry

Scanning electrochemical microscopy (SECM) has been proved to be a unique technique for combinatorial screening of localized phenomena for different electrocatalysts potentially used in new energy conversion and storage systems. This mini-review provides a brief summary of different SECM working modes, such as direct mode, feedback mode, generation-collection mode, redox competition mode and noise mode, which are especially applied for characterizing the oxygen reactions. Particularly, a series of important development in SECM screening of electrocatalysts for oxygen reduction reaction and oxygen evolution reaction from the author and W. Schuhmann’s group in Germany has been highlighted and overviewed. Finally, some prospects …

Syntheses Of Carbon Paper Supported High-Index Faceted Pt Nanoparticles And Their Performance In Direct Formic Acid Fuel Cells, Long Huang, Mei Zhan, Yu-Cheng Wang, Yan-Fen Lin, Shuo Liu, Ting Yuan, Hui Yang, Shi-Gang Sun

Journal of Electrochemistry

Direct formic acid fuel fuels (DFAFCs) are promising energy source for portable electronic devices. Palladium (Pd) is more active than platinum (Pt) for the formic acid electrooxidation. However, the stability of Pd is much poorer than that of Pt. Unfortunately, the ultra-low natural abundance of the Pt makes it extremely expensive and limits its application as a fuel cell catalyst. Boosting both the activity and stability of Pt nanoparticles to enhance their efficiency is urgent. As previous works illustrated, nanoparticles enclosed with high-index facets usually bare a higher activity toward fuel cell related reactions than those nanoparticles with low-index facet. …

Dynamic Simulation Of Oxygen Reduction Reaction In Pt/C Electrode For Proton Exchange Membrane Fuel Cells, Shang Li, Fen Zhou, Lei Chen, Mu Pan

Journal of Electrochemistry

It is an urgent need to reduce the Pt loading in electrode for practical fuel cell applications worldwide. Herein, we theoretically investigate the oxygen distribution, generated current, and minimum Pt loading of Pt/C electrode for practical applications based on kinetic model of oxygen reduction reaction. The results indicate that with increasing electrode effective thickness to 40 mm, serious concentration polarization is expected for Pt/C electrode. To generate a power density of 1.4 W⋅cm^-2 (2.1A⋅cm^-2@0.67 V) for fuel cell, the cathode catalyst layer thickness in PEMFC should be as thin as 3 mm. The minimum Pt loading will …

Multi-Scaled Carbon Supported Platinum As A Stable Electrocatalyst For Oxygen Reduction Reaction, Yu-Ping Li, Lu-Hua Jiang, Su-Li Wang, Gong-Quan Sun

Journal of Electrochemistry

The stability of carbon supports is essential for electrocatalysts of fuel cells. Herein, the mesoporous carbon with the high graphitic degree (highly graphitic mesoporous carbon, HGMC) was synthesized by using resorcinol as the carbon precursor, SiO₂ as the templates and urea as the reducing agent. The as-prepared HGMC was characterized by XRD, Raman spectroscopy, TEM, N2 adsorption. The stability of HGMC was evaluated by mimicking the start-up/shut-down conditions of fuel cells in a three-electrode system referring to the NREL standard. The obtained HGMC is of moderate surface area (187.4 m²•g^-1) and is chemically stable under …

Recycling Mf Solid Waste Into Mesoporous Nitrogen-Doped Carbon With Iron Carbide Complex In Graphitic Layers As An Efficient Catalyst For Oxygen Reduction Reaction, Can-Yun Zhao, Lin Huang, Yong You, Ying-Fang Yao, Xiao-Gang Su, Hong Wan, Jian-Guo Liu, Cong-Ping Wu

Journal of Electrochemistry

Nitrogen-doped carbon materials with iron ions are known as catalytic growth agents for the oxygen reduction reaction (ORR) in fuel cells, but the design and synthesis of high-performance and low-cost catalysts still remain a significant challenge. Herein, we present a cost-effective approach to dispose of MF solid waste as the precursor for the synthesis of MCFes catalyst with the favorable structure features such as the high specific surface area, abundant active sites and suitable pore structure. The results showed that the MCFe-10/10/2 had specific surface area as high as 780.7 m²•g^-1 and high efficient catalytic activity comparable …

Synthesis Of Structurally Ordered Platinum-Iron Catalysts With Enhanced Oxygen Reduction Reaction Activity, Ye-Zheng Cai, Ming-Chuan Luo, Fang-Hui Wang, Zhao-Nan Sun, Hong Zhu

Journal of Electrochemistry

To improve oxygen reduction reaction catalytic activity of the precious metals platinum for fuel cell, the precursors of carbon-supported structurally disordered platinum-iron alloy (D-Pt₃Fe/C and D-PtFe/C) catalysts with different compositions were synthesized via a modified polyol reduction method. Then, by optimizing the annealing conditions in the inert gas, we turned the structurally disordered platinum-iron alloy to the structurally ordered platinum-iron alloy (O-Pt₃Fe/C and O-PtFe/C) catalysts. The structural characterizations of the as-prepared catalysts were performed by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The results …

Recent Progresses In Molybdenum-Based Electrocatalysts For The Hydrogen Evolution Reaction, Ze-Xing Wu, Jie Wang, Jun-Po Guo, Jing Zhu, De-Li Wang

Journal of Electrochemistry

Electrochemical catalytic production of hydrogen has been considered as a promising and sustainable strategy for clean and renewable energy technologies. Molybdenum-based non noble metal catalysts for the hydrogen evolution reaction have attracted extensive attention due to its effective catalytic performance. In this review, the recent progresses in molybdenum-carbide, phosphide, nitride and sulfide electrocatalysts are presented. In addition, the strategies to improve the catalytic performance are analyzed and the prospects for the future development trends are expected.

Preparation And Performance Of 3d Graphene Type Porous Carbon Employing Nano Fe(Oh)3 As Template For Oxygen Reduction Catalyst, Chong-Yun Sun, Zhong-Fang Li, Xue-Wei Lu, Xi-Zhan Zhong, Yu-Rong Liu

Journal of Electrochemistry

The 3D graphene type porous carbon was prepared using coal tar pitch as carbon source and nano Fe(OH)₃ as template. Optimal conditions for the catalytic oxygen reduction performance were determined as: the mass ratio of coal tar, nano Fe(OH)₃ and KOH is 6:8:4; the pyrolysis temperature is 800 ^oC. SEM images show that the products have uniformly porous structure. TEM images demonstrate that the products are porous with foam shapes. HRTEM images further indicate that the products have formed several-layers 3D graphene structure, which are also supported by XRD and Raman data, and the pore size mainly …

Nitrogen, Fluorine Co-Doped Silk-Derived Carbon For Electrochemical Oxygen Reduction With High Performance In Alkaline Solution, Fang-Fang Liu, Hong-Liang Peng, Shi-Jun Liao

Journal of Electrochemistry

A high-performance, doped carbon-based catalyst was synthesized by pyrolyzing hydrothermally treated silkworm cocoon. The effects of preparation conditions and fluorine promotion on various catalysts’ performance were investigated. The catalyst prepared under optimal conditions and doped with nitrogen and fluorine possessed the high specific surface area of more than 1000 m^2⋅g^-1 and contained 3.5 and 7.3% (by mass, the same below) N and F, respectively. The activity of the catalyst toward oxygen reduction reaction in an alkaline medium was comparable to that of commercial Pt/C, showing both superior tolerance to methanol poisoning and better durability. Doping with fluorine …

Rambling Between "Zhong Yong" And "Catalysis", Zi-Dong Wei

Journal of Electrochemistry

“Zhong Yong” represents a traditional Chinese wisdom, which was first proposed by Confucius and continuously richened by his followers. “Zhong Yong” pursues the balances among all kinds of contradictions, and insists that neither “too much” nor “not enough” is good. For a successful catalyst, on which the adsorption of reactants must be not so strong and not so weak either. On this point of view, there are the same pursuits for “Zhong Yong” and catalysis. In this paper, the author starts his story with a conversation between Confucius and his student, followed by 3 interesting stories happening in the ancient …

Optimizing Chemical & Rheological Properties Of Rejuvenated Bitumen, Dominic Nguyen, Hamzeh Haghshenas Fatmehsari, Santosh Kommidi, Yong-Rak Kim

Department of Civil and Environmental Engineering: Dissertations, Theses, and Student Research

Bitumen has long been a material used in the construction of roadways, yet new pavement only consists of low fractions of recycled materials due to poor compatibility of aged bitumen and new materials. Thus, rejuvenators, chemical additives, have been used in an attempt to re-balance the chemical composition and restore the physical properties of aged bitumen back to its virgin state. A fundamental understanding of how one particular rejuvenator, soybean oil, revitalizes bitumen was investigated using a multi-scale approach.

Fourier-transform infrared spectroscopy (FTIR) was used to determine the changes in chemical properties of pure and rejuvenated virgin and aged samples. …

Low-Temperature Artificial Maturation Studies Of Type Ii And Type Iii Kerogens: Implications For Biogenic Gas Production, Albert Willy Nguena Kamga

Chemistry & Biochemistry Theses & Dissertations

Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop …

Investigation Of The Use Of A Plasticizer-Polymer Sensor Coating With Improved Long-Term Stability In The Liquid Phase, Laura Jeanne Alderson

Master's Theses (2009 -)

Benzene is one of the volatile organic compounds present in crude oil and gasoline. Leakage from underground storage tanks or hazardous waste sites can introduce benzene contamination into nearby groundwater. Benzene is a known carcinogen and its exposure is limited by the Environmental Protection Agency to 5 parts per billion (ppb) in drinking water. Early, accurate detection of the presence of benzene contamination in groundwater supplies is extremely important. Shear horizontal surface acoustic wave (SH-SAW) devices with a chemically sensitive coating can be used for the detection of volatile organic compounds in liquid, such as BTEX (benzene, toluene, ethylbenzene and …

Targeted Metabolomics On The Shikimate And Aromatic Amino Acid Biosynthetic Pathways, Robert E. Wheeler

Open Access Theses

The shikimate and aromatic amino acid biosynthesis pathways are some of the most studied biosynthetic pathways in nature due to their fundamental importance. Interest in this field stems from synthesis of the essential amino acids, tryptophan, tyrosine and phenylalanine. The pathways also are important as generating the precursors of thousands of secondary metabolites and lignin. Inhibiting the pathway has led to discovery of herbicides, pesticides as well as tuberculosis drugs. However there is currently a lack of a comprehensive targeted method for detecting and quantifying the majority of the intermediates in these pathways. Often multiple extraction and detection methods are …

Modified Yttrium Hydroxide/Mc Nylon Nanocomposites And Scaling Effects In Multilayer Polyethylene Films, Jia Chen

USF Tampa Graduate Theses and Dissertations

In this thesis, monomer casting (MC) nylon was synthesized. MC nylon could replace nonferrous metals in certain applications, including gears, wheels, and other moving parts. However, compared with metals, MC nylon products have poor strength and stiffness, and crack easily, especially at low temperatures. In addition, the dimensional stability of MC nylon is poor, especially in the large casting nylon products, causing significant internal stresses due to shrinkage. Thus, MC nylon cracks easily when cast and molded. The yttrium hydroxide particles were modified by stearic acid and dispersed in the caprolactam. The polymerization time was short due to fast anionic …

High Temperature Electrochemical Engineering And Clean Energy Systems, Brenda L. Garcia-Diaz, Luke Olson, Michael Martinez-Rodriguez, Roderick Fuentes, Hector Colon-Mercado, Josh Gray

Journal of the South Carolina Academy of Science

Global power demand is projected to more than double by 2050 and meeting this increased power demand will require maintaining or increasing power output from all existing energy sources while adding a large amount of new capacity. The power sources that have the greatest opportunity to fulfill this demand gap over this time period are clean energy sources including solar and nuclear power. One of the areas of expertise that SRNL has been applying to help with a variety of clean energy technologies is in high temperature electrochemistry. Savannah River National Laboratory (SRNL) in collaboration with industrial and university partners …

Electrochemical Syntheses Of Graphene And Its Composites, Bo Zhao, Li Jiang, Ming-Hui Yuen, Xian-Zhu Fu, Rong Sun, Ching-Ping Wong

Journal of Electrochemistry

Graphene is a kind of ideal two-dimensional flat carbon nanomaterials which have unique chemical and physical properties. The attractive potential applications must be based on the high quality mass production of graphene. However, it remains a huge challenge. An electrochemical approach is a fast, environmental friendly and easy-operating method. single- or multi-layered graphene flakes can easily be produced in short periods of time. In this review, the structure, properties and preparation methods of graphene are first introduced. Accordingly, the electrochemical approaches used for the productions of graphene flakes, graphene/inorganic nanocomposites, graphene/polymer composites and graphene analogues are highlighted. Finally, challenges and …

Synthesis Of Fe, N-Doped Graphene/Carbon Black Composite With High Catalytic Activity For Oxygen Reduction Reaction, Chi Chen, Zhi-You Zhou, Xin-Sheng Zhang, Shi-Gang Sun

Journal of Electrochemistry

Oxygen reduction reaction (ORR) is a bottleneck for improving the efficiency of proton-exchange membrane fuel cells as a cathode reaction due to its sluggish kinetics. The exploitation of low cost and high performance non-precious metal catalysts such as Fe/N/C based materials toward ORR has attracted extensive attentions. In this work, the Fe, N-doped graphene nanosheets/carbon black composite was prepared by hydrothermal polymerization and followed by a twice-heat-treatment procedure using 2-aminoimidazole as an N precursor, FeCl₃ as an Fe precursor and KJ600 carbon black as a support. The TEM images revealed that the graphene nanosheets were separated by carbon black …

Electricity Generation Of Microbial Fuel Cell Using Stainless Steel Mesh As Cathode, Hong-Yan Dai, Hui-Min Yang, Xian Liu, Xuan Jian, Xiu-Li Song, Zhen-Hai Liang

Journal of Electrochemistry

In the present work, a dual-chamber microbial fuel cell (MFC) was constructed with aeration tank sludge as an inoculum, carbon felt as an anode and stainless steel mesh without any modification as a cathode. The influence of the cathode size was investigated in terms of voltage output, power generation and electrochemical impedance. The long-term durability of the stainless steel mesh cathode was also evaluated. Results showed that the stainless steel mesh exhibited satisfactory long-term durability as MFC cathode. When the stainless steel mesh size was 2 × 2 cm², the maximum output voltage, power density, the internal resistance …

Electrochemical Detection Of Hydrogen Peroxide At Aunps Modified Electrode Using P-Hydroxyphenylboronic Acid As A Precursor, Chun-Yan Wang, Xiao-Qiu Liu, Ying-Xin Qi

Journal of Electrochemistry

We developed a new method for electrochemical detection of hydrogen peroxide (H₂O₂) based on boronate oxidation of p-hydroxyphenylboronic acid. This method using p-aminophenol which is produced from the reaction of H₂O₂ and p-aminophenylboronic acid as a well electrochemical probe, combined with a gold nanoparticles (AuNPs) modified electrode for an indirect detection of H₂O₂. Because of the large surface area and enhanced electrocatalytic behavior by the AuNPs modified electrode, the detection sensitivity was improved. The method could detect H₂O₂ in the concentration range of 1 ~ 100 …

The Study On Comparison Of Electrochemical Performance In Microbial Fuel Cell With Glucose And Sodium Acetate Acting As Substrates, Lei Fan, Yu Zhao, Ting Li, Qin-Bo Yuan, En-Zhi Wang, Xiao-Bin Wang, Jun-Wen Wang

Journal of Electrochemistry

By inoculating aerobic sludge and anaerobic sludge from the sewage treatment plant, two sets of dual-chamber microbial fuel cells (MFCs) were built with either glucose or sodium acetate acting as a substrate. Accordingly, the electrochemical performances of MFCs were explored with the concentration of the substrates being 0.0335 mol⋅L^-1. The results of the comparative study in glucose system and sodium acetate system showed that the impedance values of anodic half cell were 222 Ω for glucose and 213.67 Ω for sodium acetate, implying no significant effect on the internal resistance in battery with the different substrates. The exchange …

Effect Of Spalled Particles Thermal Degradation On A Hypersonic Flow Field Environment, Raghava S. C. Davuluri, Huaibao Zhang, Alexandre Martin

Mechanical Engineering Faculty Publications

Two-way coupling is performed between a spallation code and a hypersonic aerothermodynamics CFD solver to evaluate the effect of spalled particles on the flow field. Time accurate solutions are computed in argon and air flow fields. A single particle simulations and multiple particles simulations are performed and studied. The results show that the carbon vapor released by spalled particles tend to change the composition of the flow field, particularly the upstream region of the shock.

Methane Emissions As Energy Reservoir: Context, Scope, Causes And Mitigation Strategies, Xiaoli Chai, David J. Tonjes, Devinder Mahajan

Technology & Society Faculty Publications

Methane (CH4) is now considered a bridge fuel between present fossil (carbon) economy and desired renewables and this energy molecule is projected to play an important role in the global energy mix well beyond 2035. The atmospheric warming potential of CH4 is 28-36 times, when averaged over a 100-year period, that of carbon dioxide (CO2) and this necessitates a close scrutiny of global CH4 emissions inventory. As the second most abundant greenhouse gas (GHG), the annual global CH4 emissions were 645 million metric tons (MMT), accounting for 14.3% of the global anthropogenic GHG emissions. Of this, five key anthropogenic sources: …

New Chemistry For The Growth Of First-Row Transition Metal Films By Atomic Layer Deposition, Joseph Peter Klesko

Wayne State University Dissertations

Thin films containing first-row transition metals are widely used in microelectronic, photovoltaic, catalytic, and surface-coating applications. In particular, metallic films are essential for interconnects and seed, barrier, and capping layers in integrated circuitry. Traditional vapor deposition methods for film growth include PVD, CVD, or the use of plasma. However, these techniques lack the requisite precision for film growth at the nanoscale, and thus, are increasingly inadequate for many current and future applications. By contrast, ALD is the favored approach for depositing films with absolute surface conformality and thickness control on 3D architectures and in high aspect ratio features. However, the …

Carinata Fame Production Process And Biofuel Oxidation, Benoit Kindo

Honors College Theses

In this experiment, the contribution of a standard production method for biofuels on their oxidative stability was investigated. Peroxide values were measured at different steps of the production process of Brassica carinata and peanut-based biofuels. The washing and drying steps in this production method showed significant increases in peroxide values for both biofuels and was identified as a major contributor of biofuel oxidation. Further analyses of the physical and thermal properties showed a more pronounced affect in the biofuel from Bassica carinata, and indicated an unusual composition much higher in saturated fatty acids much longer than those found in peanut. …

Enabling Method To Design Versatile Biomaterial Systems From Colloidal Building Blocks, Shalini Saxena, L. Andrew Lyon

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Development of materials with fine spatial control over topographical, mechanical, or chemical features has been investigated for a variety of applications. Here we present a method to fabricate an array of polyelectrolyte constructs including two-dimensionally and three-dimensionally patterned assemblies using both compressible and incompressible colloidal building blocks. This method eliminates prior constraints associated with specific chemistries, and can be used to develop modular, multi-component, patterned assemblies. In particular, development of constructs were investigated using microgels, which are colloidally stable hydrogel microparticles, polystyrene (PS) beads, and PS-microgel core-shell building blocks in conjunction with the polycation poly(ethyleneimine) (PEI). The topography, mechanical properties, …