Chemical Engineering Commons^™

Engineering Nanoelectrocatalytic Systems For Co2 And Nitrate Conversion Into Value-Added Chemicals, Abdelrahman Mohamed Abdelmohsen

Theses and Dissertations

The thesis addresses two major related environmental crises: nitrate pollution of water systems and the ever-increasing levels of atmospheric carbon dioxide. Both challenges are closely linked to anthropogenic disturbance of nitrogen and carbon cycles and require sustainable, energy efficient mitigation techniques. In this study, we investigate electrochemical conversion routes as a unified approach to convert these pollutants into value-added compounds: ammonia (NH3) via nitrate reduction (NO3-RR) and ethylene (C2H4) via carbon dioxide reduction (CO2RR). The first half of this work deals with the design and engineering of Cu-Zn alloy electrocatalysts for efficient NO3-RR. Tuning the alloy composition and surface nanostructure …

Design And Optimization Of Anode Catalysts For Direct Ethanol Fuel Cells: Advances And Challenges In C-C Bond Activation And Selective Modulation Of The C1 Pathway, Kai-Chi Qin, Meng-Tian Huo, Yu Liang, Si-Yuan Zhu, Zi-Hao Xing, Jin-Fa Chang

Journal of Electrochemistry

Direct ethanol fuel cells (DEFCs) are a promising alternative to conventional energy sources, offering high energy density, environmental sustainability, and operational safety. Compared to methanol fuel cells, DEFCs exhibit lower toxicity and a more mature preparation process. Unlike hydrogen fuel cells, DEFCs provide superior storage and transport feasibility, as well as cost-effectiveness, significantly enhancing their commercial viability. However, the stable C–C bond in ethanol creates a high activation energy barrier, often resulting in incomplete electrooxidation. Current commercial platinum (Pt)- and palladium (Pd)-based catalysts demonstrate low C–C bond cleavage efficiency (

Ionic Liquid Enhanced Proton Transfer For Neutral Oxygen Evolution Reaction, Ming-Xing Chen, Nian Liu, Zi-He Dua, Jing Qi, Rui Cao

Journal of Electrochemistry

The development of highly active catalyst in pH-neutral media for oxygen evolution reaction (OER) is critical in the field of renewable energy storage and conversion. Nevertheless, the slow kinetics of proton-coupled electron transfer (PCET) hinders the overall OER efficiency. Herein, we report an ionic liquid (IL) modified CoSn(OH)₆ nanocubes (denoted as CoSn(OH)₆-IL), which could be prepared through a facile strategy. The modified IL would not change the structural characteristics of CoSn(OH)₆, but could effectively regulate the local proton activity near the active sites. The CoSn(OH)₆-IL exhibited higher intrinsic OER performances than the pristine …

Ambient Co2 Capture And Valorization Enabled By Tandem Electrolysis Using Solid-State Electrolyte Reactor, Yan-Bo Hua, Bao-Xin Ni, Kun Jiang

Journal of Electrochemistry

Electrocatalytic carbon dioxide reduction is a promising technology for addressing global energy and environmental crises. However, its practical application faces two critical challenges: the complex and energy-intensive process of separating mixed reduction products and the economic viability of the carbon sources (reactants) used. To tackle these challenges simultaneously, solid-state electrolyte (SSE) reactors are emerging as a promising solution. In this review, we focus on the feasibility of applying SSE for tandem electrochemical CO₂ capture and conversion. The configurations and fundamental principles of SSE reactors are first discussed, followed by an introduction to its applications in these two specific areas, …

Ordering Degree Regulation Of Pt2Nico Intermetallics For Efficient Oxygen Reduction Reaction, Chen-Hao Zhang, Han-Yu Hua, Jun-Hao Yang, Qian Zhang, Chang Yang, De-Li Wang

Journal of Electrochemistry

Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction (ORR). Atomic ordered intermetallic compounds (IMC) provide unique electronic and geometrical effects as well as stronger intermetallic interactions due to the ordered arrangement of metal atoms, thus exhibiting superior electrocatalytic activity and durability. However, quantitatively analyzing the ordering degree of IMC and exploring the correlation between the ordering degree and ORR activity remains extremely challenging. Herein, a series of ternary Pt₂NiCo intermetallic catalysts (o-Pt₂NiCo) with different ordering degree were synthesized by annealing temperature modulation. Among them, the o-Pt …

Nanostructured Transition Metal Oxides For Electrochemical Co2 And Methane Conversion, Olumide O. Oladoyin

Chemical and Biological Engineering ETDs

Rising atmospheric CO₂ and CH₄ drive climate change, prompting research into their electrochemical conversion to valuable products. This study investigates electrodeposited nanostructured transition metal oxides (TMOs), unary (CuO, Co₃O₄) and dual (Cu-Co oxide) as catalysts for CO₂ reduction and CH₄ oxidation under ambient conditions. Fabricated on various substrates (Cu foil, SS316, carbon paper) and characterized by SEM, their electrochemical performance was evaluated via cyclic voltammetry.

Cu-Co oxide showed superior CO₂ reduction, leveraging the strengths of individual oxides. Co₃O₄ exhibited higher current densities for CH₄ oxidation, with SS316 proving the best substrate. Catalyst composition, morphology, and substrate significantly influenced efficiency. While …

A Cnt Intercalated Co Porphyrin-Based Metal Organic Framework Catalyst For Oxygen Reduction Reaction, Pei-Pei He, Jin-Hua Shi, Xiao-Yu Li, Ming-Jie Liu, Zhou Fang, Jing He, Zhong-Jian Li, Xin-Sheng Peng, Qing-Gang He

Journal of Electrochemistry

The poor electronic conductivity of metal-organic framework (MOF) materials hinders their direct application in the field of electrocatalysis in fuel cells. Herein, we proposed a strategy of embedding carbon nanotubes (CNTs) during the growth process of MOF crystals, synthesizing a metalloporphyrin-based MOF catalyst TCPPCo-MOF-CNT with a unique CNT-intercalated MOF structure. Physical characterization revealed that the CNTs enhance the overall conductivity while retaining the original characteristics of the MOF and metalloporphyrin. Simultaneously, the insertion of CNTs generated adequate mesopores and created a hierarchical porous structure that enhances mass transfer efficiency. X-ray photoelectron spectroscopic analysis confirmed that the C atom in CNT …

Optimization And Dft Study For Boosted Electooxidation Of Formic Acid At Niox Modified Pt Using Urea Derivatives As Blending Fuels, Aya Saada

Biochemical Engineering

This paper addresses the enhancement of formic acid electrooxidation (FAO) at Pt and Pt-NiOx nanoparticles based-catalysts assisted with urea derivatives as blending fuels. Blending formic acid with various ratios of urea derivatives showed noticeable enhancements of FAO as demonstrated by a favorable negative shift of its onset potential (Eonset) and increase of its peak current density concurrently with suppression of the amount of CO poisoning reaction intermediate. Among all the used derivatives, phenyl urea (PU) showed superior enhancing effect towards the direct FAO with a minimal CO formation together with a favorable negative shift of Eonset by 150 mV. The …

Nickel Electrocatalysts On Carbon Supports For The Hydrogen Evolution Reaction., Mohan Paudel

Electronic Theses and Dissertations

Hydrogen is an important energy storage alternative to fossil fuels due to its high energy density. Currently, most hydrogen is produced through petroleum feedstocks, which produce large amounts of carbon dioxide. However, a more eco-friendly method is the electrocatalytic splitting of water into hydrogen and oxygen. Efficient catalysts for the hydrogen evolution reaction (HER) are typically platinum group metals, which are rare and expensive. There is growing interest in developing HER electrocatalysts with earth-abundant metals for water electrolysis. Nickel, which lies in the same group in the periodic table as Pt and has similar chemical properties, is explored extensively for …

Single Nanobubble Formation On Au Nanoelectrodes And Au@Ws2 Nanoelectrodes: Voltammetric Analysis And Electrocatalysis, Xian-Zhun Luo, Xiao-Hu Chen, Yong-Xin Li

Journal of Electrochemistry

Taking advantage of the extremely small size of the gold nanodisk electrode, the single hydrogen nanobubble generated on the surface of the nanoelectrode was studied to evaluate its hydrogen evolution performance. It was found that compared with the bare gold nanodisk electrode, the bubble formation potential of the gold nanodisk electrode modified with tungsten disulfide quantum dots (WS₂ QDs) on the surface was more positive, indicating that its hydrogen evolution activity was higher. Microdynamic model analysis shows that the average standard rate constant of the rate-determining step of the hydrogen evolution reaction of gold nanoelectrodes modified with WS_{2 …}

Rational Catalyst Synthesis For Sustainable Energy Applications, Alaba Upe Ojo

Theses and Dissertations

Energy accounts for two-thirds of the global climate challenges. Effective utilization of green hydrogen or finding cleaner ways to improve energy generation is necessary to combat climate crisis and allow for a more sustainable future. This work evaluates three heterogeneous catalytic processes which contribute to a sustainable future. In chapter 2, we studied the hydrogenation of toluene to methylcyclohexane; a reaction that can potentially serve as a medium for hydrogen storage and help to overcome the safety challenges of transporting gaseous hydrogen. We found that palladium catalysts on certain carbons exhibited significantly enhanced toluene hydrogenation rates compared to activated carbons …

Engineering Electronic Properties Of Random Alloys For Catalytic Applications, Andrew N. Okafor

LSU Doctoral Dissertations

Engineering catalytic materials is a key endeavor in the catalysis science to improve the catalytic activity of existing catalysts for specific applications and reduce the dependence on rare metals and minerals. While alloying, or mixing of metals, has been extensively studied, the focus has conventionally been placed on intermetallic phases or nanostructures such as core-shell particles, which are conceptually described by simple lattice models. This research focuses on understanding the catalytic properties of structurally ordered but compositionally disordered (or random) alloys, which have remained under-explored due to complexity at the atomic scale. Existing research focuses on synthesizing multicomponent alloys and …

Advances In Electrocatalytic Dehydrogenation Of Ethylamine To Acetonitrile, Yanlin Zhu, Dezhen Wu, Jinyao Tang, Dakota Braaten, Bin Liu, Zhenmeng Peng

Faculty Publications

The electrocatalytic dehydrogenation of ethylamine (EDH), owing to its high hydrogen content, holds broad prospects in electrochemical hydrogen (H2) production, H2 storage, and addressing energy issues, thus deserving wide attention. In this feature article, we first summarized the fundamentals of thermocatalytic and electrocatalytic EDH and reviewed the recent state-of-the-art advances in catalyst research, specifically platinum group metal (PGM) catalysts and non-PGM catalysts. We systematically discussed the potential applications of electrocatalytic EDH in energy storage and conversion. Finally, we provide our perspective on the key challenges and future developments in this field. We believe this feature article will offer helpful guidance …

Recent Progress And Perspectives Of Liquid Organic Hydrogen Carrier Electrochemistry For Energy Applications, Jinyao Tang, Rongxuan Xie, Parsa Pishva, Xiaochen Shen, Yanlin Zhu, Zhenmeng Peng

Faculty Publications

Amidst the global pursuit of clean and sustainable energy, the transition towards a hydrogen economy holds immense promise, yet is encumbered by significant storage challenges. Liquid organic hydrogen carrier (LOHC) electrochemistry emerges as a promising solution to enable efficient and sustainable hydrogen storage, meanwhile broadening the horizons of LOHCs for use as clean, renewable, and intense energy carriers to store and generate electricity. In this perspective, we embark on a review of recent trends and progress in LOHC redox electrochemistry, properties, and applications. We categorize electrochemically active, regenerable LOHCs into alcohols, amines, aromatic compounds, aminoxyl species, and others, based on …

Electrochemical Advanced Treatment Of Desulfurization Wastewater From Coal-Fired Power Plants, Ju-Cai Wei, Juan Yi, Xu Wu

Journal of Electrochemistry

Zero-emission of desulfurization wastewater is one of the main demands for coal-fired power plants. As typical high salinity wastewater, it is hard to purify the desulfurization wastewater from coal-fired power plants through traditional physicochemical treatment or biochemical treatment, e.g., COD and Cl^–. A high concentration of Cl^– ion in desulfurization wastewater restricts wastewater reuse and zero-emission. Electrochemical technology is an attractive method for high salinity wastewater zero-emission, which provides a versatile, efficient, cost-effective, easily automatable, and clean industrial process. For advanced treatment of effluent after triple box process treatment in power plants, this paper reports an electrochemical …

Strain-Dependent Activity-Stability Relations In Ruo2 And Iro2 Oxygen Evolution Catalysts, Payal Chaudhary, Alexandra Zagalskaya, Herbert Over, Vitaly Alexandrov

Department of Chemical and Biomolecular Engineering: Faculty Publications

Strain engineering is an effective strategy in modulating activity of electrocatalysts, but the effect of strain on electrochemical stability of catalysts remains poorly understood. In this work, we combine ab initio thermodynamics and molecular dynamics simulations to examine the role of compressive and tensile strain in the interplay between activity and stability of metal oxides considering RuO₂ and IrO₂ as exemplary catalysts. We reveal that although compressive strain leads to improved activity via the adsorbate-evolving mechanism of the oxygen evolution reaction, even small strains should substantially destabilize these catalysts promoting dissolution of transition metals. In contrast, our results …

Grain Boundary Engineering: An Emerging Pathway Toward Efficient Electrocatalysis, Xiaomin Xu, Yijun Zhong, Magdalena Wajrak, Tejas Bhatelia, San Ping Jiang, Zongping Shao

Research outputs 2022 to 2026

Electrochemical transformation processes involving carbon, hydrogen, oxygen, nitrogen, and small-molecule chemistries represent a promising means to store renewable energy sources in the form of chemical energy. However, their widespread deployment is hindered by a lack of efficient, selective, durable, and affordable electrocatalysts. Recently, grain boundary (GB) engineering as one category of defect engineering, has emerged as a viable and powerful pathway to achieve improved electrocatalytic performances. This review presents a timely and comprehensive overview of recent advances in GB engineering for efficient electrocatalysis. The beneficial effects of introducing GBs into electrocatalysts are discussed, followed by an overview of the synthesis …

From Waste To Energy: The Electrochemical Reduction Of Co2 Using Recycled Nanostructured Catalysts, Ibrahim Badawy

Theses and Dissertations

The reduction of carbon dioxide (CO₂RR) using electrochemistry is a promising solution for the burgeoning global energy crisis. The overall vision of its implementation relies on renewable energy sources to power the reaction creating carbon neutral products and effectively closing the carbon cycle. Research in this field has come a long way since its inception in the mid-1900s. However, there remain significant hurdles and important considerations to overcome in order to reach full commercialization. Most electrocatalysts tested for CO₂RR have been designed solely for maximum performance while ignoring the environmental consequences if such a material were …

Cu/Bnx Catalysts For Electrocatalytic Reduction Of Nitrogen And Nitrate Waste, Siming Huo

Dissertations

Ammonia (NH₃) is one of the most important chemicals to the whole human society. The invention of the Haber-Bosch process enabled the industrial production of NH₃. However, owing to the high capital costs of the centralized plant and the equipment and the negative environmental impact, it is no longer suitable for today's needs of human development. As a result, there is an urgent need to investigate sustainable approaches for ammonia production. Among those reported studies, nitrogen reduction (NRR) and nitrate reduction reaction (NO₃RR) are considered applicable in the future. However, after decades of studying …

Anodic Electrocatalysis Of Glycerol Oxidation For Hybrid Alkali/Acid Electrolytic Hydrogen Generation, Xin Feng, Bo-Wen Liu, Ke-Xin Guo, Lin-Feng Fan, Gen-Xiang Wang, Su-Qin Ci, Zhen-Hai Wen

Journal of Electrochemistry

Electrolytic hydrogen production is heavily restricted by high-energy consumption majorly due to the relatively high potential of anodic oxygen evolution reaction (OER). Development of OER-alternative reaction at the anode has been recently proposed as a promising pathway to address the associated issues. In this work, we report a hybrid acid/alkali dual-electrolyte electrolyzer by coupling acidic hydrogen evolution reaction (HER) using commercial Pt/C cathode with alkaline Electrocatalytic glycerol oxidation (GOR) which is implemented by developing a nickel foam (NF) supporting Co₃O₄ nanosheets anode that shows low overpotential and high selectivity toward GOR for formate production. The hybrid acid/alkali …

Electrochemical Oxidation Of Ethylene On Palladium Electrode, Wei-Xing Wu, Ying Wang

Journal of Electrochemistry

The electrochemical oxidation of C₂H₄ is attracting increasing attention due to its vast potential market. The current electrochemical methods rely on the use of redox mediators, which may produce corrosive intermediates, while direct oxidation is still limited by its low activity and selectivity. Herein, we conducted electrochemical studies to obtain mechanistic insights into the benchmark Pd catalyst. The generated Pd(II) could be the active site for C₂H₄ oxidation. By designing the pulse sequence, we found the ratio of strongly and weakly adsorbed C₂H₄ on Pd to be 0.3:1. The result we …

A Self-Supported Ru-Cu3P Catalyst Toward Alkaline Hydrogen Evolution, Zi-Xuan Wan, Chao-Hui Wang, Xiong-Wu Kang

Journal of Electrochemistry

Transition metal phosphide (TMP) is a kind of effective catalysts toward hydrogen evolution reaction (HER) in alkaline electrolytes. However, the performance of TMP catalysts is strongly limited by water splitting. In this work, we developed a method to prepare a copper foam (CF) supported Ru-doped Cu₃P catalyst (Ru-Cu₃P/CF) by a consecutive growth of Cu(OH)₂ nanoarrays, soaking in RuCl₃ solution and phosphorization. A large surface area was obtained by the self-supported catalysts with the appropriative Ru doping. As an excellent HER catalyst, it exhibited a low overpotential of 95.6 mV at a current density of …

Perovskite-Type Water Oxidation Electrocatalysts, Xiao Liang, Ke-Xin Zhang, Yu-Cheng Shen, Ke Sun, Lei Shi, Hui Chen, Ke-Yan Zheng, Xiao-Xin Zou

Journal of Electrochemistry

The development of energy conversion/storage technologies can achieve the reliable and stable renewable energy supply, and bring us a sustainable future. As the core half-reaction of many energy-related systems, water oxidation is the bottleneck due to its sluggish kinetics of the four-concerted proton-electron transfer (CPET) process. This necessitates the exploitation of low cost, highly active and stable water oxidation electrocatalysts. Perovskite-type oxides possess diverse crystal structures, flexible compositions and unique electronic properties, enabling them ideal material platform for the optimization of catalytic performance. In this review, we provide a comprehensive summary for the crystal structures, electronic structures and synthetic methods …

Designing The Electrode Geometry And Electrolyte To Enhance The Product Selectivity And Activity In Carbon Dioxide Electroreduction, Samaneh Sharifi Golru

Dissertations, Theses, and Capstone Projects

Excessive utilization of the fossil fuels due to the rapid growth of the global population has resulted in a dramatic increase in the carbon dioxide (CO₂) level in the atmosphere which is the main reason for global warming and climate change. Therefore, green technologies are in high demand to develop carbon-neutral energy cycles. In this regard, CO₂ electroreduction (CO2ER) has been proposed as a promising approach for CO₂ utilization. CO2ER can mitigate the CO₂ level in the atmosphere as well as produce value-added chemicals and fuels at ambient conditions. Despite the benefits of CO_{2 …}

Preparation And Properties Of Gcp-Supported Palladium Particles Composite Towards Electrochemical Ammonia Synthesis, Ying-Chao Wang, Zi-Zai Ma, Yi-Fan Wu, Xiao-Guang Wang

Journal of Electrochemistry

Ammonia (NH₃) plays an essential role in agriculture and modern industries. Electrochemical fixation of nitrogen (N₂) to ammonia (NRR) under ambient conditions with renewable electricity is a promising strategy to replace the industrial Haber-Bosch method. However, it usually suffers from extremely poor ammonia yield and low Faraday efficiency due to the poor electrocatalysts. Therefore, intensive studies have been devoted to developing efficient NRR catalysts till now. Among them, palladium (Pd) can capture protons in the aqueous phase to form stable α-PdH, which balances the competitive adsorption between nitrogen and protons as well as reduces the …

Structural, Charge Transport, Gas Sensing, Magnetic, Pseudocapacitive, And Electrocatalytic Properties Of Perovskite Oxides., Surendra Bahadur Karki

Electronic Theses and Dissertations

Perovskites are functional materials with the general formula ABO₃ (A = alkali, alkaline earth or lanthanoid cations and B = transition metal or main group cations). These materials are marked by a variety of crystal structures and interesting properties such as colossal magnetoresistance, ferroelectricity, multiferroicity, superconductivity, pseudocapacitance, gas sensing, charge transport, and electrocatalytic properties. The formula of perovskite can be written as AA’BB’O₆, when there is ordering between two cations over A and B-sites. Such compounds are called double perovskite oxides. Some amount of oxygen could be lost from crystal structure without decomposition of the phase. Such …

Advances Of Phosphide Promoter Assisted Pt Based Catalyst For Electrooxidation Of Methanol, Meng Li, Li-Gang Feng

Journal of Electrochemistry

Transition metal phosphide (TMP), as an ideal catalytic promoter in methanol fuel oxidation, has received increased attention because of its multifunctional active sites, tunable structure and composition, as well as unique physical and chemical properties and efficient multi-composition synergistic effect. Some advances have been made for this catalyst system recently. In the current review, the research progresses of transition metal phosphides (TMPs) in the assisted electrooxidation of methanol including the catalysts fabrication and their performance evaluation for methanol oxidation are reviewed. The promotion effect of TMPs has been firstly presented and the catalyst systems based on the different metal centers …

Synthesis And Electrochemical Study Of Cuau Nanodendrites For Co2 Reduction, Dylan Siltamaki, Shuai Chen, Farnood Rahmati, Jacek Lipkowski, Ai-Cheng Chen

Journal of Electrochemistry

The conversion of carbon dioxide (CO₂) to carbon monoxide (CO) and other value-added products is an interesting approach for carbon-containing fuel synthesis using renewable and clean energy. The electrochemical reduction of CO₂ is one of the promising strategies for the storage of intermittent renewable energy resources. The development of electrocatalysts with high activity and stability is vital in the electrochemical CO₂ reduction process. In this study, copper and gold alloyed (CuAu) electrodes with nanodendritic structures were synthesized using a facile electrodeposition method. The CuAu nanodendrites with the atomic ratio of Cu to Au being approximately 1:1 …

Preparation Of Co1-XS-Mns@Cnts/Cnfs For Electrocatalytic Oxygen Reduction Reaction, Fang-Yan Liu, Qian Zhang, Yue-Kun Li, Feng Huang, Meng-Ye Wang

Journal of Electrochemistry

As an important cathode reaction in fuel cells and metal-air batteries, oxygen reduction reaction (ORR) is a complex reaction of slow kinetics, which severely limits performances of fuel cells and metal-air batteries. Therefore, it is of key importance to find an efficient and stable electrocatalyst to promote ORR. Carbon-based materials, which possess high conductivity, good stability and large specific surface area, are usually used in electrocatalytic ORR. However, pure carbon-based materials exhibit low efficiency. Coupling carbon-based materials with manganese (Mn) and cobalt (Co) transition metals containing 3d orbitals is an effective way to improve electrocatalytic performance. Herein, carbon nanofibers containing …

Application Of Atomically Precise Metal Nanoclusters In Electrocatalysis, Zhi-Hua Zhuang, Wei Chen

Journal of Electrochemistry

Metal nanoclusters (M NCs) consist of only several to a few hundred of metal atoms and possess core sizes less than 2 nm. Owing to the quantum size effect, the electronic states of M NCs evolve to discrete levels similar to the molecule energy gaps, other than a continuous density of states to produce plasmon characteristic of bulk metal nanoparticles (M NPs). In comparison with the conventional M NPs, M NCs exhibit dramatically unique electronic and optical properties, such as molecule-like energy gaps, strong photoluminescence and high catalytic properties, which make them promising for potential application in numerous fields, such …