Catalysis and Reaction Engineering Commons^™

Modulating Electronic Structure With Linearly Fused Pyrazine Units For High-Voltage And Stable Zinc-Organic Batteries Cathode, Min-Jian Zhao, Li-Bin Zhang, Jin-Tao Wang, Kun Ding, Hai-Mei Liu, Yong-Gang Wang

Journal of Electrochemistry

High-voltage n-type organic cathode materials are critical for constructing zinc-organic batteries (ZOBs) with high energy density and long cycle life. However, the intrinsically unfavorable electronic structures and relatively high LUMO energy levels of most n-type materials often lead to sluggish kinetics, high solubility, and suboptimal discharge voltages (< 0.8 V). Here, we design a small molecule, quinoxalino[2’,3’:5,6]pyrazino[2,3-f][1,10]phenanthroline (DPQP), as a ZOB cathode by introducing locally electron-deficient motifs into the conjugated backbone of aromatic compounds. The linearly fused pyrazine units extending the pyrazine–benzene framework effectively optimize the electronic structure, thereby significantly enhancing the discharge voltage. Meanwhile, the expanded π-conjugated plane suppresses dissolution and accelerates charge-transfer kinetics. Benefiting from these features, the DPQP electrode exhibits an exceptional increase in average operating voltage from 0.61 V to 1.07 V (vs. Zn²⁺/Zn) at 0.1 A·g^–1, with an overpotential of only 140 mV. Notably, no discernible voltage decay occurs as the current density increases, indicating rapid and highly reversible redox kinetics. Furthermore, the DPQP cathode delivers outstanding cycling stability, maintaining over 2000 h of continuous operation at 0.1 A·g^{–1 …}

(Co,Ni,Mn,Cu,Zn)O High-Entropy Oxide Nanotubes As Efficient Bifunctional Electrocatalyst For Oxygen Evolution And Hydrazine Oxidation Reactions, Pan-Yan Chen, Wan-Wan Wu, Heng Bian, Wei-Wei Li, Xin-Sheng Zhao, Lu Wei

Journal of Electrochemistry

High-entropy oxides (HEOs) present significant scientific challenges in both design and synthesis due to their multielement and high-entropy nature, which involves complex combinations of multiple metal cations and oxygen anions, typically arranged in equimolar ratios to achieve structural stability. Herein, one-dimensional (Co,Ni,Mn,Cu,Zn)O high-entropy oxide nanotubes (HEO-NTs) are fabricated by means of a gradient electrospinning strategy with a tailored polyvinyl alcohol (PVA) molecular weight distribution and controlled pyrolysis. Benefiting from the HEO features and the synergistic effect of multicomponent sites, the as-synthesized (Co,Ni,Mn,Cu,Zn)O HEO-NTs exhibit exceptional bifunctional electrocatalytic activity for the oxygen evolution and hydrazine oxidation reactions (OER/HzOR). This study offers …

Zirconium Metal-Organic Cages: Synthetic Development Of Chromium-Functionalized Ligands, Jim P. Heller, Jonathan E. Pines, Miguel I. Gonzalez

Wetterhahn Science Symposium Posters

Metal-organic cages (MOCs) are a class of highly porous molecules composed of inorganic clusters bridged by highly tunable organic ligands. The synthesis and development of various ligands could allow for more selective and efficient catalysts. Specifically, Chromium-based homogeneous catalysts have recently been commercialized due to their high selectivity in the production of 1-hexene and 1-octene. This project aims to synthesize reusable heterogeneous catalysts composed of chromium-functionalized zirconium MOCs deposited on mesoporous supports.

The current focus of this project is to synthesize and purify the "SNS Ligand." This ligand can coordinate to chromium via its S—N—S moiety. This project specifically focuses …

Techno-Economic Assessment And Life Cycle Analysis Of Electrocatalytic Reduction Of Co2 To Ethanol., Omotolani Elizabeth Oduyebo

LSU Master's Theses

This study presents a techno-economic analysis (TEA) and life cycle assessment (LCA) of the electrocatalytic reduction of CO₂ to ethanol, a multi-carbon (C₂) product with significant market value. Prior TEA studies have relied on simplified lump-sum separation cost estimates, and prior LCA studies have rarely examined the combined effect of CO₂ source and electricity supply on carbon intensity gaps that this work addresses through process-simulation-grounded analysis. An Aspen Plus process simulation was developed for an anion-exchange membrane (AEM) electrolyzer system coupled with an extractive distillation separation train using ethylene glycol as the entrainer, achieving 99.9 wt.% ethanol purity …

Synthesis And Investigation Of Tungsten–Copper Oxide Composites For Enhanced Photocatalytic Applications, Janak Paudel, John Nichols

Research and Creative Works Expo

No abstract provided.

Impact Of Biomass Type On Hydrocarbon Yield And Chain Length Distribution Produced Via Fischer-Tropsch Synthesis, Nicholas R. Hawe

Honors Scholar Theses

This paper investigates the relationship between biomass composition and hydrocarbon yield as well as chain length distribution produced by Fischer-Tropsch synthesis. Through an Aspen Plus model, the conversion of three different biomasses – digestate, sawdust, and corn stover – into hydrocarbon fuel was simulated. The model converts biomass into gaseous and liquid hydrocarbons via various unit operations and reactions. Simulation results highlight the product distribution and hydrocarbon output, allowing for an analysis of hydrocarbon yield and comparison of chain length distributions amongst the three biomasses. Overall, the simulation showed biomass composition had no significant impact on hydrocarbon yield or chain …

Development Of A Metal-Based Catalyst For The Ammonia Dehydrogenation Reaction, Othman Mohammed Abdullah Al-Amodi

Thesis/ Dissertation Defenses

Developing cost-effective and active catalysts that would replace noble metals is desirable for the ammonia decomposition reaction. Hence, this thesis focuses on the development and evaluation of a 10Ni/0.75TiO2-0.25CeO2 catalyst for ammonia decomposition, a promising route to carbon-free hydrogen production. The system parameters investigated include the effect of reaction temperature (550, 650, and 750°C) and the catalyst mass (100, 200, and 300 mg) on the performance of the ammonia decomposition process. The primary objective of this work is to investigate how catalyst composition and metal-support interactions influence activity, hydrogen production, and ammonia conversion. Catalysts were prepared by the incipient wetness …

Optimization Of Renewable Energy-Based Alkaline Electrolysis Systems For Sustainable Hydrogen Production, Shokhrukhbek Kozimjon Ugli Bakhramov

Chemical Technology, Control and Management

This paper presents a comprehensive optimization study of hydrogen production systems through alkaline water electrolysis powered by photovoltaic energy sources, with a specific focus on Central Asian applications. The research systematically investigates critical operating parameters including KOH electrolyte concentration (25-30 wt%), temperature effects (25-80°C), current density optimization (100-500 mA/cm²), and electrode material performance using cost-effective 316L stainless steel. Experimental results demonstrate that optimized systems achieve solar-to-hydrogen efficiency of 13-15%, with hydrogen production costs ranging from $2-8/kg depending on system scale. The study reveals that maximum performance occurs at 30 wt% KOH concentration, 60-80°C operating temperature, and 200-400 mA/cm² current density. …

Molecular Catalysts For Electrochemical Nitrogen Activation Toward Sustainable Ammonia Synthesis, Jin-Xiu Han, Hao Xue, Xian-Biao Fu

Journal of Electrochemistry

Homogeneous electrocatalytic nitrogen reduction reaction (NRR) provides a powerful framework to interrogate molecular nitrogen-fixation pathways under mild conditions. By tuning the metal center, ligand architecture, and reaction medium, these systems enable capturing key intermediates and delivering mechanistic insight at the molecular-level resolution. Nevertheless, advances remain constrained by highly reduced operating potentials, intense competition from the hydrogen evolution reaction (HER), limited durability in turnover, and inadequate long-term stability.

In this review, we take electron delivery to the molecular active site as the guiding principle for organizing homogeneous electrochemical N₂ activation and transformation. We classify reported systems into direct electron transfer …

Water-Driven Solid Electrolyte Interphase Governs Continuous-Flow Ammonia Electrosynthesis, Peng-Bo Liu, Sheng-Liang Zhai, Ji Huang, Zhong-Shuo Zhang, Jie Zeng, Shao-Feng Li

Journal of Electrochemistry

Flow-cell architectures have emerged as a powerful platform for continuous and stable lithium-mediated nitrogen reduction (Li-NRR), enabling ambient-condition electrochemical ammonia synthesis and offering a promising alternative to Haber-Bosch processes. However, Li-NRR is exceptionally sensitive to trace water, and even minor variations in water content can profoundly alter interfacial chemistry. Here, we systematically investigate how initial water concentration affects Li-NRR performance in a continuous-flow cell. Excess water drives the formation of a thick solid electrolyte interphase (SEI) layer, which may impede nitrogen access to metallic lithium and hinder lithium-ion transport. As a result, the ammonia Faradaic efficiency collapses from ~61% to …

Insertion Of Noble Metal Free Cathodic Catalyst Layer With Fe-N-C Catalyst For Boosted Performance Of Pemfc, Shi Zhou, Muhammad Tariq, Asif Nadeem Tabish, Muhammad Salman, Fan-Di Ning, Muhammad Rayyan Tayyab, Ran-Ran Peng, Meng-Geng Hao, Wen-Mu Li, Xiao-Chun Zhou

Journal of Electrochemistry

Economical Fe-N-C catalysts are considered as promising alternatives to platinum group metal catalysts for proton exchange membrane fuel cells (PEMFCs). Despite exhibiting robust activity on rotating disk electrodes, their performance within membrane electrode assemblies often experiences limitations, such as decreased O₂ diffusion, high H₂O₂ formation, low proton conduction, and a lower electron transfer number. In this study, key factors, including proton transport, electron conduction, and gas diffusion within air-breathing PEMFCs, have been investigated by adjusting cathode catalyst layer (CCL) compositions. From the experimental results, the optimal peak power density was obtained when the loading of Fe-N-C …

Understanding The Binding Of Nickel(Ii) Bromide To A Zirconium Metal-Organic Cage For Heterogeneous Catalysis, Luci Green

Caroliniana Undergraduate Research Journal

Heterogeneous catalysts offer inherent advantages in improving the sustainability of industrial chemical processes. Their high ease of separation and recyclability has the potential to reduce the cost, waste, and energy consumption of processes that currently rely on homogeneous catalysts. Metal–organic cages (MOCs) are an attractive material for heterogeneous catalysis due to their discrete and highly tunable structures, which can be functionalized by binding these complexes with catalytically active metals. The specific objective of this study is to provide preliminary insight into the binding of nickel(II) bromide (NiBr₂) to zirconium MOCs, which was done by studying the binding of …

Axial Sulfur-Coordination Engineering Boosting Fe–N–C Catalysts For High-Performance Proton Exchange Membrane Fuel Cells, Lin Lin, Xiu-Xuan Hou, Zhe-Chen Fan, Yi-Xuan Yin, Wei-Yi Zhao, Kai Wei, Yu-Die Zhou, Li-Na Hou, Ying Wang, Hao Wan, Jun-Jie Ge

Journal of Electrochemistry

Fe-N-C catalysts have long suffered from kinetically sluggish oxygen reduction reaction (ORR) due to excessive adsorption strength toward oxygen intermediates and low site utilization. Heteroatom doping effectively accelerates ORR reaction kinetics through electronic structure modulation of metal sites for optimal intermediate adsorption, while chemical vapor deposition (CVD) enhances the turnover frequency (TOF) of active sites. Herein, we developed an FeSNC catalyst featuring abundant FeS₁N₄ sites via a dual-precursor CVD strategy. Experimental and theoretical analyses revealed that S incorporation disrupts the symmetric coordination of active sites, which optimizes OH* adsorption energies from 0.212 eV to 1.194 eV. Moreover, …

Entropy Of Metal/Solution Interfaces: Thermodynamic Framework, Theoretical Models, And Roles Of Interfacial Water, Zeng-Ming Zhang, Zi-Xi Liang, Jun Huang

Journal of Electrochemistry

Entropy is a basic thermodynamic property of the electrical double layer (EDL) at metal/solution interfaces, yet, its definition, measurement, and theoretical treatment are dispersed in the literature, and, in some cases, ambiguous. In this paper, we revisit the thermodynamic theory of EDL, from which two variants of entropy, excess entropy and formation entropy, are obtained and compared. In terms of the formation entropy, two calculation routes are validated in the context of a primitive EDL model, namely, the Gouy-Chapman (GC) model. After clarifying the concepts and calculation routes, we investigate interfacial water effects on the EDL entropy, using a refined …

Kinetic Investigation Of The Sn2 Reaction Between Piperidine And Chloroacetic Acid Using Atr-Ftir Spectroscopy, Sadoqat O. Mamatkulova, Oytura S. Maksumova

CHEMISTRY AND CHEMICAL ENGINEERING

In this study, the kinetic characteristics of the nucleophilic substitution (SN2) reaction between piperidine and chloroacetic acid were investigated in real time at 50, 60, and 70 °C using ATR-FTIR spectroscopy. The spectral analysis revealed a gradual decrease in the C–Cl stretching vibration in the 710–730 cm⁻¹ region and a simultaneous increase in absorption bands corresponding to the C–N bond in the 1020–1250 cm⁻¹ region, confirming the consistent progression of the reaction. Analysis of the conversion function X(t) showed values of X = 0.669 at 50 °C, X = 0.826 at 60 °C, and X = 0.970 at 70 °C, …

Development Of A Catalytic System Based On N,N’,N”-Tris-(Β-Oxyethyl)Hexahydro-S-Triazine For Polyisocyanuraturethane Foam, Murod K. Karimov, Nozima M. Alimukhamedova, Lochinbek M. Khurramov, Ravshan I. Adilov, Murafar G. Alimukhamedov

CHEMISTRY AND CHEMICAL ENGINEERING

The aim of this work is to develop a catalytic system for the production of polyisocyanurateurethane foams based on N,N',N"-tris(β-hydroxyethyl)hexahydro-S-triazine (TOEGT). N,N',N"-tris(β-hydroxyethyl)hexahydro-S-triazine (TOEGT) exhibits high catalytic activity in polyurethane foam production processes. However, it exhibited moderate catalytic activity in polyisocyanurateurethane  foams, the formation of which is characterized by the sequential-parallel reactions of urethane formation, isocyanate trimerization, and foaming (isocyanate + water). By varying the composition of the catalytic mixture, the required concentrations of each component were determined, which made it possible to synthesize polyisocyanurateurethane foams that meet the requirements of casting polyurethane foams. The optimal ratio of N,N',N"-tris(β-hydroxyethyl)hexahydro-S-triazine: triethylenediamine: tin …

Current Research Progress On Electrode Materials For All-Vanadium Redox Flow Batteries, Wen-Qi Wang, Jie Jin, Li-Min Wang, Xin-Yue Liu, Tao Cheng, Yong Hou, Han Xue, Zhi-Yu Wang, Bo Liu, Jia-Bao Liu, Xu-Bin Lu

Journal of Electrochemistry

The redox active species in all-vanadium redox flow batteries (VRFBs) reside in the electrolyte, while the heterogeneous reactions occur on the electrode surface; the electrode is therefore the decisive platform for dynamic adsorption, electron transfer, and ion conversion, especially for the VO²⁺/VO₂⁺ and V²⁺/V³⁺ couples. One of the major challenges for VRFBs is the slow charge transfer in VO²⁺/VO₂⁺ and V²⁺/V³⁺ reactions, mainly caused by poor catalytic performance of electrodes and weak adhesion of catalysts to electrodes. This review focuses on the key challenges and recent …

An Electrochemiluminescence-Based Arsenic (Iii) Sensor Using Luminol On Screen-Printed Gold Electrodes, Harmesa Harmesa, Isnaini Rahmawati, Andrea Fiorani, Yasuaki Einaga, Eny Kusrini, A’An Johan Wahyudi, Asep Saefumillah, Tribidasari A Ivandini

Journal of Electrochemistry

Electrochemiluminescence (ECL) of luminol has been studied on a screen-printed gold electrode for a simple and sensitive detection of arsenic ions (As(III)). Cyclic voltammetry (CV) was applied as the proposed technique to study luminol’s electrochemical behavior and to evaluate the arsenic’s effect in the ECL system, while hydrogen peroxide (H₂O₂) served as a co-reactant to enhance luminol’s light emission under alkaline conditions. To achieve optimal electrode performance, key parameters including pH, scan rate, and the concentrations of H₂O₂ and luminol were carefully optimized. The presence of As(III) induced a quenching effect on the …

Control Of Pore Nucleation And Rearrangement Kinetics During Aluminium Anodizing In Phosphoric Acid Electrolyte, Ilya V. Roslyakov, Nikita A. Shirin, Dmitry M. Tsymbarenko, Sergei N. Pavlov, Sergey E. Kushnir, Nikolay V. Lyskov, Kirill S. Napolskii

Journal of Electrochemistry

Anodic aluminium oxide (AAO) porous films with an interpore distance of several hundred nanometers are of great interest due to their unique interaction with visible and near-infrared light, and high thermal stability up to 1500 °C. These porous films are prepared by aluminium anodizing at high voltages in weak acids, leading to a slow kinetics of initial stages of porous structure formation. Here, we propose an approach to accelerate AAO formation in electrolytes based on weak acids such as phosphoric acid. Aluminium foils, pre-patterned using first anodizing under different conditions and subsequent selective dissolution of a sacrificial AAO layer, were …

Triphenylmethane-Derived Levelers For High-Speed Redistribution Layer Copper Electroplating Of Tailored Surface Morphologies, Zi-Hao Song, Wei-Bin Wang, Xiao-Hui Liu, Xiao-Min Han, Yi Zhou, Rui Huang, Yan-Xia Jiang, Zhe Li, Xiao-Wei Liu, Mei-Ling Xiao, Hong-Gang Liao, Wei-Lin Xu, Rong Sun

Journal of Electrochemistry

Redistribution Layer (RDL), composed of layered dielectrics and electroplated copper materials, is a basic structure to rearrange numerous I/O pads on the chip surface in wafer-level advanced packaging. As the key chemicals in electrolyte baths, electroplating additives have undergone continuous development to meet the industrial needs for high-speed and fine-line/fine-pitch applications. Meanwhile, the intricate relationships between additive chemical structures and electroplated copper properties are yet to be well understood. In this work, a pair of triphenylmethane-based dye molecules, i.e., gentian violet (GV) and methyl green (MG), was comparatively investigated as levelers for high-speed RDL copper electroplating. Compared to GV, significantly …