Physical Chemistry Commons^™

Metal Oxide Semiconductor Gas Sensors For Exhaled Breath Cancer Biomarker Detection, Guang-Lan Chen, Hui-Hui Luo, Wen-Wen Peng, Shi-Yu Xu, Yu-Ting Li, Hui-Jie Ke, Si-Hui Zhong, Jia-Ao Wei, Tong Chen, Xiao-Kun Li, You-Lin Zhang, Wei Chen

Journal of Electrochemistry

Early cancer screening can significantly improve therapeutic outcomes, volatile organic compounds (VOCs) and other related gases in exhaled breath, as cancer-specific biomarkers, offer a novel approach for non-invasive diagnosis. Metal oxide semiconductor (MOS)-based gas sensors are pivotal for exhaled breath VOCs detection, featuring compact size, cost-effectiveness, and rapid response. This review summarizes the most recent five-year research advances in cancer biomarker detection, and clarifies the core mechanisms of electrical property changes from sensing material-VOCs interactions and key performance metrics including sensitivity, selectivity, humidity tolerance, response/recovery time, stability, and operating temperature. This review also highlights the optimization strategies of sensing materials …

Electrocatalytic Oxidation Of Ethylene Glycol To Glycolic Acid: From Mechanism And Catalyst Design To Emerging Neutral Electrolyte Systems, Man Zhang, Xue Li, Xin-Yu Peng, Lin Wang, Wen-Wen Chen, Yao-Yue Yang

Journal of Electrochemistry

Polyethylene terephthalate (PET) waste represents both an environmental burden and a loss of carbon resources. Alkaline depolymerization of PET yields terephthalic acid and ethylene glycol (EG). Electrocatalytic oxidation of EG to glycolic acid (GA), the monomer of biodegradable polyglycolic acid (PGA), offers a sustainable route driven by renewable electricity. However, the ethylene glycol oxidation reaction (EGOR) involves competing pathways toward C2 products (GA and oxalic acid) and C1 products (formic acid and CO₂), making selective GA production a central challenge. This review provides a comprehensive overview of recent progress in selective EG-to-GA electrooxidation from catalyst design, mechanistic understanding, …

Regularization-Based Crystallite Size Distribution Analysis Of Pt/C Catalysts From X-Ray Diffraction, Cheng-Long Ma, Wei-Yu Shi, Zhong-Jun Hou

Journal of Electrochemistry

Accurate determination of the platinum crystallite size distribution in carbon-supported platinum (Pt/C) catalysts is critical for evaluating both the initial performance and long-term durability of proton exchange membrane fuel cells (PEMFCs). Conventional characterization approaches—including transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and the Scherrer equation—are limited by restricted statistical sampling, sensitivity to support interference, or the inability to resolve the full breadth of the size distribution. In this work, we present a regularization-based inversion framework that extracts the volume-weighted crystallite size distribution directly from X-ray diffraction (XRD) line profiles, without requiring any a priori assumption regarding the functional form …

Synthesis And Charge Transport Characterization Of 9,9'-Bifluorenylidene-Based Conjugated Molecules For Single-Molecule Conductance, Zach Moughamian, Jahnavi Badiganti, Jinjia Xu

Undergraduate Research Symposium

Molecular electronics explores the use of individual molecules as functional components in nanoscale electronic devices. In this project, fluorenone-based π-conjugated molecules including 9,9'-bifluorenylidene-S and triphenylamine-substituted derivatives were synthesized to investigate structure-property relationships relevant to molecular charge transport. The synthesized compounds were obtained in 13% and 27% yield respectively. ¹H NMR spectroscopy confirms characteristic aromatic resonances in the 7-9 ppm region consistent with the conjugated framework. UV–Vis spectroscopy reveals absorption maxima at 459 nm and 470 nm, indicating extended π-conjugation and donor-acceptor effects. Single-crystal X-ray diffraction confirms the structure of 9,9'-bifluorenylidene-S, which crystallizes in the monoclinic system (space group P2₁/c). In …

Characterization Of Combined Adsorption Using Fermi Levels, Molecular Dynamics, And Monte Carlo Simulations To Prevent Cu–Zn (111) Alloy Corrosion, Mushtaq Jerri Meften, Ammar Abdul Jabbar Kadhim, Mohammed Shafeeq Abed

Makara Journal of Science

Experimentally developing corrosion inhibitors requires a significant amount of money and time. In silico advancement empowers selecting inhibitor molecules based on their properties derived from theoretical studies, thereby reducing costs. Our main approaches include theoretical studies such as Fermi levels, electrostatic potential surface (EPS), Fukui indices, molecular dynamics stimulations, and Monte Carlo as indispensable tools to investigate the adsorption mechanisms of molecules 6-((5-(((3S,5R)-2-oxo-5-((2-(pyrazin-2-yloxy) thiazol-5-yl) thio) tetrahydro-2H-thiopyran-3-yl) oxy)isothia-zol-3-yl)thio) nicotinic acid (PTT), and (S)-2-((5-((6-((3-(2-thioxoethoxy)-1,2,4-thiadiazol-5-yl)thio)-1,6-dihydropyra-zin-2-yl)oxy)-1,3,4-thiadiazol-2-yl) thio) acetaldehyde (TTD) on the Cu/Zn (111) alloy. We electronically characterized PTT and TTD, which were proven effective inhibitors. Notably, all results suggested that the two exhibited high …

Dense Platinum Nanoparticles Confined In Mn-N-C Nanocages For Robust Heavy-Duty Pemfcs, Lei Zhao, Zhen-Min Cao, Jia-Yu Zuo, Ming-Liang Yang, Hong-Yan Qiao, Jun-Song Chen, Rui Wu

Journal of Electrochemistry

High-loading Pt cathodes are essential for heavy-duty proton exchange membrane fuel cells but suffer from a critical tradeoff between ionomer sulfonate poisoning and nanoparticle instability. Herein, we report a spatial confinement strategy to encapsulate dense Pt nanoparticles (~51.8 wt%) within Mn/N-co-doped mesoporous carbon nanocages (denoted as Pt-MnNC). This architecture excludes bulky ionomers to create an ionomer-shielded environment against sulfonate poisoning, while Mn-N_x-mediated strong metal-support interactions anchor the Pt nanoparticles to prevent agglomeration and further boost durability. In the 5 × 5 cm² membrane electrode assembly tests, the Pt-MnNC catalyst delivers an exceptional power density of 1.26 W·cm …

Efficient Acidic H2O2 Electrosynthesis Over Co Atoms Anchored On Nitrogen-Doped Hierarchical Porous Carbon, Xiao Huang, Zi-Hao Zhan, Hao-Xu Niu, Guan-Yu Luo, Jin-Tao Huang, Bo-Xuan Jin, De-Li Wang

Journal of Electrochemistry

The two-electron oxygen reduction reaction (2e⁻ ORR) presents a promising route for the on-site production of hydrogen peroxide (H₂O₂), offering a green alternative to energy-consuming anthraquinone process. However, the high selectivity toward the competing 4e⁻ ORR over the desired 2e⁻ pathway leads to low Faradaic efficiency for H₂O₂, posing a critical challenge in catalyst design. In this work, a nitrogen-doped hollow hierarchical porous carbon with anchored Co atoms (CoN/HPC) was constructed for high-performance H₂O₂ production. The as-prepared Co-N/HPC catalyst showed excellent 2e⁻ ORR performance, achieving …

Engineering Small-Sized Cations With Strong Solvation For High-Voltage Supercapacitors, Tong Huo, Pan Liu, Hao Chen, Peng Zhang, Zhen-Lei Chen, Guo-Fu Sun, Zhi-Qiang Shi, Jing Wang

Journal of Electrochemistry

Supercapacitors (SCs) have attracted much attention in the field of energy storage due to their high power density and long cycle life. However, their relatively low energy density limits their application in a wider range of fields. Methods to increase energy density include enhancing specific capacitance and extending operating voltage window. Herein, we report a novel electrolyte salt, tetramethylammonium bis(fluorosulfonyl)imide (TMA-FSI), the resulting electrolyte formed with propylene carbonate (PC), designated as TMF, exhibited a wide electrochemical stability window (ESW) of 5.09 V. On the one hand, we found that the small size of TMA⁺ enables it to enter the …

Electrolyte Development And Interfacial Reactions At Multivalent Metal Anode For Next Generation Energy Storage Systems, Leslie Gates

Graduate Masters Theses

The increasing demand for safe, sustainable, and high-performance energy storage systems has driven significant interest in multivalent-ion batteries, including aluminum, magnesium, and zinc-based systems. These technologies have attracted attention due to their high theoretical energy densities, natural abundance, low cost, and environmentally benign nature. However, their development remains hindered by a limited fundamental understanding of electrolyte development and interfacial processes at the electrode–electrolyte interface, where complex electrochemical interactions govern battery performance and stability.

This thesis investigates electrode–electrolyte interactions in both a novel aluminum electrolyte and divalent magnesium and zinc systems. Beginning with the development and characterization of a novel aluminum …

Neural Network Driven By Electrochemical Performance Data For Predicting The Discharge Termination Time Of Seawater Electrolyte-Based Metal-Air Batteries, Peng-Peng Shen, Yi-Chi Pan, Yu-Rong Liu, Lu-Dan Zhang, Ning Niu, Guan-Jun Wang, De-Kun Yang, Xin-Long Tian, Peng Rao

Journal of Electrochemistry

Seawater electrolyte-based metal-air batteries exhibit great promise for marine energy supply systems. However, conventional statistical analysis methods, though applicable to seawater metal-air battery lifetime prediction, have inherent limitations of insufficient prediction accuracy and large error. Herein, a deep time-series regression framework based on InceptionTime and incorporating prior-biased attention pooling is proposed to construct a nonlinear mapping between electrochemical performance sequences and the discharge termination time of catalysts. Specifically, chronoamperometric profiles are employed to extract long-term stability features, while prior knowledge derived from linear sweep voltammetry is introduced to strengthen the attention weighting over critical potential regions. Under a nested leave-one-catalyst-out …

Microwave-Assisted Synthesis Of Core-Shell Structured Pd@Pdptcufe Recessed Truncated Octahedral Nanocrystals For Multifunctional Electrocatalysis, De-Zhong Hu, Wen-Dan Jiang, Wei Keat Ng, Jun Yang, Xiong-Wu Kang

Journal of Electrochemistry

Developing cost-efficient and durable multifunctional electrocatalysts of hydrogen evolution reaction, oxygen reduction reaction and oxygen evolution reaction is crucial for improving energy conversion efficiency in electrolytic water splitting electrolyzer and advancing rechargeable zinc-air batteries. Polyhedral shaped nanocrystals with well-defined crystal facets represent a type of model catalysts that enables the exploration of structure-activity relationships. However, it is still very challenging to prepare alloy nanocrystals with multiple metal components due to their complicated redox potentials and mixing enthalpy. Herein, we report a rapid microwave-assisted polyol reduction method for syntheses of core-shell Pd@PdPtCu, Pd@PdPtCuNi, Pd@PdPtCuCo and Pd@PdPtCuZn octahedral nanocrystals, and recessed truncated-octahedral …

In Situ Electrochemical Characterization Techniques For Active Hydrogen In Electrocatalytic Nitrate Reduction To Ammonia, Hong-Mei Li, Mei Yi, Zhao-Yu Jin, Ming-Hao Xie, Khalid M. Omer, Yong Guo, Pan-Pan Li

Journal of Electrochemistry

Electrocatalytic nitrate reduction to ammonia (NitRR) represents a sustainable pathway that integrates environmental remediation with the production of high-value ammonia. However, the activity and selectivity of this process are limited by the generation, consumption, and dynamic equilibrium of the key transient intermediate—active hydrogen (*H). Precise modulation of *H necessitates a comprehensive understanding of its behavior, which relies fundamentally on advanced in situ electrochemical characterization techniques. However, a systematic review dedicated to the rational selection and application of in situ electrochemical techniques for the specific characterization of *H in NitRR, with clear definitions of each technique's "detectable targets, quantitative accuracy, and …

Structure And Dynamics Of Associative Polymers Under Quiescent State And Flow, Rosita Sivaraj

All Dissertations

Associative polymers, including ionizable polymers, are widely used in membranes, coatings, fuel cells, energy storage, and other advanced soft materials. Their properties are governed by ionic aggregation and associative interactions, which influence chain mobility, phase behavior, self-assembly, interdiffusion, and flow response. This dissertation employs large-scale molecular dynamics (MD) simulations to investigate the structure, dynamics, phase behavior, interdiffusion, and extensional flow response of ion-containing and associative polymer systems under quiescent and nonequilibrium conditions.

The influence of molecular architecture is first examined by comparing ring and linear associative polymers using the Kremer–Grest bead-spring model. In linear chains, their closed-loop architecture reduces interchain …

Preparation And Performance Study Of In-Situ Self-Assembled Biphasic Smmn2O5-Nimn2O4 Composite Cathode, Neng-Chu Xia, Yu Zhou, Qin Wang, Jia-You Zhang, Chun Yu, Yang Zhang, Wan-Bing Guan, Jian-Xin Wang

Journal of Electrochemistry

Mullite-structured oxides exhibit excellent oxygen reduction reaction activity, possess a low thermal expansion coefficient due to their unique crystal structure, and can eliminate the need for a barrier layer and simplify the preparation process as they contain no alkaline earth elements. Thus, they hold great promise as novel cathode materials for solid oxide fuel cells. In this work, a mullite-spinel-structured SmMn₂O₅-NiMn₂O₄ (SMO-NMO) composite cathode was one-step synthesized via a solid-liquid composite route, and its in-situ self-assembly enabled good compatibility with the electrolyte without any barrier layer. Characterization results showed that the SMO:NMO = …

In Situ Stm Visualization Of Molecular Structural Evolution During Electrochemical Oxidation Coupling Of Para-Aminothiophenol On Au(111), Zi-Wei Ma, Tai-Rui Wu, An-Ni Zheng, Lai-Ke Chen, Yuan-Hui Xiao, Zhao-Bin Chen, Qing-Na Zheng, Jian-Zhang Zhou, Jia-Wei Yan, De-Yin Wu

Journal of Electrochemistry

Para-aminothiophenol (PATP) is not only a widely-used probe molecule in the field of surface-enhanced Raman spectroscopy (SERS), but also an important model molecule for interfacial reactions, exhibiting distinct photo- and electro-oxidation pathways, so that PATP is selectively activated under different external fields. The evolution of products and intermediates during electrochemical oxidative coupling remains unknown. In this study, we have investigated the dynamic electrochemical oxidation process of PATP on the Au(111) surface using cyclic voltammetry, electrochemical (EC)-SERS, and in situ electrochemical scanning tunneling microscopy (EC-STM). The results showed that PATP forms an unsaturated adsorption coverage on Au(111) in an acidic solution. …

Exploring The Nature And Role Of Local Cation Ordering In Disordered Rock Salt Cathodes For Li- And Na-Ion Batteries, You Wang

Chemistry and Chemical Biology ETDs

Cation-disordered rock-salt (DRX) cathodes provide a highly tunable platform for next-generation Li- and Na-ion batteries, but their electrochemical behavior is strongly influenced by local structural features hidden in average crystal structures. This dissertation systematically investigates local cation ordering in Li- and Na-based DRX cathodes to understand its effects on Li+/Na+ transport, redox activity, structural evolution, and electrochemical performance. In Li-based systems, Raman spectroscopy and electrochemical analysis reveal that local layered cation ordering in Mn- and Fe-based DRX cathodes is closely correlated with electrochemical behavior. Over-stoichiometric Li-based DRX oxyfluorides further demonstrate that excess Li can regulate local cation ordering, improve Li+ …

Dynamic Reconstruction Engineering Of Anti-Corrosion Ni-Based Anodes For Alkaline Seawater Electrolysis, Yi-Gang Zhang, Wen-Wen Xu, Tian-Yu Zhang, Zhi-Yi Lu

Journal of Electrochemistry

Green hydrogen production via alkaline seawater electrolysis offers an environmentally sustainable and potentially cost-effective route to address both energy and climate challenges. Achieving long-term anode stability under complex ionic environments and industrial current densities remains a central bottleneck. Specifically, Ni-based anodes exhibit intense surface reconstruction during the oxygen evolution reaction, necessitating dynamic anti-corrosion strategies. This mini review systematically summarizes reconstruction engineering approaches to develop anti-corrosion Ni-based anodes of alkaline seawater electrolysis across increasingly complex ionic environments from simulated seawater to real seawater: (i) Cl^– dominated; (ii) Cl^– with co-existing oxyanions, and (iii) Cl^–  with co-existing Br^{– …}

Distinct Co2 Electroreduction Behaviors Over Planar And Non-Planar Cobalt Molecular Catalysts, Ru Jia, Cheng-Biao Zhu, Zi-Mo Zhang, Tuo Wang, Kai-Cong Yang, Guang-Zhe Wang, Yang Hu, Ting-Ting Zhang, Zhen-Wei Wei, Li Xiao, Gong-Wei Wang, Lin Zhuang

Journal of Electrochemistry

Molecular catalysts serve as ideal platforms for studying electrocatalytic reaction mechanisms. While current research mainly focuses on modulating central metals or surrounding ligands, the influence of molecular spatial configuration remains largely unexplored. Herein, we synthesized two cobalt complexes with similar ligand environments but distinct spatial geometries, a planar cobalt hexaazamacrocyclic complex (CoHAM) and a non-planar acyclic Co(phen)₂Cl₂, and evaluated their performance in CO₂ reduction reaction (CO₂RR). The planar CoHAM exhibited dramatically superior CO₂RR performance compared to the non-planar Co(phen)₂Cl₂. Through a series of combined analyses using in-situ …

Li+/Na+ Hybrid Ion Conduction Mechanism In The Superionic Conductor Li3–XNaXZr2Si2Po12, Yi-Hong Wu, Xia Xie, Lei Zhu, Mu-Ran Yu, Guo-Tai Zhang, Jun-Chao Chen, Shu-Ying Sun, You-Wei Wang, Wei-Ping Tang

Journal of Electrochemistry

Hybrid ion conductors that transport multiple ionic conductive species provide a useful platform for understanding how mixed-ion transport governs ionic conductivity within a single phase. However, the controlled introduction of multiple mobile ions into solid-state electrolytes and a mechanistic understanding of their migration within the framework remain challenging. Herein, a skeleton-retained Li⁺↔Na⁺ cationic exchange was used to simultaneously induce Li⁺ and Na⁺ cations into the NASICON-type framework of Li_3–xNa_xZr₂Si₂PO₁₂ (0 < x < 3). We show that the interpenetration of NaO₆ and NaO₈ coordination polyhedra significantly influences the ionic conductivity of hybrid ion conductors. Computational …

Distribution And Transport Of Lithium Ions At Interfaces Between Graphite And Carboxymethyl Celluloses, Zi-Jun Huang, Zhen-Ying Zheng, Hua-Wei Cao, Jian Wang, Qing-Feng Zhang, Sheng-Li Chen

Journal of Electrochemistry

Carboxymethyl cellulose (CMC) is a water-processable binder widely used for graphite anodes. However, a microscopic understanding of why the identity of CMC counterions (Li⁺/Na⁺/K⁺) strongly affects electrode performance remains limited. Here, molecular dynamics (MD) simulations are used to track Li⁺ transport accessibility across electrolyte/CMC/graphite three-phase interfaces, comparing pure CMC-Li, CMC-Na, CMC-K, and mixed-counterion CMC binders. We find that CMC-Li sustains a continuous Li⁺ transport pathway from the electrolyte through the binder phase toward graphite. In contrast, in CMC-Na and CMC-K, Na⁺/K⁺ ions preferentially enrich at the graphite/binder interface, forming …

Lafe0.925ti0.075o3 Perovskite Coated With Ethyl Cellulose: A High-Stability, Low-Hysteresis Platform For Advanced Humidity Sensing, Akhmad Futukhillah Fataba Alaih, Djoko Triyono, Rifqi Almusawi Rafsanjani

Makara Journal of Science

Humidity sensors are pivotal in numerous sectors, such as environmental monitoring, industrial automation, and health-care. This study presents the fabrication and detailed evaluation of an advanced humidity sensor using ethyl cellulose (EC)-coated LaFe_0.925Ti_0.075O₃ (LFTO) perovskite nanoparticles synthesized via the sol-gel method. The LFTO nanopar-ticles exhibited a mesoporous structure with an enhanced surface area, which significantly improved their moisture adsorption capabilities. The innovative application of EC coating addresses critical substrate adhesion issues, enhancing mechanical stability without compromising sensor sensitivity. Comprehensive performance evaluations revealed minimal hysteresis (

Tuning Ion Mobility And Molecular Confinement In High-Performance Polymer Electrolytes For Energy Storage, Ezzeldien Yousef Muhammed Yousef

Theses and Dissertations

This research addresses the critical energy density limitations of aqueous supercapacitors, which are traditionally constrained by the narrow electrochemical stability window (ESW) of water 1.23 V. By employing two distinct molecular engineering strategies, this study developed high-performance electrolyte systems that significantly extend voltage stability and thermal resilience.

The first system, CsBr@PAM/HA, utilizes a polyacrylamide and hyaluronic acid hydrogel matrix. This system exploits the chaotropic nature of Cs⁺ ions to disrupt the aqueous hydrogen-bonding network, enhancing ionic conductivity to 104 mS cm^-1. Through systematic salt screening, CsBr was identified as the optimal electrolyte, enabling a stable 2.0 V …

Mediating Energy And Charge Transfer Dynamics Of Lead Halide Perovskite Nanocrystals Via Surface Chemical Approaches, Aaron S. Malinoski

Dissertations, Theses, and Capstone Projects

Energy and charge transfer are the fundamental mechanisms by which semiconductor nanocrystals interact with their external environment and underpin all light-conversion related applications. Lead halide perovskite nanocrystals (PNCs) are a relatively new class of semiconductor nanocrystals that possess a unique and dynamic surface chemical environment. Investigations into the influence of these surface chemical conditions on the electronic coupling between surface-bound molecular acceptors and the perovskite nanocrystals, and how the surface chemistry can be manipulated, in turn controlling the charge and energy transfer mechanisms, is the focus of this dissertation. Through ligand-shell engineering using commercially available, inexpensive small molecules, the surface …

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 …

Computational-Experimental Synergy As A Predictive And Interpretive Tool Through Metal-Organic Framework Investigations, Cristian Sayers

Graduate Student Theses and Dissertations

In the search for tunable materials platforms capable of addressing both clean energy conversion and viable post-combustion carbon capture, metal-organic frameworks (MOFs) have emerged as a uniquely versatile class of porous solids offering high specific surface area, structural tunability, and chemically addressable metal nodes and organic linkers. Realizing their potential requires understanding behavior that spans atomic-scale electronic structure and bulk-scale property response, a regime in which neither computation nor experiment alone is sufficient. This work attempts to develop a tighter integration between density functional theory (DFT) and laboratory investigation, treating the two modalities as mutually informing probes of the same …

Nanoscale Structure And Spontaneous Self-Assembly Of Hydrothermal Organic Products, Glorianne P. Dorce

Chemistry and Chemical Biology ETDs

Carbon nanomaterials derived from citric acid and urea exhibit behaviors that challenge conventional structure–property models based on static bulk descriptions. This study examines how precursor pairing and reaction duration, post‑synthetic thermal history, and time‑dependent aging govern nanoscale organization and optical response. Through controlled synthesis and processing, distinct nanostructures with tunable structural and spectroscopic profiles are generated.

A multiscale framework integrating nano‑FTIR, atomic force microscopy, and thermal analysis reveals chemical heterogeneity and continuous structural reorganization across length scales. By correlating local chemical environments with optical behavior, we show that fluorescence efficiency and photostability depend on specific nanoscale architectures rather than average …

Hollow Nickel-Iron Nanoshells As Electrocatalysts For The Oxygen Evolution Reaction, Jonathan Batey

Chemistry & Biochemistry Undergraduate Honors Theses

The development of highly active and affordable catalysts for the oxygen evolution reaction is crucial to achieve a future where hydrogen is generated cleanly using renewable methods. Ni-Fe nanocatalysts show great promise in this area, as they are affordable and highly active. However, to overcome the industrial dominance of steam methane reforming, their activity needs improvement. This work aims to increase the activity of Ni-Fe nanocatalysts by making hollow nanostructures. Hollow Ni-Fe nanostructures were synthesized by coating a Cu template with Ni and Fe, followed by the etching of the Cu template. This left hollow Ni-Fe nanoshells, which were used …

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 …

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 …