Chemistry Commons^™

Which Factor Dominates Battery Performance: Metal Ion Solvation Structure-Derived Interfacial Behavior Or Solid Electrolyte Interphase Layer?, Hao-Ran Cheng, Zheng Ma, Ying-Jun Guo, Chun-Sheng Sun, Qian Li, Jun Ming

Journal of Electrochemistry

Solid-electrolyte interphase (SEI) layer formed on the electrode by electrolyte decomposition has been considered to be one of the most important factors affecting the battery performance. We discover that the metal ion solvation structure can also influence the performance, particularly, it can elucidate many phenomena that the SEI cannot. In this review, we summarize the importance of the metal ion solvation structure and the derived metal ion de-solvation behaviors, by which we can build an interfacial model to show the relationship between the interfacial behavior and electrode performance, and then apply to different electrode and battery systems. We emphasize the …

Helium Nanodroplets As An Efficient Tool To Investigate Hydrogen Attachment To Alkali Cations, Siegfried Kollotzek, José Campos-Martínez, Massimiliano Bartolomei, Fernando Pirani, Lukas Tiefenthaler, Marta I. Hernández, Teresa Lázaro, Eva Zunzunegui-Bru, Tomás González-Lezana, José Bretón, Javier Hernández-Rojas, Olof E. Echt, Paul Scheier

Faculty Publications

We report a novel method to reversibly attach and detach hydrogen molecules to positively charged sodium clusters formed inside a helium nanodroplet host matrix. It is based on the controlled production of multiply charged helium droplets which, after picking up sodium atoms and exposure to H₂ vapor, lead to the formation of Na_m⁺(H₂)_n clusters, whose population was accurately measured using a time-of-flight mass spectrometer. The mass spectra reveal particularly favorable Na⁺(H₂)_n and Na₂⁺(H₂)_n clusters for specific “magic” numbers of attached hydrogen molecules. …

Theoretical Studies Of Molecule-Surface Interactions And Dynamics, Yingqi Wang

Chemistry and Chemical Biology ETDs

Gas-surface scattering involves the conversion of energy in different forms in the impinging molecule, possible bond breaking and forming, and the energy transfer across gas-solid interface. Possible energy dissipation channels include adiabatic energy transfer to the motion of surface phonons and non-adiabatic interactions with surface electron-hole pairs. A complete understanding of the interplay of energy dissipation and physical/chemical changes in the molecule is vital for many important applications such as materials fabrication and heterogenous catalysis.

Gas-surface encounters may occur where non-adiabatic effects are negligible. Two such systems were investigated, both with ample experimental data. One is concerned with the scattering …

Photoionization Energetics And Dissociation Pathways Of Hydroperoxyethyl Formate Produced In The Reaction Of Ch3Choo + Formic Acid, Vincent J. Esposito, Trent A. Mchenry, Marsha I. Lester

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The bimolecular reaction of Criegee intermediates, zwitterionic carbonyl oxide species produced in alkene ozonolysis, with organic acids leads to formation of functional hydroperoxides implicated in the generation of atmospheric aerosols. This theoretical study using high-level explicitly correlated coupled-cluster theory examines the low energy conformers of hydroperoxyethyl formate [HOOCH(CH₃)OCHO, HPEF] formed in the bimolecular reaction of CH₃CHOO, a simple alkyl-substituted Criegee intermediate, with formic acid, and the detection of HPEF via photoionization. The vertical and adiabatic ionization energies of HPEF are computed, along with the pathways for dissociative ionization that produce HO₂ or OCHO fragments with …

Agricultural Aerosols: The Impact Of Farming Activity On Ice Nucleating Particles, Joseph Robinson

The Journal of Purdue Undergraduate Research

Farming activities cause particles such as soil dust and plant material to be emitted into the air. Some of these aerosols can become ice nucleating particles (INPs), serving as seeds for ice and mixed-phase clouds. While there have been ground-based studies of these particles in the western Great Plains and a single air-based study in Indiana, there is a distinct lack of ground-based studies in the Midwest. In Indiana, over two-thirds of the state is farmland, with over 75% of land in Tippecanoe County used for agriculture. Despite farming being such an essential part of life in Indiana, the connection …

Electrochemical Syntheses Of Nanomaterials And Small Molecules For Electrolytic Hydrogen Production, Jia-Qi Wei, Xiao-Dong Chen, Shu-Zhou Li

Journal of Electrochemistry

Hydrogen is a clean, efficient, renewable energy resource and the most promising alternative to fossil fuels for future carbon-neutral energy supply. Therefore, sustainable hydrogen production is highly attractive and urgently demanded, especially via water electrolysis that has clean, abundant precursors and zero emission. However, current water electrolysis is hindered by the sluggish kinetics and low cost/energy efficiency of both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this regard, electrochemical synthesis offers prospects to raise the efficiency and benefit of water electrolysis by fabricating advanced electrocatalysts and providing more efficient/value-adding co-electrolysis alternatives. It is an eco-friendly and facile …

Alkaline Water Electrolysis For Efficient Hydrogen Production, Wen-Fu Xie, Ming-Fei Shao

Journal of Electrochemistry

Hydrogen production from water electrolysis is a sustainable and environmentally benign strategy in comparison with fossil fuel-based hydrogen. However, this promising technique suffers from the high energy consumption and unsatisfactory cost due to the sluggish kinetics of both half reaction and inferior stability of electrocatalysts. To address this challenge, herein, we present a timely and comprehensive review on advances in alkaline water electrolysis that is already commercialized for large scale hydrogen production. The design principles and strategies with aiming to promote the performance of hydrogen generation are discussed from the view of electrocatalyst, electrode, reaction and system. The challenges and …

Alkaline Seawater Electrolysis At Industrial Level:Recent Progress And Perspective, Tao Zhang, Yi-Pu Liu, Qi-Tong Ye, Hong-Jin Fan

Journal of Electrochemistry

Industrial hydrogen generation through water splitting, powered by renewable energy such as solar, wind and marine, paves a potential way for energy and environment sustainability. However, state-of-the-art electrolysis using high purity water as hydrogen source at an industrial level would bring about crisis of freshwater resource. Seawater splitting provides a practical path to solve potable water shortage, but still faces great challenges for large-scale industrial operation. Here we summarize recent developments in seawater splitting, covering general mechanisms, design criteria for electrodes, and industrial electrolyzer for direct seawater splitting. Multi-objective optimization methods to address the key challenges of active sites, reaction …

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 …

Catalytic Effect Of Disordered Ru-O Configurations For Electrochemical Hydrogen Evolution, Xue Sun, Ya-Jie Song, Ren-Long Li, Jia-Jun Wang

Journal of Electrochemistry

Phase engineering is considered as an effective method for modulating the electronic structure and catalytic activity of catalysts. The disordered conformation of amorphous materials allows flexible reforming of the surface electronic structure, showing their attractiveness as catalysts for hydrogen evolution reaction (HER). Herein, we designed and developed an amorphous ruthenium dioxide (a-RuO₂) catalyst with a disordered Ru-O configuration. The conformational relationship between Ru-O ordering and HER performance is established by combining advanced electron microscopic techniques with detailed electrochemical tests. Specifically, the disordered Ru-O coordination significantly enhanced the HER catalytic activity in both acidic and alkaline media, ultimately leading …

Spectroscopic Properties Of The Astrochemical Molecules [Al, O, Si]X (X = 0, +1), Jacqueline M. Friskey, Vincent J. Esposito, Tarek Trabelsi, Joseph S. Francisco

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Aluminum and silicon are present in large quantities in the interstellar medium, making the triatomic species consisting of both elements intriguing with regard to the foundations of astrochemistry. Spectroscopic parameters have been calculated via high-level ab initio methods to assist with laboratory and observational detection of [Al, O, Si]^x(x = 0,+1). All [Al, O, Si]M^x(x = 0,+1) isomers exist in the linear geometry, with linear AlOSi (X ²Π) and linear AlOSi⁺ (X¹Δ) being the most stable neutral and cationic species, respectively. Formation of the neutral species most likely occurs via reaction of …

Solvation Of Large Polycyclic Aromatic Hydrocarbons In Helium: Cationic And Anionic Hexabenzocoronene, Miriam Kappe, Florent Calvo, Johannes Schöntag, Holger F. Bettinger, Serge Krasnokutski, Martin Kuhn, Elisabeth Gruber, Fabio Zappa, Paul Scheier, Olof E. Echt

Faculty Publications

The adsorption of helium on charged hexabenzocoronene (Hbc, C₄₂H₁₈), a planar polycyclic aromatic hydrocarbon (PAH) molecule of D_6h symmetry, is investigated by a combination of high-resolution mass spectrometry and classical and quantum computational methods. The ion abundance of He_nHbc⁺ complexes versus size n features prominent local anomalies at n = 14, 38, 68, 82, and a weak one at 26, indicating that for these “magic” sizes the helium evaporation energies are relatively large. Surprisingly, mass spectra of anionic He_nHbc^– complexes feature a different set of anomalies, namely at …

Investigation Of Carbon Dioxide Oxidation Reaction Pathways On Rh(111) Via Reflection Absorption Infrared Spectroscopy (Rairs), Elizabeth A. Jamka

Dissertations

CO oxidation, RAIRS, Rh(111), Surface Science, UHV

Converting Hydrazone-Based Photoswitches Into Functional Materials, Sirun Yang

Dartmouth College Ph.D Dissertations

The development of new classes of molecular switches with enhanced performance and brand-new functionalities enables practitioners to push the frontiers of adaptive materials. In the realm of photoswitches, the bistability of hydrazones (i.e., molecules that incorporate the C=N-NH functional group) allows for the kinetic trapping of polymer and supramolecular assemblies resulting in multistate actuation and emergent phenomena that are not tractable with other photoswitches. This property has transformed hydrazone photoswitches into powerful tools that can be used in understanding fundamental molecular interactions and how to apply them in modulating the physicochemical properties of materials.

Progressing from disordered to …

Estimation Of The Bubble Point Pressure Of Multicomponent Reservoir Hydrocarbon Fluids, Benjamin Sunday Usen, Chidi Obi

Makara Journal of Science

This study developed a novel C-sharp (C#) programming language for the estimation of bubble point pressure (BPP) of various hydrocarbon mixtures at equilibrium state. The methodology was based on vapor–liquid equilibrium calculation using Peng Robinson equation of state implementation, thermodynamic equilibrium calculation and Newton-Raphson’s method for the successive substitution of the unknown variables. The equal fugacity constraint can be satisfied by obtaining the equilibrium which serves as a criterion for two or more phases to exist at equilibrium. The problem was resolved by searching for a pressure that will satisfy the two constraints. Complex calculation was performed by successively substituting …

Symmetry-Resolved Co Desorption And Oxidation Dynamics On O/Ru(0001) Probed At The C K-Edge By Ultrafast X-Ray Spectroscopy, Jerry Larue, Boyang Liu, Gabriel L. S. Rodrigues, Chang Liu, Jose Antonio Garrido Torres, Simon Schreck, Elias Diesen, Matthew Weston, Hirohito Ogasawara, Fivos Perakis, Martina Dell'angela, Flavio Capotondi, Devon Ball, Conner Carnahan, Gary Zeri, Luca Giannessi, Emanuele Pedersoli, Denys Naumenko, Peter Amann, Ivaylo Nikolov, Lorenzo Raimondi, Carlo Spezzani, Martin Beye, Johannes Voss, Hsin-Yi Wang, Filippo Cavalca, Jörgen Gladh, Sergey Koroidov, Frank Abild-Pedersen, Manuel Kolb, Piter S. Miedema, Roberto Costantini, Tony F. Heinz, Alan C. Luntz, Lars G. M. Pettersson, Anders Nilsson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

We report on carbon monoxide desorption and oxidation induced by 400 nm femtosecond laser excitation on the O/Ru(0001) surface probed by time-resolved x-ray absorption spectroscopy (TR-XAS) at the carbon K-edge. The experiments were performed under constant background pressures of CO (6 × 10⁻⁸ Torr) and O2 (3 × 10⁻⁸ Torr). Under these conditions, we detect two transient CO species with narrow 2π* peaks, suggesting little 2π* interaction with the surface. Based on polarization measurements, we find that these two species have opposing orientations: (1) CO favoring a more perpendicular orientation and (2) CO favoring a more parallel orientation …

Preface To Special Issue On Water Electrolysis For Hydrogen Production, Li Li, Jin-Song Hu, Zi-Dong Wei

Journal of Electrochemistry

No abstract provided.

The Rapid Preparation Of Efficient Mofeco-Based Bifunctional Electrocatalysts Via Joule Heating For Overall Water Splitting, Ao Zhou, Wei-Jian Guo, Yue-Qing Wang, Jin-Tao Zhang

Journal of Electrochemistry

Water electrolysis is an available way to obtain green hydrogen. The development of highly efficient electrocatalysts is a current research hotspot for water splitting, but it remains challenging. Herein, we demonstrate the synthesis of a robust bifunctional multi-metal electrocatalysts toward water splitting via the rapid Joule-heating conversion of metal precursors. The composition and morphology were well regulated via altering the ratio of metal precursors. In particular, the trimetal MoC/FeO/CoO/carbon cloth (CC) electrode revealed the outstanding bifunctional electrocatalytic performance due to the unique composition and large electrochemical active surface area. Typically, the MoC/FeO/CoO/CC catalyst needed low overpotentials of 121 and 268 …

Self-Supporting Nife Ldhs@Co-Oh-Co3 Nanorod Array Electrode For Alkaline Anion Exchange Membrane Water Electrolyzer, Dan-Dan Guo, Hong-Mei Yu, Jun Chi, Zhi-Gang Shao

Journal of Electrochemistry

The development of efficient and durable electrodes for anion exchange membrane water electrolyzers (AEMWEs) is essential for hydrogen production. In this work, 2D NiFe layered double hydroxides (NiFe LDHs) nanosheets were grown on the 1D cobaltous carbonate hydroxide nanowires array (Co-OH-CO₃) and the unique 3D layered self-supporting nanorod array (NiFe LDHs@Co-OH-CO₃/NF) electrode was obtained. Importantly, we demonstrated an efficient and durable self-supporting NiFe LDHs@Co-OH-CO₃/NF electrode for oxygen evolution reaction (OER) and as the anode of the AEMWE. In a three-electrode system, the self-supporting NiFe LDHs@Co-OH-CO₃/NF electrode showed excellent catalytic activity for OER, …

Surface Structure Engineering Of Feni-Based Pre-Catalyst For Oxygen Evolution Reaction: A Mini Review, Jia-Xin Li, Li-Gang Feng

Journal of Electrochemistry

Nitrite, a widespread raw material, is harmful to human health for long-term consumption. At present, the detection methods of nitrite mainly include chemical analysis, fluorescence, ultraviolet spectrophotometry and chromatography. These methods have ideal sensitivity and selectivity, but also have some characteristics: cumbersome operation, expensive equipment and professional personnel. Therefore, the development of a simple and sensitive nitrite assay is of great significance. In this paper, the Au/rGO/FeOOH composite materials, which revealed good synergistic catalytic performance among the three elements in the composite, were prepared by simple hydrothermal method and reduction method for the first time with large specific surface area …

A Co Porphyrin With Electron-Withdrawing And Hydrophilic Substituents For Improved Electrocatalytic Oxygen Reduction, Hong-Bo Guo, Ya-Ni Wang, Kai Guo, Hai-Tao Lei, Zuo-Zhong Liang, Xue-Peng Zhang, Rui Cao

Journal of Electrochemistry

Understanding factors that influence the catalyst activity for oxygen reduction reaction (ORR) is essential for the rational design of efficient ORR catalysts. Regulating catalyst electronic structure is commonly used to fine-tune electrocatalytic ORR activity. However, modifying the hydrophilicity of catalysts has been rarely reported to improve ORR, which happens at the liquid/gas/solid interface. Herein, we report on two Co porphyrins, namely, NO₂-CoP (Co complex of 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin) and 5F-CoP (Co complex of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin), and their electrocatalytic ORR features. By simultaneously controlling the electronic structure and hydrophilic property of the meso-substituents, the NO₂-CoP showed higher electrocatalytic activity than …

Recent Development Of Low Iridium Electrocatalysts Toward Efficient Water Oxidation, Jing Ni, Zhao-Ping Shi, Xian Wang, Yi-Bo Wang, Hong-Xiang Wu, Chang-Peng Liu, Jun-Jie Ge, Wei Xing

Journal of Electrochemistry

Developing high-performance and low-cost electrocatalysts for oxygen evolution reaction (OER) is the key to implementing polymer electrolyte membrane water electrolyzer (PEMWE) for hydrogen production. To date, iridium (Ir) is the state-of-the-art OER catalyst, but still suffers from the insufficient activity and scarce earth abundance, which results in high cost both in stack and electricity. Design low-Ir catalysts with enhanced activity and stability that can match the requirements of high current and long-term operation in PEMWE is thus highly desired, which necessitate a deep understanding of acidic OER mechanisms, unique insights of material design strategies, and reliable performance evaluation norm, especially …

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 …

Sensitized Photooxidation Of Prenylated Compounds: Mechanisms Of Downstream Dark Effects And Phototoxicity Priming, Shakeela Jabeen

Dissertations, Theses, and Capstone Projects

This thesis consists of four chapters as detailed below.

Chapter 1 discusses a singlet oxygen priming mechanism. Airborne singlet oxygen derived from photosensitization of triplet dioxygen is shown to react with an alkene surfactant (8-methylnon-7-ene-1 sulfonate) leading to ‘ene’ hydroperoxides that in the dark inactivate planktonic E. coli. The ‘ene’ hydroperoxide photoproducts are not toxic on their own, but they become toxic after the bacteria are pretreated with singlet oxygen. The total quenching rate constant (k_T) of singlet oxygen of the alkene surfactant was measured to be 1.1 × 10⁶ M⁻¹ s^{− …}

Quantitative Lithium Composite As 3d Lithium Foam Anode For Lithium Metal Battery, Hu-Dong Li, Wei-Shang Jia, Xin-Xiu Yan, Yao-Yue Yang

Journal of Electrochemistry

Lithium (Li) metal as an anode material for batteries has extremely high specific capacity and extremely low redox potential, which can significantly improve the energy density of the battery. However, the main problems faced by the use of Li metal anodes are Li dendrite growth, interfacial side reaction and volumetric change of electrode. Herein, a strategy to prepare the three-dimensional (3D) Li foam by combining 3D scaffold with quantitative Li was proposed to suppress Li dendrites growth and alleviate electrode volumetric change. The 3D Li foam facilitated the efficient utilization of Li metal by suppressing the Li dendrite growth, mitigating …

Optimized Electrochemical Performance Of Si@C Prepared By Hydrothermal Reaction And Glucose Carbon Source, Si Chen, Song-Sheng Zheng, Lei-Ming Zheng, Ye-Han Zhang, Zhao-Lin Wang

Journal of Electrochemistry

Silicon (Si) has been considered as the potential material for the next-generation lithium-ion batteries (LIBs) for its high capacity (4200 mAh·g^-1, Li₂₂Si₅) and suitable working voltage (about 0.25 V vs. Li/Li⁺). However, the cycling stability and electrochemical performance of Si anode become significant challenges because of low intrinsic conductivity and huge volume variation (about 400%) during cycling processes. In addition, the repeated formation and destruction of surface solid electrolyte interphase (SEI) film will continuously consume the electrolyte and cause damage to LIBs. Carbon (C) materials, such as graphite, carbon spheres and tubes, …

Facile One-Step Solid-State Synthesis Of Ni-Rich Layered Oxide Cathodes For Lithium-Ion Batteries, Jing-Yue Wang, Rui Wang, Shi-Qi Wang, Li-Fan Wang, Chun Zhan

Journal of Electrochemistry

Nickel-rich layered oxide is one of the dominate cathode materials in the lithium ion batteries, due to its high specific energy density meeting the range requirement of the electric vehicles. Typically, the commercial Ni-rich layered oxides are synthesized from co-precipitated precursors, while precision control is required in the co-precipitation process to ensure the atomic level mixing of the cations such as Ni, Co and Mn, et.al. In this work, a one-step solid-state method was successfully applied to synthesize the Ni-rich layered oxide materials with ultra-high Ni content. By choosing the nickel hydroxides as the precursor with layered structure similar to …

A Novel Electrochemical Sensor Based On Au/Rgo/Feooh For One-Step Detection Of Nitrite, Da-Juan Luo, Bing-Qian Liu, Meng-Yan Qin, Rong Gao, Li-Xia Su, Yong-Huan Su

Journal of Electrochemistry

Nitrite, a widespread raw material, is harmful to human health for long-term consumption. At present, the detection methods of nitrite mainly include chemical analysis, fluorescence, ultraviolet spectrophotometry and chromatography. These methods have ideal sensitivity and selectivity, but also have some characteristics: cumbersome operation, expensive equipment and professional personnel. Therefore, the development of a simple and sensitive nitrite assay is of great significance. In this paper, the Au/rGO/FeOOH composite materials, which revealed good synergistic catalytic performance among the three elements in the composite, were prepared by simple hydrothermal method and reduction method for the first time with large specific surface area …

Low-Crystallinity And Heterostructured Aupt-Ru@Cnts As Highly Efficient Multifunctional Electrocatalyst, Tuan-Jie Gan, Jian-Ping Wu, Shi Liu, Wen-Jun Ou, Ling Bin, Xiong-Wu Kang

Journal of Electrochemistry

The catalytic activity of the catalysts is strongly dependent on the structure of the catalysts, and the exploration of their correlation and structure-controlled synthesis of the high-performance catalysts are always at the central. Currently, platinum (Pt) is the optimum catalyst for hydrogen evolution reaction (HER), oxygen reduction reaction (ORR) and alcohol oxidation reaction, while ruthenium (Ru) behaves as the champion catalyst for oxygen evolution reaction (OER) during water splitting. Preparing alloy catalysts with these precious metals can modulate the catalytic activity of these catalysts from the perspective of strain effect, ensemble effect and ligand effect. Here, we developed a strategy …

Adsorption Of Helium And Hydrogen On Triphenylene And 1,3,5-Triphenylbenzene, Bergmeister Bergmeister, Kollotzek Kollotzek, Florent Calvo, Elisabeth Gruber, Fabio Zappa, Paul Scheier, Olof E. Echt

Faculty Publications

The adsorption of helium or hydrogen on cationic triphenylene (TPL, C₁₈H₁₂), a planar polycyclic aromatic hydrocarbon (PAH) molecule, and of helium on cationic 1,3,5-triphenylbenzene (TPB, C₂₄H₁₈), a propeller-shaped PAH, is studied by a combination of high-resolution mass spectrometry and classical and quantum computational methods. Mass spectra indicate that He_nTPL⁺ complexes are particularly stable if n = 2 or 6, in good agreement with the quantum calculations which show that for these sizes the helium atoms are strongly localized on either side of the central carbon ring for n = …