Review
Chemistry, Multidisciplinary
Nianjun Yang, Siyu Yu, Wenjun Zhang, Hui-Ming Cheng, Patrice Simon, Xin Jiang
Summary: This study introduces a method to improve the energy density of electrochemical capacitors (ECs) by using confined soluble redox electrolytes and porous electrodes. The method utilizes the diffusion-controlled faradaic processes of confined redox electrolytes at the surface of a porous electrode, combining the high power densities of ECs and high energy densities of batteries. Significant progress has been made in this field, and strategies to improve performance are highlighted.
ADVANCED MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Qinglin Zhu, Yuemeng Yang, Hongxiao Gao, Li-Ping Xu, Shutao Wang
Summary: Superwettable materials have shown great potential in electrochemical biosensors, offering advantages such as large electrochemical active areas and optimized mass transfer. Progress has been made in different types of superwettable electrodes, and superwettable materials can also be used in wearable electrochemical sensors.
Article
Chemistry, Physical
Changjin Guo, Jiyang Xie, Jing Wang, Lun Li, Zhu Zhu, Lin Xie, Yongyun Mao, Wanbiao Hu
Summary: The novel structural active orientation strategy successfully achieved the thinning of transition-metal fluoride BaCoF4, leading to significantly enhanced electrochemical redox performance. The high specific capacitance, approximately five times higher compared to its bulk counterpart, confirms the effectiveness of this strategy. Moreover, the asymmetric electrochemical capacitor fabricated with [31 over bar 0]-BaCoF4 and activated carbon exhibited an ultrahigh energy density, much higher than the majority of existing AEC systems.
ADVANCED ENERGY MATERIALS
(2021)
Letter
Chemistry, Physical
Ziyang Wei, Florian Goltl, Stephan N. Steinmann, Philippe Sautet
Summary: Electrocatalysis plays a crucial role in sustainable energy conversion and storage. This study introduces a novel approach combining the grand canonical treatment of electrons with many-body perturbation theory to model electrocatalytic reactions. The results show that this approach provides more accurate energetics and significantly improves the agreement with experimental data compared to commonly used approximations. This development is expected to open up new possibilities for electrochemical applications using RPA.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Electrochemistry
Byunghoon Hwang, Jeongwoo Yang, Dohyeun Kim, Won Chan Yun, Jae W. Lee
Summary: We designed a membraneless potassium bromide electrochemical capacitor (ML-PBEC) single cell that generates high energy density and reduces self-discharge. Highly porous carbon with a hierarchical structure was synthesized from CO2 gas, and the effect of nitrogen doping on the CO2-derived carbon materials' electrochemical performance was investigated. The ML-PBEC single cell, using the synthesized carbon as electrodes and a Br-/Br3- redox active aqueous electrolyte, achieved enhanced energy density by suppressing the cross-diffusion of soluble bromine molecules through electrostatic interaction between N-doped sites' protons and polybromide anions even without a membrane.
ELECTROCHIMICA ACTA
(2023)
Article
Engineering, Electrical & Electronic
Juanqin Xue, Yuzhu Shi, Wenqiao Wang, Yongqi Yu, Changbin Tang
Summary: Recently, MXene has been widely used as an electrode material for electrochemical capacitors due to its excellent electrochemical performance. Its properties can be further enhanced by compounding it with other materials. In this study, MXene was obtained by selective etching, and MXene/PTh composites with different mass ratios were synthesized using the vacuum filtration self-assembly method. The results showed that the M/PTh-3 composite exhibited the best capacitance performance, with good cyclic stability, making it a promising material for high-performance electrochemical capacitors.
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
(2022)
Article
Chemistry, Analytical
Min Jiang, Ling Zhu, Yuqiao Liu, Junmin Li, Yunqi Diao, Chengcheng Wang, Xishan Guo, Dajing Chen
Summary: In this work, a facile method for fabricating laser induced versatile graphene-metal nanoparticles (LIG-MNPs) electrodes with redox molecules sensing capabilities was developed. The electrodes were engraved using a simple synthesis process, allowing for rapid preparation, modification, and replacement of metal particles. The LIG-MNPs electrodes showed high sensitivity and efficient sensing of H2O2 and H2S, and successfully achieved real-time monitoring of these molecules. This work provides a universal and versatile protocol for quantitatively detecting a wide range of hazardous redox molecules.
Review
Chemistry, Multidisciplinary
Keke Du, Dongyan Zhang, Shuangbao Zhang, Kam Chiu Tam
Summary: This review provides a comprehensive overview of the development of functional cellulose nanofiber (CNF) as electrode materials through the layer-by-layer (LbL) approach. The electrodes prepared using this method exhibit excellent properties such as high specific surface area, outstanding electrical conductivity, superior electrochemical activity, and exceptional mechanical stability.
Article
Electrochemistry
Bipinlal Unni, Ian J. Burgess
Summary: The electron transfer kinetics of TEMPO monolayers were studied, revealing that the density of TEMPO groups is approximately 20% of a full monolayer coverage. Standard heterogeneous rate constants were extracted from SAMs of different chain lengths, and ATR-SEIRAS was used to show conformational changes induced by oxidation of the TEMPO radical.
ELECTROCHIMICA ACTA
(2021)
Article
Nanoscience & Nanotechnology
Yoo-Bin Kwon, Jae-Ho Kim, Young-Kwan Kim
Summary: An efficient protection strategy has been developed to enhance the adhesion force and stability of silver nanowire-based transparent electrodes. Chitin nanofibers (CNFs) and alkali lignin (AL) are assembled on the surface of AgNW TEs through layer-by-layer (LBL) assembly. The resulting CNF/AL bilayer-coated TEs show improved adhesion force and durability without compromising their electrical conductivity and transmittance.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Inorganic & Nuclear
Seulgi Kim, Jihye Oh, Ki-Min Park, Shim Sung Lee, In-Hyeok Park
Summary: The formation of pseudocapsule type homo- and heteromultinuclear complexes of calix[6]-mono-crown-5 (H-4 L) encapsulating from 4 to 6 alkali metal ions is reported. The complexes are formed through interligand interactions and C-H center dot center dot center dot pi interactions. The preference for metal ions and their positions in forming the pseudocapsules are demonstrated. Solution studies support the superior binding affinity of Rb+ over K+ toward the crown loop.
INORGANIC CHEMISTRY
(2023)
Article
Electrochemistry
Junhao Chen, Azadeh Nilghaz, Xinyu Chen, Shan Liu, Junfei Tian
Summary: This study presents a novel strategy for fabricating a third-generation glucose sensor on a screen-printed carbon electrode (SPCE). The direct electron transfer (DET) between glucose oxidase (GOx) and SPCE was achieved by immobilizing GOx in poly (3,4-ethylenedioxythiophene) (PEDOT) functionalized electrodes. This strategy eliminates the need for a mediated agent and shows high electrochemical responses of glucose in human blood plasma.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Justin C. Bui, Eric W. Lees, Lalit M. Pant, Iryna V. Zenyuk, Alexis T. Bell, Adam Z. Weber
Summary: Electrochemical synthesis using renewable energy to convert feedstocks into chemicals and fuels is promising, but understanding phenomena in porous electrode systems is challenging. Continuum modeling aids in understanding observed behaviors and guiding next-generation device design. Simulating multiscale phenomena in porous electrodes helps understand and improve the performance of electrochemical synthesis devices.
Article
Chemistry, Physical
Hyo Chan Lee, Yoong Ahm Kim, Hee-Jo Lee, Bo-Hye Kim
Summary: This paper presents the capacitive behavior of N-enriched carbon nanofiber/MnO2/carbon nanofibers with a triple layer structure prepared by continuous electrospinning. The introduction of N-functional groups in different layers of the triplex leads to various structural and electrochemical properties. The optimized material exhibits excellent capacitance retention, high energy density, and cycling stability, making it a promising electrode for high-voltage asymmetric supercapacitors in aqueous electrolytes.
Article
Chemistry, Physical
Selin Bac, Abhilash Patra, Kareesa J. Kron, Shaama Mallikarjun Sharada
Summary: This paper provides an overview of state-of-the-art techniques for efficiently calculating second and higher nuclear derivatives of quantum mechanical energy. Machine learning, automatic differentiation, and matrix completion are emerging methods that show promise in overcoming the challenges of high costs and memory for such calculations. These methods enable reliable predictions of quantum mechanical energy responses to nuclear perturbations.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Yao Yang, Rishi G. Agarwal, Phillips Hutchison, Ruben Rizo, Alexander Soudackov, Xinyao Lu, Enrique Herrero, Juan M. Feliu, Sharon Hammes-Schiffer, James M. Mayer, Hector D. Abruna
Summary: This study reveals that Pt(111) exhibits higher ORR activity in D2O compared to H2O, and the inverse kinetic isotope effects (KIEs) are closely related to the coverage and binding strength.
Review
Chemistry, Multidisciplinary
Elsa C. Y. Yan, Ethan A. Perets, Daniel Konstantinovsky, Sharon Hammes-Schiffer
Summary: Chemists have been fascinated by the interplay of chirality, water, and interfaces, and its potential in elucidating biological functions. However, technical challenges have hindered the study of this chemistry. Using chiral SFG, researchers have been able to detect protein folding and DNA structures as well as water behaviors at interfaces. This method shows promise in probing the intricate chemical interplay of chirality, water, and interfaces.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Editorial Material
Chemistry, Multidisciplinary
Michelle L. Personick
Article
Chemistry, Physical
Tao E. Li, Sharon Hammes-Schiffer
Summary: Within the NEO framework, the RT-NEO-TDDFT approach allows simulation of coupled electronic-nuclear dynamics. The BO approximation within this approach enables larger time steps and fixes the unphysical asymmetric Rabi splitting observed in previous simulations. Furthermore, it provides a foundation for various chemical and biological applications.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Mathew Chow, Eleftherios Lambros, Xiaosong Li, Sharon Hammes-Schiffer
Summary: This study introduces a new nuclear-electronic orbital (NEO) QM/MM approach for simulating chemical reactions in atomistic and heterogeneous environments. It allows the quantization of specified nuclei, such as protons, using NEO-density functional theory. The approach considers proton delocalization, polarization, anharmonicity, and zero-point energy in geometry optimizations and dynamics. The study provides expressions for the energies and gradients associated with the NEO-QM/MM method and demonstrates its potential application in solvation and dynamics studies.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Physical
Ahmed Mohamed, Sean C. Edington, Maxim Secor, James R. Breton, Sharon Hammes-Schiffer, Mark A. Johnson
Summary: Cryogenic ion vibrational spectra are used to characterize the intrinsic spectroscopic responses of D2-tagged cyanobenzoate derivatives. The location of the -CO2- headgroup on the ring and its interaction with divalent metal ions are analyzed. The ortho isomer shows a unique tridentate binding motif and different spectral responses upon metal ion complexation. Electronic structure calculations provide insights into the origins of these spectroscopic features and their implications for metal binding in chemical and biological systems.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Daniel Konstantinovsky, Ethan A. Perets, Ty Santiago, Kristian Olesen, Zhijie Wang, Alexander V. Soudackov, Elsa C. Y. Yan, Sharon Hammes-Schiffer
Summary: We develop an electrostatic map that directly responds to the biological complexity of protein NH stretch, which is crucial for interpreting chiral sum frequency generation spectroscopy (chiral SFG). By linking the local electric field to vibrational frequencies and transition dipoles, we improve the agreement with experimental results and show the importance of couplings between NH and OH vibrations in the interpretation of chiral SFG spectra. This work enhances the utility of NH stretch in biomolecular spectroscopy.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Correction
Chemistry, Physical
Daniel Konstantinovsky, Ethan A. Perets, Ty Santiago, Kristian Olesen, Zhijie Wang, Alexander V. Soudackov, Elsa C. Y. Yan, Sharon Hammes-Schiffer
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Eleftherios Lambros, Benjamin Link, Mathew Chow, Sharon Hammes-Schiffer, Xiaosong Li
Summary: To account for nuclear quantum effects and solvent environments in simulations of chemical processes, the nuclear-electronic orbital approach is combined with a polarizable continuum model (PCM). This NEO-PCM approach is employed to investigate the influence of solvation on nuclear polarization by studying a water dimer and a series of protonated water tetramers. Nuclear polarization is analyzed based on changes in proton density and oxygen-hydrogen bond length. The results reveal that solvation enhances nuclear polarization as the dielectric constant increases. In the water dimer, the internally hydrogen-bonded proton polarizes more than the externally free proton. Additionally, proton quantization leads to greater solvent polarization through their mutual polarization. These calculations emphasize the intricate interplay among electronic, nuclear, and solvent polarization in chemical systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Phillips Hutchison, Corey J. Kaminsky, Yogesh Surendranath, Sharon Hammes-Schiffer
Summary: Surface immobilized catalysts are highly promising for energy conversion reactions, and understanding their mechanistic principles is crucial for rational design. This study investigates the behavior of CoTPP on a graphitic surface using density functional theory calculations. The results reveal that the adsorbed molecule undergoes concerted proton-coupled electron transfer, forming a cobalt hydride and avoiding redox reactions. These findings have important implications for electrocatalysis and surface immobilized catalysts.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Physical
Maxim Secor, Alexander V. Soudackov, Sharon Hammes-Schiffer
Summary: Developing cost-effective catalysts with nonprecious metals is crucial for chemical-to-electrical conversion. Artificial neural networks were trained to predict binding free energies of metal-nitrogen-doped carbon complexes, enabling the discovery of efficient catalysts for electrochemical energy conversion.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Joseph A. Dickinson, Qi Yu, Sharon Hammes-Schiffer
Summary: The nuclear-electronic orbital multistate density functional theory (NEO-MSDFT) approach is developed to describe hydrogen tunneling systems involving multiple quantum protons. This approach quantizes the transferring protons and treats them with molecular orbital techniques on the same level as the electrons. The study provides a foundation for nuclear-electronic quantum dynamics simulations of multiple proton transfer processes.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Mohammad Sahil, Tejender Singh, Soumya Ghosh, Jagannath Mondal
Summary: In this study, a multisubstrate-bound state, named the 3site state, was discovered in cytochrome P450cam. This state involves the simultaneous binding of three camphor molecules in different locations around P450cam, which communicate with each other and cooperate to make the enzyme functional. The 3site state fits the NMR data better than previously known bound states and suggests a departure from the conventional understanding of cytochrome P450.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Xiaofan Jia, Kai Cui, Jose L. Alvarez-Hernandez, Carrie L. Donley, Albert Gang, Sharon Hammes-Schiffer, Nilay Hazari, Sungho Jeon, James M. Mayer, Hannah S. Nedzbala, Bo Shang, Eric A. Stach, Eleanor Stewart-Jones, Hailiang Wang, Alexa Williams
Summary: Three molecular Re hydrides with silatrane functional groups were synthesized for attachment on metal oxide surfaces. These complexes demonstrated similar electronic properties to a control compound and acted as electrocatalysts for CO2 reduction in solution. However, when immobilized on surfaces, the hydride ligand was lost and the complexes degraded. This work exemplifies the challenges of attaching molecular hydride complexes to metal oxide surfaces.
Article
Chemistry, Physical
Ruozhu Feng, Ying Chen, Xin Zhang, Benjamin J. G. Rousseau, Peiyuan Gao, Ping Chen, Sebastian T. Mergelsberg, Lirong Zhong, Aaron Hollas, Yangang Liang, Vijayakumar Murugesan, Qian Huang, Eric Walter, Sharon Hammes-Schiffer, Yuyan Shao, Wei Wang
Summary: Redox flow batteries with strategically designed proton regulators demonstrate improved kinetics and performance, enhancing rate capability, capacity, and cycling. The addition of b-cyclodextrin organic additive in fluorenone-based flow batteries allows for increased alcohol oxidation rates. This study provides a new avenue for enhancing the kinetics of aqueous organic flow batteries by modulating the reaction pathway with a homogeneous catalyst.