Article
Chemistry, Physical
Jiuli Chang, Wenyu Wang, Dapeng Wu, Fang Xu, Kai Jiang, Yuming Guo, Zhiyong Gao
Summary: Efficient catalytic electrodes are crucial for producing green hydrogen via water electrolysis. The replacement of oxygen evolution reaction by tailored electrooxidation of certain organics enables co-production of hydrogen and value-added chemicals, saving energy and ensuring safety.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Physical
E. P. Antonova, A. V. Khodimchuk, E. S. Tropin, A. V. Fetisov, N. M. Porotnikova
Summary: The effect of electrode polarization on the electrochemical activity of La2NiO4+d and La1.9Ca0.1NiO4+d electrodes in contact with the Ce0.8Sm0.2O1.9 electrolyte is studied by impedance spectroscopy. Anodic polarization facilitates electrode reaction and decreases the polarization resistance. The effect of cathodic polarization differs between the electrodes: the polarization resistance of La2-NiO4+d electrode slightly increases, while the polarization resistance of La1.9Ca0.1NiO4+d electrode strongly decreases. The polarization mostly affects the low-frequency stage of the electrode reaction.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Multidisciplinary
Yaqian Yu, Kang Jiang, Min Luo, Yang Zhao, Jiao Lan, Ming Peng, Frank M. F. de Groot, Yongwen Tan
Summary: By utilizing a self-activation strategy, an atomic nickel decorated nanoporous iridium catalyst was created to enable efficient hydrogen evolution reaction (HER) over a wide pH range.
Article
Chemistry, Multidisciplinary
Kazutaka Ikeda, Fumika Fujisaki, Toshiya Otomo, Hidetoshi Ohshita, Takashi Honda, Toru Kawamata, Hiroshi Arima, Kazumasa Sugiyama, Hitoshi Abe, Hyunjeong Kim, Kouji Sakaki, Yumiko Nakamura, Akihiko Machida, Toyoto Sato, Shigeyuki Takagi, Shin-ichi Orimo
Summary: The study revealed the mechanism of catalyzing Al-Ti alloy in NaAlH4 with TiCl3, indicating that Al was partially substituted by Ti during the first desorption process, leading to the formation of highly dispersed nanosized Al-Ti alloy.
APPLIED SCIENCES-BASEL
(2021)
Article
Chemistry, Physical
Shi Tao, Guikai Zhang, Bin Qian, Jun Yang, Shengqi Chu, Chencheng Sun, Dajun Wu, Wangsheng Chu, Li Song
Summary: Heterostructured compounds with engineered interfaces have been widely studied as efficient electrocatalysts for oxygen evolution reaction (OER). However, the mechanism behind their intrinsic activities remains unclear. In this study, a NiSe2/FeSe2 heterostructure catalyst was fabricated through the selenization of Ni-Fe Prussian-blue analog templates, showing low overpotential (230 mV at 10 mA cm(-2)) and long-term durability. In-situ/operando Raman spectroscopy and synchrotron-based X-ray absorption spectroscopy (XAS) were used to investigate the catalytic process, revealing that the surface reconstruction into Ni-O-Fe configurations and the presence of high-valence NiIII-O-FeIII moieties in Ni-FeOOH are responsible for the high oxygen evolution activity. Density functional theory (DFT) simulations further confirmed that electron transfer driven by strong Ni-Fe synergistic effect in the NiSe2/FeSe2 heterostructure not only enhances the density of Ni/Fe active sites but also modulates their nature. This work provides insights into the intrinsic activities of metal compound heterostructures and the relationship between dynamic surface structural evolution and catalytic activity.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Analytical
Bruna F. Baggio, Yvonne Grunder
Summary: This article reviews the progress in material studies using X-ray techniques from an electrochemistry perspective, focusing on in situ/in operando surface X-ray scattering, X-ray absorption spectroscopy, and the combination of both methods. Key examples of in situ and in operando investigation of liquid-solid and liquid-liquid interfaces are presented. The article highlights the importance of X-ray scattering and spectroscopy in understanding electrocatalysis, electrodeposition, and battery materials, and discusses recent developments in the field.
ANNUAL REVIEW OF ANALYTICAL CHEMISTRY, VOL 14, 2021
(2021)
Article
Chemistry, Physical
G. T. Chavan, Anuja Yadav, B. Y. Fugare, Nanasaheb M. Shinde, M. S. Tamboli, S. S. Kamble, A. Sikora, J. Warycha, B. J. Lokhande, Seok-Won Kang, Ahyun Kim, Chan-Wook Jeon
Summary: This study explores the potential application of Co1-xCuxS/CoCuS thin films as materials for supercapacitors. The as-deposited thin films were characterized using various techniques. The results demonstrate that the sample-C-3 (x = 0.075) is suitable for energy storage applications, showing excellent supercapacitive performance and cycling stability, which suggests its potential as an alternative for efficient energy storage devices.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Article
Multidisciplinary Sciences
Jun Huang, Yanxia Chen, Michael Eikerling
Summary: This paper reveals that the surface-charging behaviors of the electrodes in an electrochemical cell are not independently described by their electric double-layer properties. Instead, they are correlated and determined by the electric double-layer and reaction kinetics of both electrodes. Two fundamental equations are derived to describe the correlated surface-charging behaviors, and approximate analytical solutions are provided for low and high current densities for better understanding. The implications of this conceptual analysis for theoretical and computational electrochemistry are discussed, and a strategy to modulate the activity of one electrode by tuning the electric double-layer parameters of the other electrode in a two-electrode electrochemical cell is demonstrated.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Nanoscience & Nanotechnology
Niamat Khuda, Subramaniam Somasundaram, Ajay B. Urgunde, Christopher J. Easley
Summary: A variety of EC biosensors are critical in disease diagnostics, with DNA-based EC sensors showing promise in detecting different analyte classes. This study used methylene blue-labeled DNA strands to monitor the kinetics of DNA hybridization at the electrode surface. By varying the position of the DNA segment relative to the electrode surface and the ionic strength of the solution, interference with DNA hybridization was observed closer to the surface, with greater interference at lower ionic strength. This work highlights the importance of salt concentration and DNA hybridization site in designing DNA-based EC sensors that directly measure hybridization at the electrode surface.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Rhone Brocha P. Silalahi, Yongsung Jo, Jian-Hong Liao, Tzu-Hao Chiu, Eunsaem Park, Woojun Choi, Hao Liang, Samia Kahlal, Jean-Yves Saillard, Dongil Lee, C. W. Liu
Summary: The first hydride-containing 2-electron palladium/copper alloys, PdHCu11 and PdHCu12, were synthesized. X-ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex-missing Cu-11 cuboctahedron and complete Cu-12 cuboctahedron, respectively. PdHCu11 shows excellent HER activity, with an onset potential of -0.05 V (at 10 mA cm(-2)) and consistent HER activity during 1000 cycles in 0.5 M H2SO4.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Joop Enno Frerichs, Mirco Ruttert, Jonas Koppe, Mathis Radzieowski, Martin Winter, Tobias Placke, Michael Ryan Hansen
Summary: Lithium alloying materials are considered as promising candidates to replace the current graphite negative electrode materials in lithium-ion batteries due to their high specific capacity and relatively low cost. The study investigates the electrochemical performance of TiSnSb as a negative electrode material, with a focus on the effect of pre-lithiation on cycling stability, revealing improvements in performance can be achieved through pre-lithiation. Additionally, the mechanism of lithiation of TiSnSb is systematically studied, showing the formation of ternary Li-Sb-Sn species during lithiation.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Physical
Yuta Ito, Changhee Lee, Yuto Miyahara, Shigeaki Yamazaki, Takaya Yamada, Kentaro Hiraga, Takeshi Abe, Kohei Miyazaki
Summary: This study found that F- anions can be electrochemically inserted or deinserted into or from carbon based materials using graphite fluoride (GF) and a high potential Li-based organic electrolyte. The study also observed the formation of amorphous carbon and LiF after insertion, with a discharge capacity almost in line with the theoretical value. The electrochemical properties were determined to be the result of the reversible insertion and deinsertion of F- anions triggered by the formation of LiF.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Analytical
Cindy Peto-Gutierrez, Genaro Vazquez-Victorio, Mathieu Hautefeuille
Summary: In this work, a benchtop fabrication technique for obtaining a planar array of gold nanowrinkled surface electrodes (ANSE) is presented for the construction of electrochemical cells to monitor soluble biomarkers in cell culture environments. The array is characterized and its response as an electrochemical cell is studied. The sensitivity of the sensor to detect nitric oxide (NO) is evaluated, and the influence of environmental conditions on electrochemical measurements is investigated. The electrochemical sensor is then applied to detect nitric oxide released from stimulated endothelial cells as proof of concept.
Article
Chemistry, Physical
Shuang Yang, Zhaochun Liu, Hongyu An, Sven Arnouts, Jim de Ruiter, Floriane Rollier, Sara Bals, Thomas Altantzis, Marta C. Figueiredo, Ivo A. W. Filot, Emiel J. M. Hensen, Bert M. Weckhuysen, Ward van der Stam
Summary: Bimetallic electrocatalysts with tin (Sn) doping in copper oxide (CuO) have demonstrated improved catalytic performance for CO2 reduction reaction. Sn doping enhances the Faradaic efficiency for CO formation and prolongs the catalyst stability. The in situ characterization techniques reveal that Sn doping lowers the binding energy of the adsorbed *CO intermediate, favoring CO desorption.
Article
Chemistry, Multidisciplinary
Kaoruho Sakata, Masako Suzuki-Sakamaki, Kenta Amemiya
Summary: In this study, real-time observation of the evolving oxidation process of a Co thin film was achieved using fluorescence-yield wavelength-dispersive X-ray absorption spectroscopy, revealing the increase of oxide component from the surface to deeper regions as the reaction progresses. The oxidation progress in the depth direction was interpreted by the reaction with O-2 gas at the surface and the interlayer reaction by oxygen migration.
Article
Chemistry, Physical
Jinwon Oh, Arik Beck, Emmett D. Goodman, Luke T. Roling, Anthony Boucly, Luca Artiglia, Frank Abild-Pedersen, Jeroen A. van Bokhoven, Matteo Cargnello
Summary: This study demonstrates that both surface and vapor-mediated ripening occur in distinct temperature regimes, and the sintering mechanism can be altered by adjusting the particle distance. The findings have significant implications for understanding and stabilizing catalysts.
Article
Chemistry, Physical
Prashant Acharya, Jiyun Hong, Ryan Manso, Adam S. S. Hoffman, Laszlo Kekedy-Nagy, Jingyi Chen, Simon R. R. Bare, Lauren F. F. Greenlee
Summary: Operando X-ray absorption spectroscopy (XAS) can be used to study the phase and structural changes of transition metal oxide electrocatalysts during electrocatalytic reactions. In this work, time-resolved changes in the Ni K-edge of a FeNiO (x) bimetallic nanoparticle electrocatalyst were successfully captured. The observed changes are related to the Ni redox transition and the phase transition from hydroxide to oxyhydroxide.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Adam S. Hoffman, Oliver Mueller, Jiyun Hong, Griffin A. Canning, Chia-Yu Fang, Jorge E. Perez-Aguilar, Bruce C. Gates, Simon R. Bare
Summary: Quick-scanning X-ray absorption fine structure (QXAFS) measurements were used to investigate the exchanges of ethylene and CO ligands on a zeolite HY-supported single-site Rh complex. The results showed reversible exchange of the two ligands on the rhodium, with C2H4-for-CO exchange following first-order kinetics and decreasing rate with increasing temperature. Fourier-transform infrared spectra revealed a decrease in the amount of C2H4 sorbed in the zeolite with increasing temperature, consistent with the decrease in exchange rate. These findings illustrate the broad applicability of QXAFS technique in characterizing the dynamics of reactive intermediates on catalysts.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Wanghui Zhao, Gaomou Xu, Zhaochun He, Cheng Cai, Frank Abild-Pedersen, Tao Wang
Summary: In this study, a new theoretical strategy was proposed to achieve both facile CO dissociation and C/O hydrogenation on a catalyst by introducing confined dual active sites. The DFT-based microkinetic modeling showed that the designed Co-Cr2/G dual-site catalyst provided 4-6 orders of magnitude higher turnover frequency for CH4 production compared to cobalt step sites. We believe that this strategy will provide essential guidance for designing state-of-the-art methanation catalysts under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Hemanth Somarajan Pillai, Yi Li, Shih-Han Wang, Noushin Omidvar, Qingmin Mu, Luke E. K. Achenie, Frank Abild-Pedersen, Juan Yang, Gang Wu, Hongliang Xin
Summary: This study uses quantum chemistry and machine learning to understand the reaction mechanism and design efficient electrocatalysts for the electrochemical conversion of ammonia to nitrogen. By training graph neural networks on ab initio data, the authors explore the design space of ternary Pt alloy nanostructures and predict site reactivity, surface stability, and catalyst synthesizability. The machine-learned representation of site motifs provides important insights into chemical bonding at metal surfaces and guides the design of high-performance catalytic systems.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
V. A. Niemann, P. Benedek, J. Guo, Y. Xu, S. J. Blair, E. R. Corson, A. C. Nielander, T. F. Jaramillo, W. A. Tarpeh
Summary: Humans have changed the nitrogen cycle, producing nitrogen commodities while releasing nitrogen contaminants into the environment. These contaminants pose a threat to human and environmental health, but nitrogen commodities are essential for a good quality of life. A possible solution to this global challenge is the removal and recovery of nitrogen contaminants as commodities, which has gained attention from the fields of electrocatalysis and separations. In this perspective, the authors propose the co-design of nitrogen separations and electrocatalytic technologies to address the gaps in understanding and develop tailored technology for nitrogen management challenges. The ultimate goal is to transition to a circular nitrogen economy for a food-safe and environmentally friendly future.
Article
Chemistry, Multidisciplinary
Jinyu Guo, Paige Brimley, Matthew J. Liu, Elizabeth R. . Corson, Carolina Munoz, Wilson A. . Smith, William A. Tarpeh
Summary: The electrochemical nitrate reduction reaction (NO3RR) can be used to clean nitrate-polluted wastewater and produce ammonia in a sustainable way. This study investigates the influence of interfacial electrolyte on NO3RR performance, specifically focusing on the effects of mass transport conditions. Through simulations and experiments, the researchers found that diffusion layer thickness and electrolyte concentration affect NO3RR activity, while interfacial pH determines NO3RR selectivity. By optimizing these factors, they successfully increased the ammonia-to-nitrite selectivity by three times.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Materials Science, Multidisciplinary
Hirohito Ogasawara, Han Wang, Jorgen Gladh, Alessandro Gallo, Ralph Page, Johannes Voss, Alan Luntz, Elias Diesen, Frank Abild-Pedersen, Anders Nilsson, Markus Soldemo, Marc Zajac, Andrew Attar, Michelle E. Chen, Sang Wan Cho, Abhishek Katoch, Ki-Jeong Kim, Kyung Hwan Kim, Minseok Kim, Soonnam Kwon, Sang Han Park, Henrique Ribeiro, Sami Sainio, Hsin-Yi Wang, Cheolhee Yang, Tony Heinz
Summary: We conducted optical pumping and x-ray absorption spectroscopy experiments on a graphene monolayer adsorbed on copper using a free electron laser. Our analysis suggests that the excitation of graphene is primarily due to indirect excitation from hot electron-hole pairs created in the copper. However, once the excitation occurs in graphene, its decay follows a similar path as in previous studies of graphene adsorbed on semiconductors, involving rapid excitation of strongly coupled optical phonons and eventual thermalization. The lifetime of the hot electron-hole pairs in copper likely influences the lifetime of the electronic excitation in graphene.
PHYSICAL REVIEW MATERIALS
(2023)
Article
Electrochemistry
Matthew J. Liu, William A. Tarpeh
Summary: Ammonia is an indispensable compound for modern society, playing a crucial role in fertilizer production and chemical manufacturing. The global demand for ammonia currently exceeds 150 million tons per year and is expected to grow by over 2% annually. The majority of ammonia production, about 96%, is achieved through the energy-intensive Haber-Bosch process, resulting in significant energy consumption and anthropogenic CO2 emissions. The accumulation of reactive nitrogen, particularly from untreated wastewater, disrupts the global nitrogen cycle, leading to imbalanced ecosystems and water quality issues. Finding ways to directly utilize reactive nitrogen in waste streams can offer substantial energy, emission, and cost savings, aligning with the goal of managing the nitrogen cycle and protecting ecosystems.
ELECTROCHEMICAL SOCIETY INTERFACE
(2023)
Article
Environmental Sciences
Valerie A. Niemann, Marten Huck, Hans-Georg Steinrueck, Michael F. Toney, William A. Tarpeh, Sharon E. Bone
Summary: This study investigated the fouling of RO membranes by calcium and silicon under realistic feed conditions using mu-X-ray fluorescence (mu-XRF) mapping and mu-X-ray absorption near-edge fine structure (mu-XANES) spectroscopy. The results showed that both calcium and silicon were abundant in the fouling layer. Additionally, organic compounds were closely related to the presence of calcium and silicon on the RO membrane. These findings provide important insight into the mechanism of RO membrane fouling.
Article
Nanoscience & Nanotechnology
Heng Dong, Xiaohan Shao, Shane Hancox, Sean T. McBeath, William A. Tarpeh, Michael R. Hoffmann
Summary: This study compares the chlorine evolution reaction (CER) catalytic activities of a series of anode samples with different Sb/Co ratios using scanning electrochemical microscopy, demonstrating that Sb sites exhibit higher catalytic activity and the Sb/Co ratios affect the CER selectivity. The high activity of Sb sites highlights the significance of electronic polarization in changing the oxidation states of Co and Sb.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Nanoscience & Nanotechnology
Lars Ostervold, Adam Smerigan, Matthew J. Liu, Leah R. Filardi, Fernando D. Vila, Jorge E. Perez-Aguilar, Jiyun Hong, William A. Tarpeh, Adam S. Hoffman, Lauren F. Greenlee, Ezra Lee Clark, Michael J. Janik, Simon R. Bare
Summary: This study shows that electrolyte cations can have a direct impact on the performance of oxide electrocatalysts by incorporating into their lattice. By investigating the transformation of copper electrodes in alkaline electrolytes, it is found that in Ba(OH)2 electrolytes, ordered BaCuO2 phase is formed and further oxidized to a Cu3+-like Ba- x Cu- y O (z) phase. Moreover, Cu-O bonds and Cu-Ba scattering persist even during reduction. This is the first evidence of direct oxidative incorporation of an electrolyte cation into the bulk lattice to form a mixed oxide electrode. The results suggest a new route for the in situ formation of active and selective oxidation electrocatalysts.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Shyama Charan Mandal, Frank Abild-Pedersen
Summary: The design of heterogeneous catalysts can be accelerated by identifying relevant descriptors that link binding and activation energies to reactivity. This study investigated scaling relations between binding energies of various hydrocarbon-based adsorbates on different Pt surfaces and metal binding energies estimated via the alpha-scheme model. The findings show that the binding energies of certain groups of adsorbates can be used to predict the binding energies of more complex hydrocarbon-based adsorbates.
Article
Chemistry, Multidisciplinary
Benjamin Yeh, Saumil Chheda, Steven D. Prinslow, Adam S. Hoffman, Jiyun Hong, Jorge E. Perez-Aguilar, Simon R. Bare, Connie C. Lu, Laura Gagliardi, Aditya Bhan
Summary: A mixed-valence oxotrimer metal-organic framework (MOF), Ni-MIL-127, with a missing linker defect on the nickel atom catalyzes propylene oligomerization without any cocatalysts or initiators. The catalyst is stable for over 20 hours at 500 kPa and 473 K. The majority of Ni species in the MOF framework catalyze propylene oligomerization, as validated by various analytical techniques.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
