Article
Chemistry, Physical
Adam Baz, Adam Holewinski
Summary: This paper explores the relationships between kinetic observables such as the Tafel slope, apparent activation energy, and apparent reaction orders, and the generalized degree of rate control (DRC). By linking these quantities to DRC, a better understanding of the operative mechanisms of complex electrocatalytic processes can be achieved. Furthermore, it discusses potential impacts of nonidealities on these relationships.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Physical
Janina Willkomm, Sara Bouzidi, Erwan Bertin, Viola Birss, Warren E. Piers
Summary: A [Re(bipyridine)]-carbon hybrid material was developed for efficient CO2 to CO conversion in water, with Re catalyst incorporated into a nanoporous colloid-imprinted carbon powder via electrochemical polymerization. The higher catalyst loadings led to higher Faradaic efficiencies for CO formation and better long-term stability, demonstrating the potential for energy conversion applications using this hybrid material. The study highlights the versatility of (electro)polymerization techniques in combination with nanoporous CIC for preparing hybrid materials.
Article
Electrochemistry
Francesca Greenwell, Gaia Neri, Verity Piercy, Alexander J. Cowan
Summary: A nickel cyclam catalyst modified with pyrene has been synthesised and characterised, showing activity towards CO production in aqueous electrolyte. The non-covalent interaction between the pyrene functional group and carbon electrode supports helps to maintain the electroactivity of the catalyst.
ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Physical
Libo Sun, Vikas Reddu, Shibo Xi, Chencheng Dai, Yuan Sheng, Tan Su, Adrian C. Fisher, Xin Wang
Summary: Ligands play a critical role in the electrocatalytic CO2 reduction reaction (CO2RR) based on heterogeneous molecular catalysts. This study explores the development of new N4 cobalt complexes based on pyridine subunits, which exhibit CO2RR activity with high selectivity and excellent performance on carbon nanotubes.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Physical
Fang-Bing Liu, Nan Lin, Lin-Chuan Cong, Xin-Xin Li, Fu-Yu Han, De-Yuan Xin, Hai-Bo Lin
Summary: In this study, pure beta-Ni(OH)(2) and amorphous Ni(OH)(2) were synthesized on nickel foam (NF) using a stepwise electrodeposition technique and their catalytic performances for the oxidation of 5-hydroxymethylfurfural (HMF) were evaluated. The beta-Ni(OH)(2) nanosheets-decorated electrode (beta-NiNS/NF) showed excellent interfacial lattice matching with the substrate nickel, leading to enhanced electron transfer, electrocatalytic activity, interfacial stability, and HMF adsorption capability. Consequently, the beta-NiNS/NF electrode exhibited improved HMF conversion and selectivity, achieving a high furan dicarboxylic acid (FDCA) yield.
Article
Chemistry, Multidisciplinary
Difei Xiao, Xiaolei Bao, Dujuan Dai, Yugang Gao, Shenghe Si, Zeyan Wang, Yuanyuan Liu, Peng Wang, Zhaoke Zheng, Hefeng Cheng, Ying Dai, Baibiao Huang
Summary: This study synthesized a series of Ni3S2/NiOx-n catalysts with controllable compositions and well-defined structures using a novel in situ controlled surface reconstruction strategy, for the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), aiming to enhance the efficient production of biomass-derived high-value-added chemicals. It was found that by adjusting the ratio of NiOx to Ni3S2 on the catalysts surface, the adsorption behavior of HMF and OH- can be continuously adjusted, achieving a balance of competitive adsorption and improving the performance and stability of the catalyst.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Cong Guo, Yunying Huo, Qiao Zhang, Kai Wan, Guangxing Yang, Zhiting Liu, Feng Peng
Summary: The electrocatalytic conversion of biomass into high-value-added chemicals is an effective method of green chemistry. Catalyst materials derived from metal-organic frameworks (MOFs) have unique physicochemical properties, making them a popular choice. In this study, a non-precious metal CoxNiyS electrocatalyst derived from MOFs was used for the oxidation of biomass-derivative 5-hydroxymethylfurfural (HMF). The results showed that the Co:Ni ratio influenced the HMF conversion rate, with the highest rate achieved at a ratio of 2:1.
Article
Chemistry, Physical
Sean J. Hoehn, Sarah E. Krul, Michael M. Pogharian, Erqian Mao, Carlos E. Crespo-Hernandez
Summary: This Letter compares the photostability and excited-state dynamics of 5mCyd with those of Cyd. The results show that 5mCyd has a higher fluorescence yield and a longer excited-state lifetime. Importantly, the photodegradation rate of 5mCyd is 3 times smaller than that of Cyd, primarily due to internal conversion.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Correction
Chemistry, Multidisciplinary
Yang Gao, Yurui Xue, Taifeng Liu, Yuxin Liu, Chao Zhang, Chengyu Xing, Feng He, Yuliang Li
Summary: Hydrogen energy plays a significant role in promoting the development of modern society, requiring efficient hydrogen production methods and technologies. The study on bimetallic oxide clusters on a graphdiyne heterostructure demonstrates outstanding electrocatalyst properties with high activity and durability.
Article
Chemistry, Multidisciplinary
Chao Wang, Yueying Chu, Min Hu, Wenjin Cai, Qiang Wang, Guodong Qi, Shenhui Li, Jun Xu, Feng Deng
Summary: The study demonstrates that electron-deficient cyclopentenyl cations in ZSM-5 zeolite can capture compounds produced in the MTO reaction through noncovalent interactions, including alkanes, methanol, and olefins. These carbocation-induced noncovalent interactions modulate the product selectivity of the hydrocarbon pool reaction. The research identified intermolecular spatial proximities/interactions through two-dimensional C-13-C-13 correlation solid-state NMR spectroscopy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Retraction
Chemistry, Multidisciplinary
D. Gopi, E. Shinyjoy, A. Karthika, S. Nithiya, L. Kavitha, D. Rajeswari, Tingting Tang
Summary: Retraction of the article "Single walled carbon nanotubes reinforced mineralized hydroxyapatite composite coatings on titanium for improved biocompatible implant applications" by D. Gopi et al., RSC Adv., 2015, 5, 36766-36778, https://doi.org/10.1039/C5RA04382D.
Correction
Chemistry, Multidisciplinary
Ali Nazari, Ali Maghsoodpoor, Jay G. Sanjayan
Summary: This study investigates the effects of NaOH concentration and curing temperature on boroaluminosilicate geopolymers.
Article
Chemistry, Physical
Natsumi Orimo, Yo-ichi Yamamoto, Shutaro Karashima, Alexie Boyer, Toshinori Suzuki
Summary: Ultrafast extreme ultraviolet photoelectron spectroscopy was conducted on 6methyluracil (6mUra) and 5-fluorouracil (5FUra) in the gas phase, and on 6mUra and 5fluorouridine in an aqueous environment. In the gas phase, internal conversion (IC) from 1 pi pi* to 1n pi* states occurs in tens of femtoseconds, followed by intersystem crossing to the 3 pi pi* state in several picoseconds. In an aqueous solution, 6mUra undergoes IC almost exclusively to the ground state (S0) in about 100 fs, which is similar to unsubstituted uracil but faster than thymine (5-methyluracil). The different dynamics for C5 and C6 methylation suggest that IC from 1 pi pi* to S0 is facilitated by the out-of-plane (OOP) motion of the C5 substituent. The slow IC for C5-substituted molecules in an aqueous environment is due to the required solvent reorganization for this OOP motion to occur. The slow rate for 5FUrd may be attributed to an increased barrier height caused by C5 fluorination.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Nanoscience & Nanotechnology
Jyoti Rohilla, Sahil Thakur, Keshav Kumar, Raghubir Singh, Varinder Kaur
Summary: The present study synthesized Sn-NaMOF using solvothermal method and used it as a support for Pd nanoparticles. The resulting Pd NPs/Sn-Na MOF showed excellent catalytic activity for the conversion of fructose to 5-HMF. The catalyst exhibited fast conversion, recyclability, and high yield of 5-HMF in aqueous medium without the formation of side products.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Analytical
Ping Lei, Jiehui Liu, Shuyuan Zhuge, Zhe Lu
Summary: The NASICON-structure Na3V2(PO4)3 has attracted attention for its ion diffusion channels, discharging platform, and volume deformation, making it a potential cathode material for aqueous zinc-ion batteries. However, this study found that NVP@C undergoes a structural phase change and converts to a composite after 50 cycles. By cycling the NVP@C batteries at 60 degrees C for only 1 cycle, the in-situ generation of composite (NVP@C-60 degrees C) was achieved, which exhibited high capacity and excellent rate performance.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Takeshi Nishimoto, Tatsuya Shinagawa, Takahiro Naito, Kazuhiro Takanabe
Summary: This study explores the impact of buffer ions on OER performance using a model IrOx electrocatalyst, finding that the OER kinetics is more efficient with OH- oxidation compared to H2O. The research highlights how the presence of a buffer can significantly reduce overpotential and improve performance by facilitating local OH- supply kinetics.
Article
Chemistry, Multidisciplinary
Sangwook Park, Angel T. Garcia-Esparza, Hadi Abroshan, Baxter Abraham, John Vinson, Alessandro Gallo, Dennis Nordlund, Joonsuk Park, Taeho Roy Kim, Lauren Vallez, Roberto Alonso-Mori, Dimosthenis Sokaras, Xiaolin Zheng
Summary: This study demonstrates the promoting effect of MoOx on the thermal oxidation of MoS2 monolayers, and shows that removing MoOx can increase the thermal oxidation onset temperature of monolayer MoS2.
Article
Chemistry, Physical
Xiaofei Lu, Hassan Ait Ahsaine, Busra Dereli, Angel T. Garcia-Esparza, Marco Reinhard, Tatsuya Shinagawa, Duanxing Li, Karim Adil, Mohamed Rachid Tchalala, Thomas Kroll, Mohamed Eddaoudi, Dimosthenis Sokaras, Luigi Cavallo, Kazuhiro Takanabe
Summary: In this study, it was demonstrated that iron porphyrin-based molecular catalysts can achieve nearly 100% selectivity in electrocatalytic CO2 reduction to CO in water. By combining in operando experiments and theoretical calculations, the presence of Fe(II) species as catalytic sites accommodating CO during the cathodic reaction was identified. Density functional calculations suggested that the ligand-reduced state with oxidized Fe predominates in the catalytic cycle prior to the rate-controlling step.
Article
Chemistry, Multidisciplinary
Takahiro Naito, Tatsuya Shinagawa, Takeshi Nishimoto, Kazuhiro Takanabe
Summary: This study demonstrates that electrolyte engineering and the use of a glass sheet as a gas separator can reduce gas crossover and bubble permeation in near-neutral pH water electrolysis, leading to higher purity of hydrogen production.
Article
Chemistry, Physical
Duanxing Li, Shintaro Yoshida, Bhavin Siritanaratkul, Angel T. Garcia-Esparza, Dimosthenis Sokaras, Hirohito Ogasawara, Kazuhiro Takanabe
Summary: The study investigated the oxidative coupling of methane over a K2WO4/SiO2 catalyst, finding that the addition of H2O increased CH4 conversion rate and C2 selectivity. The presence of K2O2 and KO2 species at high temperatures was shown to catalyze H2O activation for OH radical generation, contributing to the OCM reaction.
Article
Chemistry, Multidisciplinary
Angel T. Garcia-Esparza, Sangwook Park, Hadi Abroshan, Oscar A. Paredes Mellone, John Vinson, Baxter Abraham, Taeho R. Kim, Dennis Nordlund, Alessandro Gallo, Roberto Alonso-Mori, Xiaolin Zheng, Dimosthenis Sokaras
Summary: This study reveals the presence of clustered S-vacancies on the basal plane of monolayer MoS2 and provides insights into their role in catalytic reactions through in situ X-ray absorption spectroscopy and first-principles calculations.
Article
Chemistry, Physical
Shuai Yuan, Jiayu Peng, Bin Cai, Zhehao Huang, Angel T. Garcia-Esparza, Dimosthenis Sokaras, Yirui Zhang, Livia Giordano, Karthik Akkiraju, Yun Guang Zhu, Rene Huebner, Xiaodong Zou, Yuriy Roman-Leshkov, Yang Shao-Horn
Summary: The oxygen evolution reaction plays a central role in the production of chemicals and energy carriers using electrons. Metal hydroxide-organic frameworks have been demonstrated to be a tunable catalytic platform for this reaction, with stability being dictated by π-π interactions and activity being modulated by transition metals. By combining the high tunability of enzymatic systems with known oxide-based catalysts, it is possible to achieve both high activity and stability. This study reports on the synthesis of metal hydroxide-organic frameworks that act as a tunable catalytic platform for the oxygen evolution reaction, with stability being determined by π-π interactions between adjacent stacked linkers and catalytic activity being influenced by the nature of transition metals in the hydroxides. Substituting Ni-based metal hydroxide-organic frameworks with acidic cations or electron-withdrawing linkers significantly enhances the activity of the oxygen evolution reaction, with Fe substitution achieving a mass activity of 80 A g(catalyst)(-1) at 0.3 V overpotential for 20 hours. Density functional theory calculations correlate the enhanced activity with the modulation of Ni redox and the optimized binding of oxygenated intermediates by the metal hydroxide-organic frameworks.
Article
Chemistry, Multidisciplinary
Hiroki Komiya, Tatsuya Shinagawa, Kazuhiro Takanabe
Summary: Direct seawater electrolysis simplifies the process and reduces the cost of green hydrogen production, but impurities in seawater, especially chloride ions, can cause electrode corrosion. The CoFeOxHy/Ti electrode with carefully tuned properties shows efficient oxygen evolution reaction catalysis with an active site motif and enlarged surface area.
Article
Chemistry, Multidisciplinary
Takeshi Nishimoto, Tatsuya Shinagawa, Takahiro Naito, Kazuki Harada, Masaaki Yoshida, Kazuhiro Takanabe
Summary: Efficient oxygen evolution reaction (OER) with high current density reaching 1 A cm(-2) was achieved through interactive optimization of electrolyte and electrode at non-extreme pH levels. The OER performance was improved by introducing Cu or Au as the third element during electrode preparation, leading to enhanced electrochemical surface area.
Article
Chemistry, Physical
Marco Reinhard, Dean Skoien, Jacob A. Spies, Angel T. Garcia-Esparza, Benjamin D. Matson, Jeff Corbett, Kai Tian, James Safranek, Eduardo Granados, Matthew Strader, Kelly J. Gaffney, Roberto Alonso-Mori, Thomas Kroll, Dimosthenis Sokaras
Summary: We have developed a dedicated end-station for solution phase high repetition rate picosecond hard x-ray spectroscopy at the Stanford Synchrotron Radiation Lightsource. Using a high-power ultrafast ytterbium-doped fiber laser and gating the x-ray detectors, we achieved time-resolved x-ray measurements with a high signal-to-noise ratio. This end-station enables systematic time-resolved science programs using the monochromatic beam at the Stanford Synchrotron Radiation Lightsource.
STRUCTURAL DYNAMICS-US
(2023)
Article
Chemistry, Multidisciplinary
Xingyu Qi, Tatsuya Shinagawa, Xiaofei Lu, Yuhki Yui, Masaya Ibe, Kazuhiro Takanabe
Summary: By externally controlling the electrochemical potential of catalysts, this study successfully reduces high coverage of a substance to improve thermal-catalytic rates, leading to a significant increase in CO2 formation rate.
Article
Chemistry, Multidisciplinary
Jinkyu Lim, Angel T. Garcia-Esparza, Jae Won Lee, Gihun Kang, Sangyong Shin, Sun Seo Jeon, Hyunjoo Lee
Summary: The selectivity of CO2 reduction to formic acid can be enhanced by synthesizing Sn-Cu@Sn dendrites with a core@shell architecture, showing great potential for large-scale applications.
Review
Chemistry, Inorganic & Nuclear
Takahiro Naito, Tatsuya Shinagawa, Takeshi Nishimoto, Kazuhiro Takanabe
Summary: This article reviews studies from the past decade on the role of iridium oxides in the OER, illustrating possible catalytic cycles and highlighting discrepancies in proposed mechanisms. Future comprehensive and systematic in situ studies are called for to address variations in experimental conditions. Additionally, a recent approach for improving the activity and stability of OER catalysts is discussed.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Elisa Biasin, Daniel R. Nascimento, Benjamin I. Poulter, Baxter Abraham, Kristjan Kunnus, Angel T. Garcia-Esparza, Stanislaw H. Nowak, Thomas Kroll, Robert W. Schoenlein, Roberto Alonso-Mori, Munira Khalil, Niranjan Govind, Dimosthenis Sokaras
Summary: By leveraging recent advances in high-energy-resolution tender X-ray spectroscopy and theoretical calculations, novel insights into the chemical bonding of a series of Ru(ii)- and Ru(iii)-complexes are revealed. The experimental Ru 2p4d resonant inelastic X-ray scattering (RIXS) and theoretical calculations accurately assign spectral features and quantify metal-ligand bonding interactions. This combined experimental and theoretical approach reliably characterizes the ground and excited valence states of Ru complexes, serving as a basis for future investigations in biological and chemical applications of ruthenium or other 4d metals.
Review
Chemistry, Multidisciplinary
Xingyu Qi, Tatsuya Shinagawa, Fuminao Kishimoto, Kazuhiro Takanabe
Summary: This paper discusses the chemical potential of electrons in solid catalysts during thermal catalysis, and proposes the use of electrochemical tools to quantify the illdefined chemical potentials of solids. Additionally, electrochemical means can directly perturb catalyst potentials, affecting the coverage of adsorbates.
