Article
Chemistry, Multidisciplinary
Akbar Mahdavi-Shakib, K. B. Sravan Kumar, Todd N. Whittaker, Tianze Xie, Lars C. Grabow, Robert M. Rioux, Bert D. Chandler
Summary: H-2 adsorption on Au catalysts is weak and reversible, posing challenges for quantitative studies. By investigating H-2 adsorption on Au/TiO2 catalysts, electron transfer to the support was observed, leading to shifts in FTIR background signals, which were used to quantify H-2 adsorption. Additionally, a new H-O-H bending vibration associated with proton adsorption on distinct metal-support interface sites was identified, providing new insights into the nature and dynamics of H-2 adsorption at the Au/TiO2 interface.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Akihiro Nakayama, Ryusei Sodenaga, Yuvaraj Gangarajula, Ayako Taketoshi, Toru Murayama, Tetsuo Honma, Norihito Sakaguchi, Tetsuya Shimada, Shinsuke Takagi, Masatake Haruta, Botao Qiao, Junhu Wang, Tamao Ishida
Summary: Cation-and anion-substituted hydroxyapatites (sHAPs) supported gold catalysts exhibit strong metal support interaction (SMSI) under oxidative atmosphere, enhancing the cationic properties of gold and increasing catalytic activity. Controlling the degree of SMSI allows for tuning the electronic state of metal nanoparticles and providing highly active and durable catalysts for target reactions.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Yifan Yang, Jun Ma, Mengqin Yao, Shuo Geng, Fei Liu
Summary: The sluggish kinetics of the hydrogen evolution reaction (HER) in alkaline media can be overcome by using a catalyst consisting of metallic Ni on Fe-doped MoOx nanosheets (Ni/FeMoOx) to promote water dissociation. The Ni/Fe-MoOx catalysts exhibit better HER performance than Ni/MoOx catalysts, requiring lower overpotentials to achieve the same current densities. This is attributed to the stronger water dissociation ability caused by Fe doping, which provides more available protons in the alkaline medium. Furthermore, Fe doping enhances the oxygen evolution reaction (OER) performance of the catalysts, resulting in a low cell voltage and excellent stability in a water splitting device.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Chemistry, Physical
Shu Yang, Wei Li, YiFu Li, XiuMin Chen, Huan Zhang, Baoqaing Xu, Bin Yang
Summary: Density functional theory calculations were used to investigate the structural and electronic properties of AgnSnn clusters. It was found that the Ag4Sn4 cluster has a unique magic size and the addition of Sn atoms enhances the catalytic performance of silver clusters.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Valery Muravev, Alexander Parastaev, Yannis van den Bosch, Bianca Ligt, Nathalie Claes, Sara Bals, Nikolay Kosinov, Emiel J. M. Hensen
Summary: The size and structure of supported transition metals, which act as active sites, can be adjusted to optimize the catalytic performance of heterogeneous catalysts. In single-atom metal catalysts, the support itself has a significant impact on catalytic properties. In this study, we demonstrate that the size of the CeO2 support determines the reactivity of atomically dispersed Pd in CO oxidation. Small CeO2 nanocrystals (around 4 nanometers) show high activity in CO-rich conditions, while medium-sized CeO2 (around 8 nanometers) is preferred for lean conditions. Detailed spectroscopic investigations reveal size-dependent redox properties at the Pd-CeO2 interface.
Article
Chemistry, Inorganic & Nuclear
Jing Sun, Xiaodan Yan, Lingzheng Wang, Zhenlang Xie, Guolong Tian, Lin Wang, Ayisha He, Simin Li, Qingxiang Guo, Jinlu He, Hui Shen
Summary: A family of 29 copper nanoclusters with precise structures has been prepared, showing different surface properties but the same Cu-13 kernel. These clusters exhibit distinct optical profiles and catalytic performance, indicating the importance of surface structure in shaping the behaviors of copper nanomolecules. This work not only exemplifies the efficiency of surface engineering for controlling properties of well-defined copper nanoclusters but also provides a new family of Cu materials with controlled surface motifs.
INORGANIC CHEMISTRY
(2023)
Article
Physics, Applied
Long Zhang, Jing Pan, Min Li, Ivo A. W. Filot, Emiel J. M. Hensen, Hui Wang
Summary: In this study, the structures and compositions of CeO2-supported Cu-based bimetallic clusters in an oxygen-rich environment were investigated using first-principles calculations, genetic algorithm, and grand canonical Monte Carlo methods. It was found that the catalytic activity and reaction mechanism of the oxide-supported alloy catalysts vary with the composition and oxidation state of the alloy nanocluster under the reaction conditions.
PHYSICAL REVIEW APPLIED
(2023)
Article
Chemistry, Physical
Wenxiu Yan, Yongli Shen, Chao An, Lina Li, Rui Si, Changhua An
Summary: This study utilized room-temperature plasma to convert Fe3+-doped Ni(OH)(2) nanosheets into porous hcp Ni engineered by FeOx clusters, forming Ni-O-Fe bonds to catalyze the oxygen evolution reaction. The interaction between FeOx clusters and Ni interface stimulated the generation of active intermediates, promoting the OER rate.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Review
Chemistry, Physical
Chao Yang, Yeshuang Wang, Meisheng Liang, Zhelin Su, Xuan Liu, Huiling Fan, Teresa J. Bandosz
Summary: This article focuses on the importance of room temperature H2S catalytic oxidation on carbon-based materials, highlighting the various factors influencing catalyst performance and summarizing recent research findings and possible catalytic oxidation mechanisms.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Multidisciplinary
Tianqi Gao, Yongli Shen, Lin Gu, Zhaocheng Zhang, Wenjuan Yuan, Wei Xi
Summary: The excellent low-temperature oxidation performance and stability of nanogold catalysts have attracted significant interest. In situ electron microscopy and mass spectrometry results show that nitrogen is oxidized, and the catalyst surface undergoes reconstruction during the process. Strain analysis of the catalyst surface and first-principles calculations show that the tensile strain of the catalyst surface affects the oxidation performance of gold catalysts by enhancing the adsorption ability and dissociation of O-2. The newly formed active oxygen atoms on the gold surface act as active sites in the nitrogen oxidation reaction, significantly enhancing the oxidation ability of gold catalysts. This study provides evidence for the dissociation mechanism of oxygen on the gold surface and new design concepts for improving the oxidation activity of gold catalysts and nitrogen activation.
Review
Chemistry, Multidisciplinary
Shuohao Li, Shenguang Fu, Yuqing Gong, Nuojie Wu, Lei Wang, Liang Wang
Summary: This review summarizes the synthesis methods and specific contributions of supports to the catalytic performance of supported gold cluster catalysts, as well as the deep interaction mechanisms. Additionally, it discusses the opportunities and challenging issues in improving catalytic performance and structural stability of supported gold clusters in catalysis applications.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shuhui Liu, Hua Xu, Dongdong Liu, Hao Yu, Fan Zhang, Peng Zhang, Ruolin Zhang, Wei Liu
Summary: Atom dispersion in metal supported catalysts is crucial for their catalytic performances. Traditional spectroscopy methods are unable to accurately distinguish different structures. By using a methodology called electron-microscopy-based atom recognition statistics (EMARS), catalyst dispersion can be redefined at atomic precision in real space.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Li-Juan Ma, Jianfeng Wang, Jianfeng Jia, Hai-Shun Wu
Summary: In this study, defects and interstitial B are utilized to enhance the stability and H2 dissociation ability of palladium nanoparticles supported by graphene. The results indicate that defects can effectively avoid the desorption competition between palladium nanoparticles and hydrogen molecules, and the introduction of interstitial B can decrease the energy barrier for hydrogen dissociation on the surface.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Physical
Huan Zhang, Juan Wang, Fengqi Qin, Huiling Liu, Cheng Wang
Summary: This study fabricated a V-doped Ni3N/Ni heterostructure catalyst through nitridation treatment, showing comparable high activity and durability to commercial Pt/C under alkaline conditions.
Article
Chemistry, Multidisciplinary
Jia Dong, Ze-Hua Gao, Qian-Fan Zhang, Lai-Sheng Wang
Summary: The research reports the synthesis and characterization of a gold nanohydride protected by diphosphine ligands. The nanohydride consists of an Au-22 core with two Au-11 units bridged by four H atoms and delocalized Au-H-Au bonds. It exhibits various transformations related to hydrogen and serves as a versatile model catalyst for understanding hydrogen reactions on gold nanoparticle surfaces.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Masato Kobayashi, Yuta Oba, Tomoko Akama, Tetsuya Taketsugu
Summary: This paper proposes a practical electronic calculation method for lanthanide complexes, which introduces the frozen core potential approximation and relaxation of rotational degrees of freedom to improve the accuracy and convergence of the calculations.
JOURNAL OF MATHEMATICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Takao Tsuneda, Hiroki Sumitomo, Masatoshi Hasebe, Takuro Tsutsumi, Tetsuya Taketsugu
Summary: It has been established that the reactive orbital energy theory (ROET) can theoretically reproduce the rule-based electronic theory diagrams of organic chemistry. By studying the charge transfer natures of typical organic carbon-carbon and carbon-heteroatom bond formation reactions, the ROET provides insights into the reactive orbitals and charge transferability indices. The ROET analyses also reveal the detailed orbital-based mechanisms for these reactions, explaining the pi-bond formations in acidic conditions and sigma-bond formations at alpha-carbons in basic conditions. Moreover, it is suggested that the methyl group plays a role in accepting and donating electrons in these reactions.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jiang Deng, Min Gao, Jun-ya Hasegawa, Xiaoyu Zhang, Aiyong Wang, Aling Chen, Dengsong Zhang
Summary: Metal oxides have been used as supports for heterogeneous catalysis for many years, but they are prone to coking in high-temperature applications. In this study, we found that a boron nitride (BN)-immobilized nickel (Ni) catalyst exhibits remarkable coking resistance in dry reforming of methane. The key to this coking resistance lies in the selective activation of the C-H bond by the BN-supported Ni catalyst.
Article
Chemistry, Physical
Masatsugu Nishida, Tomoko Akama, Masato Kobayashi, Tetsuya Taketsugu
Summary: In this study, a time-dependent Hartree-Fock-Bogoliubov (HFB) method is proposed for treating the excited states of molecules with static correlations at a reasonable computational cost. The canonical basis variant of the TDHFB method proposed by Ebata et al. is also considered to avoid electron number violations. Calculation results for the elongated hydrogen molecule show that the TDHFB method can partially incorporate two-electron excited determinants.
CHEMICAL PHYSICS LETTERS
(2023)
Article
Chemistry, Physical
Hung Cuong Dinh, Ganesan Elumalai, Hidenori Noguchi, Andrey Lyalin, Tetsuya Taketsugu, Kohei Uosaki
Summary: In this study, the electrocatalytic activities of gold (Au) electrodes for the oxygen reduction reaction (ORR) were enhanced by modifying the Au surface with size-selected hexagonal boron nitride nanosheets (BNNS). The smaller the size of the BNNS, the lower the overpotential for ORR and the higher the ORR activity. The smallest BNNS size range (0.1-0.22 μm) reduced the overpotential by as much as 330 mV compared to a bare Au electrode, and it exhibited an ORR activity only 80 mV higher than that of a platinum (Pt) electrode.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Masatoshi Hasebe, Takuro Tsutsumi, Tetsuya Taketsugu, Takao Tsuneda
Summary: This study compares the effects of the long-range correction (LC) and CCSD method on the total and orbital electron densities of molecules. The LC stabilizes electrons in the long-range interaction regions of kinetic energy density, while the CCSD method stabilizes electrons in the long-range interaction regions in the vertical molecular planes. The LC has a similar effect to the CCSD method on unoccupied orbitals, but differs for occupied orbitals.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Kai Oshiro, Min Gao, Lupeng Han, Dengsong Zhang, Jun-ya Hasegawa
Summary: In this study, the role of induced Fe and H2SO4 in preventing alkali poisoning was investigated. The results showed that Fe and H2SO4 can promote the formation of oxygen vacancies and generate characteristic adsorption sites, protecting NH3 adsorption sites on the catalyst surface from potassium poisoning. These findings are important for understanding the ability of metal oxide-based catalysts with sulfate ion against alkali poisoning and facilitating the tailored design of alkali tolerance catalysts.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Can Liu, Bang Lu, Hiroko Ariga-Miwa, Shohei Ogura, Takahiro Ozawa, Katsuyuki Fukutani, Min Gao, Jun-ya Hasegawa, Ken-ichi Shimizu, Kiyotaka Asakura, Satoru Takakusagi
Summary: In this study, the dynamic behavior of methoxy intermediate on a Pt/TiO2(110) surface during methanol decomposition has been investigated using STM, TPD, and DFT calculations. The results showed that the methoxy intermediates migrate on the TiO2 support surface to seek and find active Pt sites. This work provides a deeper understanding of the role of intermediate adsorbate migration in controlling the catalytic performance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Tianwei Lan, Min Gao, Jun-ya Hasegawa, Yongjie Shen, Wenqiang Qu, Qingmin Hu, Jiang Deng, Danhong Cheng, Dengsong Zhang
Summary: This study demonstrates the successful utilization of CuO nanocatalysts with isolated Pt atoms for selective oxidation of NH3, which significantly reduces fine particulate matter air pollution. The investigation reveals that the reaction field separation strategy and the weaker adsorption of NO2 intermediate on Cu sites contribute to the improved performance.
Article
Chemistry, Physical
Jiang Deng, Sixiang Cai, Min Gao, Jun-ya Hasegawa, Heyan Yao, Yongjie Shen, Zhiping Si, Jiayu Song, Dengsong Zhang
Summary: In this study, a catalyst comprising alpha-Fe2O3 crystals embedded in amorphous FeVO4 was engineered to exhibit remarkable resistance to metal poisons during the catalytic elimination of nitric oxide. The amorphous FeVO4 provided an ion channel for the migration of poisons away from the surface-active sites, while the crystal-in-amorphous structure enabled the catalyst to be universally resistant to metal poisons. The embedded alpha-Fe2O3 crystals acted as a stabilizing skeleton for the amorphous FeVO4, ensuring good robustness of the catalyst even after aging.
Article
Chemistry, Multidisciplinary
Keisuke Tashiro, Masato Kobayashi, Kiyotaka Nakajima, Tetsuya Taketsugu
Summary: A comprehensive reaction-path search using quantum chemical calculations was conducted to understand the mechanism of humin formation in the oxidation of HMF to FDCA. The study identified multiple reaction paths with low barriers for the reaction of HMF with OH-. It was also confirmed computationally that acetal protection of HMF could suppress humin formation.
Article
Chemistry, Multidisciplinary
Kewei Sun, Kazuma Sugawara, Andrey Lyalin, Yusuke Ishigaki, Kohei Uosaki, Oscar Custance, Tetsuya Taketsugu, Takanori Suzuki, Shigeki Kawai
Summary: In this study, complex organometallic oligomers were systematically synthesized on Cu(111) through sequential ring opening and bonding of phenanthroline derivatives by multiple Cu atoms. Characterization using scanning tunneling microscopy and density functional theory calculations revealed the role of Cu adatoms in the chiral oligomers. Furthermore, the strength of the bonds against sliding friction was found to be sufficient.
Article
Chemistry, Multidisciplinary
Satoi Wada, Takuro Tsutsumi, Kenichiro Saita, Tetsuya Taketsugu
Summary: Recently, surface-hopping ab initio molecular dynamics (SH-AIMD) simulations have been used to study the mechanisms and dynamics of excited-state chemical reactions. In this study, the authors investigate the effects of spin-orbit coupling (SOC) on the results of dynamics simulations using spin-pure and spin-mixed states for the hydride MH2 (M = Si, Ge, Sn, Pb). The results show that spin-mixed state potential energy surfaces are essential for simulating intersystem crossing in systems containing Sn and Pb elements.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)