Article
Chemistry, Physical
Carlota Bozal-Ginesta, Reshma R. Rao, Camilo A. Mesa, Xinyi Liu, Sam A. J. Hillman, Ifan E. L. Stephens, James R. Durrant
Summary: Hydrous iridium oxides (IrOx) have been proven to be the best oxygen evolution electrocatalysts for operation in acidic environments. This study utilizes time-resolved operando spectroelectrochemistry to investigate the redox-state kinetics of IrOx electrocatalyst films for both water and hydrogen peroxide oxidation, identifying different redox species and quantifying their concentrations as a function of applied potential. The generation of Ir4.y+ states is found to be the potential-determining step for catalytic water oxidation, while H2O2 oxidation is observed to be driven by the generation of Ir4+ states.
Article
Multidisciplinary Sciences
Yanyan Zhao, Sheng Dai, Ke R. Yang, Sufeng Cao, Kelly L. Materna, Hannah M. C. Lant, Li Cheng Kao, Xuefei Feng, Jinghua Guo, Gary W. Brudvig, Maria Flytzani-Stephanopoulos, Victor S. Batista, Xiaoqing Pan, Dunwei Wang
Summary: Atomically dispersed catalysts have shown high activity for selective oxidation of carbon monoxide with excess hydrogen, but their stability is not ideal. This study demonstrates that introducing a structural component to minimize the diffusion of the active metal center significantly improves stability without compromising activity. By using a dinuclear iridium heterogeneous catalyst as a study platform, two types of oxygen species, interfacial and bridge, are identified to work together for both activity and stability. This work provides important insights into the synergistic effect between the active metal center and the supporting substrate, with potential broad applications for atomically dispersed catalysts.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Physical
Akira Ohnuma, Koki Takahashi, Hironori Tsunoyama, Tomoya Inoue, Pei Zhao, Archana Velloth, Masahiro Ehara, Nobuyuki Ichikuni, Masao Tabuchi, Atsushi Nakajima
Summary: This study demonstrates the enhanced catalytic activity of Pt sub-nanoclusters (containing three to nine Pt atoms) based on charge redistribution. These sub-nanoclusters exhibit higher activity compared to standard Pt/C catalysts and could potentially be used as efficient catalysts in future fuel cell technologies.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Multidisciplinary Sciences
Maodi Wang, Zhenchao Zhao, Chunzhi Li, He Li, Jiali Liu, Qihua Yang
Summary: The authors report a hydrogenation mode in which hydrogen species relay from supported metal nanoparticles to organometallic complexes, resulting in a synergistic effect for NAD(P)H regeneration. This mode offers high selectivity and activity, providing a new approach to address challenging hydrogenation reactions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Pascal Knorr, Nicolas Lentz, Martin Albrecht
Summary: In this study, a triazolylidene iridium complex was modified with two alcohol groups and integrated into a polymeric assembly. Both monomeric complexes and polymerized systems exhibited comparable catalytic performance in water oxidation driven by cerium ammonium nitrate. However, a partial loss of iridium from the polymer into the aqueous phase under catalytic conditions suggested the need for more robust polymer supports.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jiajia Yi, Shaoqi Zhan, Lin Chen, Qiang Tian, Ning Wang, Jun Li, Wenhua Xu, Biaobiao Zhang, Marten S. G. Ahlquist
Summary: In this study, two facile and effective design strategies were introduced to facilitate the coupling of two catalytic units via electrostatic interactions, resulting in significantly improved catalytic performance. The intermolecular electrostatic interactions in these two systems were fully identified and found to play a key role in enhancing catalytic performance. The successful strategies demonstrated here can be utilized in designing other intercatalyst coupling systems for activation and synthesis of small molecules and organic compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Jing Wang, Wenji Wang, Xiongyu Yang, Jingwen Liu, Haizhou Huang, Mingxin Chang
Summary: In this study, a practical homogeneous direct reductive amination (DRA) procedure using iridium catalysis was reported. The reaction conditions were mild and additive-free, allowing for the formation of structurally and functionally diverse amine products, including drugs and compounds from late-stage manipulation. DFT studies revealed that the reaction proceeds via an outer-sphere H-addition pathway with important roles played by pi-pi interactions and H-bonding.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yingying Wen, Wei Liu, Peifang Wang, Huinan Che, Chunmei Tang, Bin Liu, Yanhui Ao
Summary: In this study, a C-layer coated ZnO (C-ZnO) with modulated electronic structure was constructed for piezo-catalytic hydrogen peroxide (H2O2) generation. The C-ZnO showed ultrahigh piezocatalytic activity for H2O2 yield in pure water and excellent piezo-catalytic performance for the degradation of different pollutants. This research provides a promising way for efficient H2O2 production in pure water using mechanical energy and opens a new avenue for designing highly active piezo-catalytic systems for pollutants degradation.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Kentaro Yonesato, Seiji Yamazoe, Soichi Kikkawa, Daisuke Yokogawa, Kazuya Yamaguchi, Kosuke Suzuki
Summary: The properties of metal nanoclusters depend on their structures and electronic states. However, controlling the electronic states is still challenging. Recently, we achieved reversible control of the electronic states of atomically precise Ag nanoclusters by utilizing the acid/base nature of polyoxometalates as inorganic ligands.
Review
Chemistry, Inorganic & Nuclear
Victoria A. Vaillard, Pablo D. Nieres, Santiago E. Vaillard, Fabio Doctorovich, Biprajit Sarkar, Nicolas Neuman
Summary: Metallocorroles have emerged as interesting and versatile catalysts for various redox reactions, with their diversity and richness offering endless possibilities for research.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Lianshun Luo, Rongchao Jin
Summary: Significant progress has been made in integrating atomically precise metal nanoclusters (NCs) with metal-organic frameworks (MOFs) to create unique composites with improved catalytic properties. MOFs play a crucial role in enhancing the catalytic performance of NCs in various reactions. Future research should focus on exploring the potential of NCs/MOF composites for functional materials.
Article
Chemistry, Multidisciplinary
Jian Zhang, Wu-Lin Yang, Hanliang Zheng, Yi Wang, Wei-Ping Deng
Summary: This study reports an unprecedented asymmetric gamma-allylic alkylation method using the Sc/Ir dual catalysis system, which provides synthetically versatile gamma-allylic crotonaldehydes with high efficiency and excellent selectivities. The dienolates, without essential auxiliary groups, are generated in situ through scandium triflate-mediated Meinwald rearrangement in an atom-economical manner. A Sc/Ir bimetallic catalytic cycle is proposed to explain the reaction mechanism using computational density functional theory calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chen Wang, Panlong Zhai, Mingyue Xia, Yunzhen Wu, Bo Zhang, Zhuwei Li, Lei Ran, Junfeng Gao, Xiaomeng Zhang, Zhaozhong Fan, Licheng Sun, Jungang Hou
Summary: This study reports an efficient oxygen evolution reaction (OER) catalyst that combines iridium clusters and high-valence cobalt species, achieving non-concerted proton-electron transfer at the atomic scale to trigger OER activity at multiple active sites. Experimental evidence confirms the importance of lattice oxygen oxidation mechanism, while theoretical simulations suggest that the catalyst's OER performance is mainly dominated by the LOM pathway, facilitating reaction kinetics.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shao-Yu Yuan, Li -Wen Jiang, Jin-Song Hu, Hong Liu, Jian-Jun Wang
Summary: In this article, we report an effective strategy for implanting fully dispersed iridium-oxide atomic clusters onto hematite, which significantly improves the photoelectrochemical water oxidation in acidic solution. The resulting photoanode achieves a record-high photocurrent of 1.35 mA cm-2 at 1.23 V, demonstrating the merits of high atomic utilization of Ir.
Article
Biochemistry & Molecular Biology
Tingting Wang, Changmeng Liu, Dong Xu, Jiaxi Xu, Zhanhui Yang
Summary: A highly chemoselective method for converting alpha, beta-disubstituted nitroalkenes to ketones has been developed using an acid-compatible iridium catalyst. Nitroalkenes can be readily converted to ketones at a certain ratio with high isolated yields. A new mechanistic mode has been proposed, and the pH value is found to play a crucial role in controlling the chemoselectivity.
Editorial Material
Chemistry, Physical
Damien Alloyeau, Vincenzo Amendola, Catherine Amiens, Pascal Andreazza, Joost M. Bakker, Francesca Baletto, Stephan Barcikowski, Noelia Barrabes, Michael Bowker, Fuyi Chen, Emmanuel Cottancin, Wolfgang E. Ernst, Riccardo Ferrando, Georg Daniel Forster, Alessandro Fortunelli, Didier Grandjean, Hazar Guesmi, Graham J. Hutchings, Ewald Janssens, Miguel Jose Yacaman, Christian Kuttner, Lebohang Macheli, Eric Marceau, Marcelo M. Mariscal, Jette K. Mathiesen, John McGrady, Christine Mottet, Diana Nelli, Pinkie Ntola, Cameron J. Owen, Micha Polak, Jonathan Quinson, Cesare Roncaglia, Leonid Rubinovich, Rolf Schafer, Manoj Settem, Jeff Shield, Mzamo Shozi, Swathi Swaminathan, Stefan Vajda, Hans-Christian Weissker
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Juraj Jasik, Stanislav Valtera, Mykhailo Vaidulych, Muntaseer Bunian, Yu Lei, Avik Halder, Hana Tarabkova, Martin Jindra, Ladislav Kavan, Otakar Frank, Stephan Bartling, Stefan Vajda
Summary: The effects of composition and support on the catalytic activity and selectivity in the oxidative dehydrogenation of cyclohexene were investigated. The study found that ultra-nanocrystalline diamond supported clusters were highly active and mainly produced benzene, while some mixed clusters produced cyclohexadiene. TiO2-supported tetramers solely produced benzene without any combustion to CO2. The selectivity of zirconia-supported mixed CuPd clusters and monometallic Cu cluster differed significantly, with the former producing significant fractions of cyclohexadiene.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Ethan P. Kamphaus, Jessica Catharine Jones, Nannan Shan, Alex B. F. Martinson, Lei Cheng
Summary: Routes to area and site-selective atomic layer deposition (ALD) are challenging. This study computationally identifies conditions for site-selective ALD by hydrating surface defects and demonstrates the mechanistically clear path to site-selective ALD through in situ ellipsometric measurements.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Multidisciplinary Sciences
Jaianth Vijayakumar, Tatiana M. Savchenko, David M. Bracher, Gunnar Lumbeeck, Armand Beche, Jo Verbeeck, Stefan Vajda, Frithjof Nolting, C. A. F. Vaz, Armin Kleibert
Summary: This paper provides a detailed understanding of the oxidation process of cobalt nanoparticles and evaluates the development of models for metal oxidation and magnetic phenomena at the nanoscale. Understanding the chemical reactivity and magnetism of 3d transition metal nanoparticles is essential for applications in spintronics and catalysis.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zachary D. Hood, Anil U. Mane, Aditya Sundar, Sanja Tepavcevic, Peter Zapol, Udochukwu D. Eze, Shiba P. Adhikari, Eungje Lee, George E. Sterbinsky, Jeffrey W. Elam, Justin G. Connell
Summary: Sulfide-based solid-state electrolytes (SSEs) have high ionic conductivity and favorable mechanical properties, making them promising for next-generation solid-state batteries. Thin Al2O3 coatings grown on Li6PS5Cl powders using atomic layer deposition simultaneously address the stability issues and improve cell performance. These coated powders exhibit higher ionic conductivities, lower electronic conductivities, and improved stability at the Li-SSE interface, leading to significantly improved battery cycle life.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Ashley R. R. Bielinski, Ethan P. P. Kamphaus, Lei Cheng, Alex B. F. Martinson
Summary: In this study, in situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate the surface reactions in atomic layer deposition of zirconium oxide. The results revealed that the reaction heat is dependent on factors such as growth rate, equilibrium surface hydroxylation, and extent of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jessica C. Jones, Ethan P. Kamphaus, Jeffrey R. Guest, Anil U. Mane, Lei Cheng, Alex B. F. Martinson
Summary: Unique atomic arrangements on material surfaces can exhibit distinct reactivity, providing opportunities for selective surface chemistry. However, site-selective atomic layer deposition (ALD) processes have not been widely achieved experimentally. This study presents evidence for site-selective ALD targeting oxygen vacancies on TiO2 single crystals. In situ ellipsometry and atomic force microscopy (AFM) imaging confirm the site-specific growth mechanism dependent on surface oxygen vacancy density. This approach may offer future opportunities for targeted remediation of electronically imperfect interfaces.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Jiaxin Duan, Hafeera Shabbir, Zhihengyu Chen, Wentuan Bi, Qin Liu, Jingyi Sui, Luka Dordevic', Samuel I. Stupp, Karena W. Chapman, Alex B. F. Martinson, Alice Li, Richard D. Schaller, Subhadip Goswami, Rachel B. Getman, Joseph T. Hupp
Summary: Researchers have successfully fabricated agglomeration-immune, reactant-accessible polythiometalates (PTMs) clusters without capping ligands, which are periodically arranged in a water-stable, hierarchically porous Zr-metal-organic framework (MOF). These clusters exhibit electrocatalytic and photocatalytic activity for hydrogen evolution in reduction reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Materials Science, Coatings & Films
Thabiso Kunene, Alex B. F. Martinson
Summary: Sequential infiltration synthesis (SIS) is a vapor phase synthesis technique that allows precise control of metal oxyhydroxide incorporation into polymer scaffolds. By varying the number of SIS cycles and processing parameters, we observed size-dependent properties and coordination changes of InOx(OH)(y) clusters deposited within a polymethylmethacrylate (PMMA) matrix. This incorporation of indium oxyhydroxide in PMMA via SIS presents an opportunity to enhance the CO2 absorption capacity and gas selectivity of affordable polymers.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2023)
Article
Polymer Science
Qiming He, Yijun Qiao, Carlos Medina Jimenez, Ryan Hackler, Alex B. F. Martinson, Wei Chen, Matthew Tirrell
Summary: Zwitterionic brushes were synthesized and their structure was investigated using various techniques. The PCysMA brushes showed an antipolyelectrolyte effect related to the Hofmeister series of anions. The presence of divalent and trivalent ions had different impacts on the dimensions of the PCysMA brushes and their chelating interactions.
Article
Chemistry, Multidisciplinary
Dianlong Zhao, Ming Cong, Zhun Liu, Zhiwei Ma, Kai Wang, Guanjun Xiao, Bo Zou
Summary: This study reveals the quantitative steric hindrance effect of different organic components in hybrid perovskites and successfully prepares 2D hybrid perovskite (NAPH)2PbCl4 nanoplates using 1-(2-naphthyl)methanamine. The research also demonstrates the reversal phenomenon of pressure-induced emission and establishes the correlation between PIE retention and steric hindrance, providing improved material design and synthesis for applications in white light-emitting diodes and scintillators.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Physical
Jessica C. Jones, Nazar Delegan, F. Joseph Heremans, Alex B. F. Martinson
Summary: In this paper, we developed a precise control of surface termination and interfacial interactions using atomic layer deposition (ALD) technique on diamond surface, which is critical for advanced solid-state quantum applications. The effect of morphology on ALD nucleation was studied by selecting diamond substrates with smooth and rough surfaces. In situ spectroscopic ellipsometry with sub-angstrom resolution was used to monitor the surface reaction and evaluate the nucleation of an ALD Al2O3 process. Hydrogen termination effectively passivated both smooth and rough surfaces, while triacid cleaning only passivated smooth surface with striking effectiveness.
Article
Chemistry, Multidisciplinary
Tomas Strysovsky, Martina Kajabova, Robert Prucek, Ales Panacek, Karolina Simkovicova, Stefan Vajda, Zdenek Bastl, Libor Kvitek
Summary: Converting CO2 to value-added products is significant, and this study demonstrates the temperature-dependent selectivity of copper-decorated indium oxide catalysts.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Nanoscience & Nanotechnology
Jacklyn N. Hall, Alon Chapovetsky, Uddhav Kanbur, Yu Lim Kim, Katherine E. McCullough, Zoha H. Syed, Christopher S. Johnson, Magali S. Ferrandon, Cong Liu, A. Jeremy Kropf, Massimiliano Delferro, David M. Kaphan
Summary: The development of new methods for catalyst synthesis to discover new materials for energy and chemical applications is important. This study investigates the generality of oxidative grafting of organometallic and molecular metal precursors onto redox-active surfaces. The supported structures and oxidation states are analyzed using X-ray absorption and photoelectron spectroscopy, revealing intercalation of metal ions and intact molecular fragments on the surface. The concept is proven by demonstrating diverse catalytic performance in the conversion of cyclohexane and low-temperature oxidation of carbon monoxide.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Materials Science, Multidisciplinary
Ping-Ru Wu, Ming-Hao Zhang, Gao Xu, Xin-Gen Liu, Zhun Liu, Qi-Feng Liang
Summary: This article reviews the progress of node line semimetals in tungsten-based materials, focusing on their symmetry-based protection, characteristic electronic band structures, and response to spin-orbit coupling and breaking of time-reversal symmetry.
