Article
Chemistry, Inorganic & Nuclear
Frank Czerny, Keith Searles, Petr Sot, Johannes F. Teichert, Prashanth W. Menezes, Christophe Coperet, Matthias Driess
Summary: There is a growing interest in using earth-abundant nonprecious metals to replace expensive precious metal catalysts. A well-defined supported nickel hydrogenation catalyst was synthesized using surface organometallic chemistry and immobilized on silica. This immobilized catalyst can catalyze alkenes and alkynes at low temperatures without prior activation.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Yun-Dong Cao, Wen-Xia Mu, Mengdi Gong, Lin-Lin Fan, Jie Han, Hong Liu, Bin Qi, Guang-Gang Gao
Summary: In this study, PMo10V2@Fe3O4/C and PMo10V2@Co3O4/C catalysts were designed and achieved efficient conversion of HMF into DFF with almost 100% selectivity. These catalysts showed exceptional stability and recyclability.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Analytical
Yuanyuan Ge, Yuzhe Wang, Guozhong Xu, Zhigang Fang, Jinfeng Bai, Chao Li
Summary: Activated carbon with micropore and mesopore structure was prepared using soybean straw as a carbon source. A composite material PMo12/SSAC-OP was obtained by introducing redox-active H3PMo12O40 into SSAC-OP. The composite material exhibited both electric double layer capacitance and pseudocapacitance characteristics, with high specific capacitance and good cycling stability.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhao Xue, Zhang Ange, Tian Hongrui, Wang Henan, Huo Haiyan, Liu Shuxia
Summary: Two inorganic-organic hybrids based on Keggin-type heteropolyacids were prepared, showing iso-structural features with Cu2+ as six-coordinated in a 2D cation layer. The compounds exhibited significant photodegradation activity for methylene blue, indicating potential catalytic applications.
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES-CHINESE
(2021)
Article
Chemistry, Inorganic & Nuclear
Ramin Nemati, Dawood Elhamifar, Ali Zarnegaryan, Masoumeh Shaker
Summary: This study successfully synthesized a novel W6O19/amine-containing magnetic silica nanocomposite as a powerful nanocatalyst for the synthesis of spirooxindole-pyrans. The designed catalyst exhibited high thermal and chemical stability, as well as excellent magnetic properties and spherical morphology. Moreover, the nanocomposite could be recovered and reused multiple times without significant decrease in its activity.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
He Liu, Qilong Shen
Summary: This review provides a summary of the preparation and characterization of various types of copper(III) complexes, as well as the discussion on their reactivities and reaction mechanisms.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Xiudan Zhao, Liying Guo, Tiejun Xu, Rongrong Zheng, Haiyue Wang
Summary: A series of Keggin-type monosubstituted polyoxometalate-ionic liquid catalysts were synthesized and studied for their performance and mechanism in catalytic reactions. Among them, the tin monosubstituted zinc-tungstate ionic liquid catalyst showed the best performance under specific process parameters, exhibiting high selectivity and thermal stability.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Physical
Fariba Mohammadi-Nejati, Shahrokh Shahhosseini
Summary: In this study, Keggin and Dawson type vanadium-containing heteropolyacids (HPAs) were covalently immobilized on amine-functionalized magnetic graphene oxide (APTES-MGO). The supported HPA catalysts (HPAs@APTES-MGO) showed higher conversion and desulfurization efficiency compared to their bulk form.
SUSTAINABLE ENERGY & FUELS
(2023)
Article
Chemistry, Physical
Fujie Liu, Ming Zhang, Yongkang Gao, Haojie Tan, Hongping Li, Chao Wang, Wenshuai Zhu, Huaming Li
Summary: In this work, a magnetic ionic liquid supported silica prepared by a facile ball milling method was used for the desulfurization of fuel oil. The material showed promising results with increased specific surface area leading to effective oxidative desulfurization, complete removal of aromatic sulfur compounds, and good recycling ability. The introduction of Fe3O4 helped with catalyst separation post-reaction without compromising desulfurization performance.
Article
Engineering, Environmental
Livius F. Muff, Sandor Balog, Jozef Adamcik, Christoph Weder, Roman Lehner
Summary: Research on polymer nanoparticles in the environment and their impact on animal and human health is growing. This study presents a method to prepare well-defined nanoparticles with tailored characteristics, allowing for their detection in complex environments and mimicking environmentally relevant morphologies.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Polymer Science
Hien The Ho, Trang N. T. Phan, Marine Bonnevide, Nicolas Malicki, Marc Couty, Jacques Jestin, Didier Gigmes
Summary: The study presents the synthesis of a new nitroxide-mediated polymerization (NMP) initiator with a photolabile ortho-nitrobenzyl (oNB) group for surface-initiated NMP preparation of well-defined photoresponsive polystyrene grafted on silica nanoparticles. The photocleavable and photoresponsive properties of the materials were demonstrated using small angle X-ray scattering (SAXS) characterization.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Timothy A. Goetjen, Julia G. Knapp, Zoha H. Syed, Ryan A. Hackler, Xuan Zhang, Massimiliano Delferro, Joseph T. Hupp, Omar K. Farha
Summary: The inherent crystallinity of metal-organic framework (MOF) catalysts allows for the understanding of the active site structure at the molecular level. This study demonstrates the competence of a MOF-supported Cr3+ catalyst for ethylene polymerization, resulting in crystalline linear polyethylene with low polydispersity. Single crystal X-ray diffraction analysis provides insight into the interaction between the co-catalyst and the active site of the pre-catalyst, offering the opportunity for the study of a structurally well-defined olefin polymerization system. This research contributes to the development of next-generation heterogeneous catalyst systems.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Agricultural Engineering
Hengyu Shen, Yangtao Zhou, Guodong Wen, Lei Xu, Qiuyan Ding, Yanan Guan, Zhenyuan Yang, Yanzhao Sun, Xin Gao, Jinsong Zhang, Xiaolei Fan, Yilai Jiao
Summary: This study developed a highly active and stable composite catalyst of polyoxometalates (POMs) supported on zeolite for the synthesis of ethyl lactate. The stability of the zeolitic support and the support heteropolyacid were found to be equally important for obtaining a stable catalyst.
BIOMASS & BIOENERGY
(2022)
Article
Chemistry, Inorganic & Nuclear
Leon Escomel, Naime Soule, Emmanuel Robin, Iker Del Rosal, Laurent Maron, Erwann Jeanneau, Chloe Thieuleux, Clement Camp
Summary: We report a novel alkane elimination approach that involves the protonolysis of triisobutylaluminum by the acidic hydrides from Cp*IrH4. This strategy allows the synthesis of well-defined iridium aluminum polyhydride clusters with original structures and reactivities.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Applied
Jonathan Martinez-Laguna, Ana Caballero, Pedro J. Perez
Summary: The review explores the use of graphenic materials as supports for transition metal-based catalysts in reactions involving the functionalization of carbon-hydrogen bonds, with reported catalytic activities comparable or better than homogeneous counterparts, enhancing the recyclability of the materials.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Vaidish Sumaria, Luan Nguyen, Franklin Feng Tao, Philippe Sautet
Summary: It has been discovered that high CO coverage triggers the restructuring of Pt catalysts, forming atomic protrusions with low-coordination Pt atoms and sub-nano islands on the terraces. Machine-learning-accelerated first-principles atomistic simulations enable exploration of tens of thousands of configurations for CO-covered restructuring catalyst. These studies provide a new avenue for achieving atomic-scale understanding of the structural dynamics of more complex metal nanoparticle catalysts under reaction conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Nanoscience & Nanotechnology
Qiankun Hou, Kang Liu, Walid Al-Maksoud, Yuchang Huang, De Ding, Yongpeng Lei, Yi Zhang, Bin Lin, Lirong Zheng, Min Liu, Jean-Marie Basset, Yin Chen
Summary: Nonprecious-metal heterogeneous catalysts with atomically dispersed active sites have shown high activity and selectivity in various reactions, but their rational design and large-scale synthesis pose a significant challenge. Current approaches involve high temperatures and tedious procedures. In this study, a straightforward and scalable strategy was demonstrated for synthesizing atomically dispersed Ni electrocatalysts in a large quantity with high yield, using two simple steps under mild conditions. The resulting catalyst exhibits excellent catalytic performance in both oxygen evolution and reduction reactions, with tunable activity, high reproducibility, and stability. The strategy provides a practical and green method for the industrial manufacturing of nonprecious-metal single-site catalysts with predictable structures.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Dongfang Cheng, Ziyang Wei, Zisheng Zhang, Peter Broekmann, Anastassia N. Alexandrova, Philippe Sautet
Summary: The dynamic restructuring of Cu surfaces in electroreduction conditions was investigated using first-principles calculations and operando electrochemical scanning tunneling microscopy experiments. The restructuring of Cu(111) in acidic electrolyte was found to be potential- and pH-dependent. The strong adsorption of H atoms on the surface induced the formation of Cu adatoms, creating highly active sites for the hydrogen evolution reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Simran Kumari, Philippe Sautet
Summary: In this study, the active site of a single Pt atom supported on indium tin oxide for the oxygen evolution reaction (OER) was theoretically investigated using density functional theory calculations and grand canonical basin hopping. It was found that the ligands on the Pt atom change from Pt-OH to PtO(OH)4 under electrochemical conditions, resulting in a decrease of 0.3 V for the OER overpotential. This highlights the importance of accurately identifying the nature of the active site under reaction conditions and the impact of adsorbates on the electrocatalytic activity. This theoretical investigation enhances our understanding of SACs for the OER.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Mustafa Karatok, Hio Tong Ngan, Xiwen Jia, Christopher R. O'Connor, J. Anibal Boscoboinik, Dario J. Stacchiola, Philippe Sautet, Robert J. Madix
Summary: Palladium-silver-based alloy catalysts have the potential for CO-free hydrogen production from formic acid. The selective decomposition of formic acid on Pd-Ag alloys was investigated, and it was found that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition. In contrast, surface Pd atoms are detrimental to selectivity. The decomposition pathways can be tailored for CO-free H2 production on Pd-Ag alloy systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Simran Kumari, Tsugunosuke Masubuchi, Henry S. White, Anastassia Alexandrova, Scott L. Anderson, Philippe Sautet
Summary: A combination of DFT and experiments was used to study the electrocatalytic activity of Ptn clusters on ITO electrodes. The activity was found to increase with increasing Ptn size and was negligible for isolated Pt atoms on ITO. The adsorption of H atoms on Ptn/ITO was found to be about double the Hupd observed for Pt bulk or nanoparticles. The study also revealed the importance of considering multiple metastable structures and their reactions to accurately predict the activity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kangze Shen, Simran Kumari, Yu-Chao Huang, Joonbaek Jang, Philippe Sautet, Carlos G. Morales-Guio
Summary: Electrochemical partial oxidation of methane to methanol using transition metal (oxy)hydroxides as catalysts is investigated. CoOx, NiOx, MnOx, and CuOx are found to be active for this reaction. Systematic studies are carried out to evaluate the effect of catalyst film thickness, overpotential, temperature, and hydrodynamics on activity and methanol selectivity. It is shown that high-valence transition metal oxides are inherently active for methane activation and oxidation to methanol, and electrocatalytic oxidation enables thermodynamically favorable production of methanol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Dipna A. Patel, Georgios Giannakakis, George Yan, Hio Tong Ngan, Peng Yu, Ryan T. Hannagan, Paul L. Kress, Junjun Shan, Prashant Deshlahra, Philippe Sautet, E. Charles H. Sykes
Summary: The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity, thus achieving the goal of nonoxidative ethanol dehydrogenation to produce acetaldehyde.
Article
Chemistry, Physical
Zahra Almisbaa, Hassan A. Aljama, Khalid Almajnouni, Luigi Cavallo, Philippe Sautet
Summary: DFT-based reaction profiles and microkinetic simulations were used to investigate the selective hydrogenation of acetylene on Ni-based intermetallic catalysts. Among the tested catalysts, NiIn showed the highest ethylene yield, while NiIn and Ni2In3 exhibited reduced ethane formation and increased oligomerization compared to Ni and Ni3In. The findings emphasize the importance of considering oligomerization reactions and coverage effects when evaluating the selectivity of catalysts. Additionally, the presence of indium on the catalytic surface was found to decrease the rate of acetylene consumption, highlighting a trade-off between activity and selectivity.
Article
Chemistry, Physical
Yichen Li, Dongfang Cheng, Ziyang Wei, Philippe Sautet
Summary: Using first-principles calculations, we found that monoclinic WO(3)(001) preferentially forms a reconstructed monolayer on anatase TiO2(001) surface. We studied the surface structure of WO3/TiO2 under ambient conditions, including gas-phase O-2/H2O or H-2/H2O at different pressures and temperatures, as well as aqueous solution at different pH and electrochemical potentials. Based on the surface structures at different potentials, we proposed the proton-coupled electron-transfer (PCET) reaction pathway during charging and the oxygen reduction reaction (ORR) pathways during discharging, which explain its reversible electron storage ability. With electronic structure analysis, we demonstrated the charge separation effect of WO3 on TiO2 and the electron storage effect of WO3.
Article
Chemistry, Physical
Junjie Shi, Hio Tong Ngan, Philippe Sautet, Jason F. F. Weaver
Summary: Dilute Ti-Cu(111) alloys are highly selective for converting ethanol to ethylene. The presence of Ti ensembles on the Cu(111) surface promotes ethanol deoxygenation and enhances the production of gaseous C2H4 and H-2. The Ti ensemble size and the adsorbed O atom released during C-O cleavage significantly influence the reaction selectivity and stability.
Article
Chemistry, Physical
Nina M. Sackers, Andree Iemhoff, Philippe Sautet, Regina Palkovits
Summary: Computational methods were used to investigate well-defined and characterized isolated Ir sites anchored on a covalent triazine framework (CTF) as a showcase for experimentally accessible single-site catalysts. The resting states of the catalyst species after immobilization and after reduction at 400 ? were identified, and they were found not to be the catalytically active species but rather pre-catalysts for the dehydrogenation of formic acid.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Simran Kumari, Anastassia N. Alexandrova, Philippe Sautet
Summary: In this study, the nature of zirconia on a copper inverse catalyst under CO2 hydrogenation to methanol conditions was comprehensively investigated using density functional theory calculations and the Grand Canonical Basin Hopping method. The research revealed significant changes in the active site induced by various reaction parameters, and suggested that the active site can be considered as a statistical ensemble of diverse structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Giyeong Son, Yichen Li, Anna V. Shneidman, Jae Hyo Han, Michael Aizenberg, Philippe Sautet, Joanna Aizenberg
Summary: Various materials have been developed to extend the function of light-absorbing devices to low-light or nighttime conditions. This study found that crystal surface engineering can be used as a powerful tool to optimize materials for electron storage.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Lujain Alrais, Walid Al Maksoud, Baraa Werghi, Anissa Bendjeriou-Sedjerari, Edy Abou-Hamad, Mohamed N. Hedhili, Jean-Marie Basset
Summary: The synthesis of heterogeneous Ti(iv)-based catalysts for ethylene polymerization according to the concepts of surface organometallic chemistry is described. These catalysts utilize a unique silica support with a 3D fibrous morphology and an aluminum-bound hydroxyl group. The combination of morphological and electronic properties of the support leads to enhanced catalytic performance in ethylene polymerization, resulting in the formation of high-density polyethylene.
CHEMICAL COMMUNICATIONS
(2023)