Light-Induced Dynamic Restructuring of Cu Active Sites on TiO2 for Low-Temperature H2 Production from Methanol and Water DOI
Shunqin Luo, Hui Song, Fumihiko Ichihara

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(37), P. 20530 - 20538

Published: Sept. 7, 2023

The structure and configuration of reaction centers, which dominantly govern the catalytic behaviors, often undergo dynamic transformations under conditions, yet little is known about how to exploit these features favor functions. Here, we demonstrate a facile light activation strategy over TiO2-supported Cu catalyst regulate restructuring active sites during low-temperature methanol steam reforming. Under illumination, thermally deactivated Cu/TiO2 undergoes structural restoration from inoperative Cu2O originally metallic caused by photoexcited charge carriers TiO2, thereby leading substantially enhanced activity stability. Given low-intensity solar irradiation, optimized displays H2 production rate 1724.1 μmol g-1 min-1, outperforming most conventional photocatalytic thermocatalytic processes. Taking advantages strong light-matter-reactant interaction, achieve in situ manipulation sites, suggesting feasibility for real-time functionalization catalysts.

Language: Английский

Design of Single-Atom Catalysts and Tracking Their Fate Using Operando and Advanced X-ray Spectroscopic Tools DOI Creative Commons
Bidyut Bikash Sarma, Florian Maurer, Dmitry E. Doronkin

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(1), P. 379 - 444

Published: Nov. 23, 2022

The potential of operando X-ray techniques for following the structure, fate, and active site single-atom catalysts (SACs) is highlighted with emphasis on a synergetic approach both topics. absorption spectroscopy (XAS) related have become fascinating tools to characterize solids they can be applied almost all transition metals deriving information about symmetry, oxidation state, local coordination, many more structural electronic properties. SACs, newly coined concept, recently gained much attention in field heterogeneous catalysis. In this way, one achieve minimum use metal, theoretically highest efficiency, design only site-so-called single catalysts. While sites are not easy especially under operating conditions, XAS as probe together complementary methods (infrared spectroscopy, electron microscopy) ideal research area prove structure these dynamic changes during reaction. review, starting from their fundamentals, various conventional photon in/out discussed detailed mechanistic situ/operando studies. We systematically summarize strategies SACs outline exploration supported by density functional theory (DFT) calculations recent machine learning tools.

Language: Английский

Citations

133
Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters DOI

Wentong Jing,

Hui Shen, Ruixuan Qin

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(9), P. 5948 - 6002

Published: Dec. 27, 2022

The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated make it challenging identify molecular-level structure active sites thus precisely control To address this challenge, atomically dispersed (ADMCs) ligand-protected precise clusters (APMCs) have been emerging as two important classes model in recent years, helping build bridge between homogeneous catalysis. This review illustrates how chemistry these types determines performance from multiple dimensions. section ADMCs starts with local at metal–support interface, then focuses on effects coordinating atoms, including basicity hardness/softness. Studies also summarized discuss cooperativity achieved by dual remote effects. In APMCs, roles ligands supports determining activity, selectivity, stability APMCs illustrated. Finally, some personal perspectives further development for presented.

Language: Английский

Citations

132
Highly efficient CeO2-supported noble-metal catalysts: From single atoms to nanoclusters DOI Creative Commons
Han Yan, Ningqiang Zhang, Dingsheng Wang

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(7), P. 1594 - 1623

Published: May 31, 2022

Language: Английский

Citations

104
Synergistic Pt-CeO2 interface boosting low temperature dry reforming of methane DOI

Dongyang Shen,

Zhe Li, Jie Shan

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 318, P. 121809 - 121809

Published: July 30, 2022

Language: Английский

Citations

101
Sustainable production of hydrogen with high purity from methanol and water at low temperatures DOI Creative Commons
Sai Zhang, Yuxuan Liu, Mingkai Zhang

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 21, 2022

Abstract Carbon neutrality initiative has stimulated the development of sustainable methodologies for hydrogen generation and safe storage. Aqueous-phase reforming methanol H 2 O (APRM) attracted particular interests their high gravimetric density easy availability. Thus, to efficiently release significantly suppress CO at low temperatures without any additives is pursuit APRM. Herein, we demonstrate that dual-active sites Pt single-atoms frustrated Lewis pairs (FLPs) on porous nanorods CeO enable efficient additive-free with a (0.027%) through APRM 120 °C. Mechanism investigations illustrate acidic cooperatively promote activation methanol. With help spontaneous water dissociation FLPs, exhibit improved *CO production generation. This finding provides promising path towards flexible utilizations.

Language: Английский

Citations

98
Selective Hydrodeoxygenation of Aromatics to Cyclohexanols over Ru Single Atoms Supported on CeO2 DOI
Kaili Zhang, Qinglei Meng, Haihong Wu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(45), P. 20834 - 20846

Published: Nov. 4, 2022

Cyclohexanols are widely used chemicals, which mainly produced by oxidation of fossil feedstocks. Selective hydrodeoxygenation lignin derivatives has great potential for producing these chemicals but is challenging to obtain high yields. Here, we report that CeO2-supported Ru single-atom catalysts (SACs) enabled the hydrogenation benzene ring and catalyzed etheric C-O(R) bond cleavage without changing C-O(H) bond, could afford 99.9% yields cyclohexanols. As far as know, this first SACs catalyze aromatic ring. The reaction mechanism was studied control experiments density functional theory calculations. In catalysts, Ru-O-Ce sites were formed one atom coordinated with about four O atoms. These catalytic realize both deoxygenation reactions efficiently, thus desired cyclohexanols generated. This work pioneers catalysis in transformation provides a novel route synthesis

Language: Английский

Citations

98
Atom‐Economical Synthesis of Dimethyl Carbonate from CO2: Engineering Reactive Frustrated Lewis Pairs on Ceria with Vacancy Clusters DOI
Lei Li,

Wenxiu Liu,

Runhua Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Oct. 29, 2022

The chemical conversion of CO2 to long-chain chemicals is considered as a highly attractive method produce value-added organics, while the underlying reaction mechanism remains unclear. By constructing surface vacancy-cluster-mediated solid frustrated Lewis pairs (FLPs), 100 % atom-economical, efficient dimethyl carbonate (DMC) was realized. taking CeO2 model system, we illustrate that FLP sites can efficiently accelerate coupling and key intermediates. As demonstrated, with rich shows improved activity achieves high yield DMC up 15.3 mmol g-1 . In addition, by means synchrotron radiation in situ diffuse reflectance infrared Fourier-transform spectroscopy, combined density functional theory calculations, on site investigated systematically in-depth, providing pioneering insights into pathway for chemicals.

Language: Английский

Citations

75
Designing Cu0−Cu+ dual sites for improved C−H bond fracture towards methanol steam reforming DOI Creative Commons
Hao Meng, Yusen Yang, Tianyao Shen

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Dec. 2, 2023

Copper-based catalysts serve as the predominant methanol steam reforming material although several fundamental issues remain ambiguous such identity of active center and aspects reaction mechanism. Herein, we prepare Cu/Cu(Al)Ox with amorphous alumina-stabilized Cu2O adjoining Cu nanoparticle to provide Cu0-Cu+ sites. The optimized catalyst exhibits 99.5% CH3OH conversion a corresponding H2 production rate 110.8 μmol s-1 gcat-1 stability over 300 h at 240 °C. A binary function correlation between surface concentrations Cu0 Cu+ is established based on kinetic studies. Intrinsic sites in are investigated situ spectroscopy characterization theoretical calculations. Namely, find that important oxygen-containing intermediates (CH3O* HCOO*) adsorb moderate adsorption strength, which promotes electron transfer from species significantly reduces barrier C-H bond cleavage CH3O* HCOO* intermediates.

Language: Английский

Citations

62
Enabling Low-Temperature Methanol Activation via Lattice Oxygen Induced Cu–O–Cr Catalysis DOI
Zhao Sun,

Shufan Yu,

Sam Toan

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(20), P. 13704 - 13716

Published: Oct. 10, 2023

Steam reforming of methanol is a promising approach to achieving hydrogen storage, transportation, and in situ supply. However, this technology restricted by its high CO selectivity catalyst deactivation. In study, CuCr2O4-based catalytic oxygen carriers are tailored for lattice participating low-temperature reforming. We found that the activation originated from Cu–O–Cr structure intensification highly activated induction. Specifically, can be at temperatures as low 160 °C, on one hand, attributed reinforcement and, other owing reactive CuO4 tetrahedron CuCr2O4 spinel. Combined with XAS Raman results, formation demonstrated. The production rate an applied carrier 53.2% higher than control group without formulation. Satisfactory cyclic stability retained after 50th induction supplement cycle, ascribing strongly intensifies Cu–Cr2O3 interactions. DFT results reveal process CH3OH → CH3O* rate-determining step. Compared Cu(111) Cr2O3(110), Cu(111)/Cr2O3(110) surface exhibits lowest potential barrier during process, promoting

Language: Английский

Citations

54
Review on developments of catalytic system for methanol steam reforming from the perspective of energy-mass conversion DOI
Weiwei Yang, Xu Ma, Xin-Yuan Tang

et al.

Fuel, Journal Year: 2023, Volume and Issue: 345, P. 128234 - 128234

Published: March 29, 2023

Language: Английский

Citations

53