Bimetallic Sites for Catalysis: From Binuclear Metal Sites to Bimetallic Nanoclusters and Nanoparticles

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4855 - 4933

Published: March 27, 2023

Heterogeneous bimetallic catalysts have broad applications in industrial processes, but achieving a fundamental understanding on the nature of active sites at atomic and molecular level is very challenging due to structural complexity catalysts. Comparing features catalytic performances different entities will favor formation unified structure-reactivity relationships heterogeneous thereby facilitate upgrading current In this review, we discuss geometric electronic structures three representative types (bimetallic binuclear sites, nanoclusters, nanoparticles) then summarize synthesis methodologies characterization techniques for entities, with emphasis recent progress made past decade. The supported nanoparticles series important reactions are discussed. Finally, future research directions catalysis based and, more generally, prospective developments both practical applications.

Language: Английский

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Single‐atom catalysis for carbon neutrality

Carbon Energy, Journal Year: 2022, Volume and Issue: 4(6), P. 1021 - 1079

Published: July 14, 2022

Abstract Currently, more than 86% of global energy consumption is still mainly dependent on traditional fossil fuels, which causes resource scarcity and even emission high amounts carbon dioxide (CO 2 ), resulting in a severe “Greenhouse effect.” Considering this situation, the concept “carbon neutrality” has been put forward by 125 countries one after another. To achieve goals neutrality,” two main strategies to reduce CO emissions develop sustainable clean can be adopted. Notably, these are crucial for synthesis advanced single‐atom catalysts (SACs) energy‐related applications. In review, we highlight unique SACs conversion into high‐efficiency energy, example, through photocatalytic, electrocatalytic, thermal catalytic hydrogenation technologies, convert hydrocarbon fuels (CO, CH 4 , HCOOH, 3 OH, multicarbon [C 2+ ] products). addition, introduce technologies devices replace polluting such as photocatalytic electrocatalytic water splitting produce hydrogen oxygen reduction reaction (ORR) fuel cells. Impressively, several representative examples (including d ‐, ds p f ‐blocks) conversion, H ORR discussed describe methods, characterization, corresponding activity. Finally, review concludes with description challenges outlooks future applications contributing toward neutrality.

Language: Английский

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Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2

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

Published: Feb. 27, 2023

Photochemical conversion of CO2 into high-value C2+ products is difficult to achieve due the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for C3H8 prepared by implanting Cu single atoms on Ti0.91O2 atomically-thin layers. promote formation neighbouring oxygen vacancies (VOs) matrix. These modulate electronic coupling interaction between adjacent Ti form a unique Cu-Ti-VO unit A high electron-based selectivity 64.8% (product-based 32.4%), 86.2% total hydrocarbons 50.2%) are achieved. Theoretical calculations suggest that may stabilize key *CHOCO *CH2OCOCO intermediates reduce their energy levels, tuning both C1-C1 C1-C2 couplings thermodynamically-favourable exothermal processes. Tandem catalysis mechanism potential reaction pathway tentatively proposed formation, involving overall (20e- - 20H+) reduction three molecules at room temperature.

Language: Английский

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Thermo-, Electro-, and Photocatalytic CO₂ Conversion to Value-Added Products over Porous Metal/Covalent Organic Frameworks

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(20), P. 2978 - 2997

Published: Sept. 26, 2022

ConspectusThe continuing increase of the concentration atmospheric CO2 has caused many environmental issues including climate change. Catalytic conversion using thermochemical, electrochemical, and photochemical methods is a potential technique to decrease simultaneously obtain value-added chemicals. Due high energy barrier however, this method still far from large-scale applications which requires activity, selectivity, stability. Therefore, development efficient catalysts convert different products urgent. With their well-engineered pores chemical compositions, surface area, elevated adsorption capability, adjustable active sites, porous crystalline frameworks metal-organic (MOFs) covalent organic (COFs) are materials for catalytic conversion. Here, we summarize our recent work on MOFs COFs thermocatalytic, electrocatalytic, photocatalytic describe structure-activity relationships that could guide design effective catalysts.The first section paper describes imidazolium-functionalized MOFs, liquid cationic with nucleophilic halogen ions, can promote thermocatalytically cycloaddition reaction epoxides toward cyclic carbonates at one bar pressure. A MOF takes role reservoir tackle low local concentrations in gas-liquid-solid heterogeneous reactions. Imidazolium-functionalized ions avoid use cocatalysts, leads milder more facile experimental conditions separation processes.In dealing electrocatalytic reduction (CO2RR), developed series conductive framework fast electron transmission capabilities, afford current densities outperform traditional COF have been reported. The intrinsically two-dimensional 2D nanosheets based fully π-conjugated phthalocyanine motif excellent transport capability were prepared, strong transporters also integrated into metalloporphyrin-based CO2RR. Cu2O quantum dots Cu nanoparticles (NPs) be uniformly dispersed MOFs/COFs synergistic and/or tandem electrocatalysts, achieve highly selective production CH4 or C2H4 CO2RR.A third efforts facilitate electron-hole photocatalysis. Our focus regulation coordination spheres fabrication architecture heterojunctions, engineering films reduction.Finally, discuss several problems associated studies consider some prospects

Language: Английский

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Constructing Synergistic Triazine and Acetylene Cores in Fully Conjugated Covalent Organic Frameworks for Cascade Photocatalytic H₂O₂ Production

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(11), P. 5232 - 5240

Published: May 16, 2022

Covalent organic frameworks (COFs) are an ideal template for photocatalytic H2O2 synthesis because of the tunable chemical structures and semiconductor properties. However, photoactivity COFs is still under-improved due to inefficient intrinsic charge generation, fast recombination photogenerated charges, limited electron transport along frameworks. Herein, spatially separated synergistic triazine acetylene units first integrated into (EBA-COF BTEA-COF) production. The spatial separation cores leads efficient suppressed recombination, C═C linkage facilitates electrons over skeletons. Both experimental computational results suggested that synergistically promote in a two-electron pathway. EBA-COF showed attractive activity with production rate 1830 μmol h–1 gcat–1, superior most other COF-based catalysts. This study provides method designing photocatalysts active sites based on vinylene-linked COFs.

Language: Английский

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Recent advances in the application of metal-organic frameworks (MOFs)-based nanocatalysts for direct conversion of carbon dioxide (CO2) to value-added chemicals

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 474, P. 214853 - 214853

Published: Oct. 7, 2022

Language: Английский

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Multiscale CO₂ Electrocatalysis to C₂₊ Products: Reaction Mechanisms, Catalyst Design, and Device Fabrication

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10530 - 10583

Published: Aug. 17, 2023

Electrosynthesis of value-added chemicals, directly from CO2, could foster achievement carbon neutral through an alternative electrical approach to the energy-intensive thermochemical industry for utilization. Progress in this area, based on electrogeneration multicarbon products CO2 electroreduction, however, lags far behind that C1 products. Reaction routes are complicated and kinetics slow with scale up high levels required commercialization, posing significant problems. In review, we identify summarize state-of-art progress synthesis a multiscale perspective discuss current hurdles be resolved generation reduction including atomistic mechanisms, nanoscale electrocatalysts, microscale electrodes, macroscale electrolyzers guidelines future research. The review ends cross-scale links discrepancies between different approaches extensions performance stability issues arise industrial environment.

Language: Английский

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Tandem Photocatalysis of CO₂ to C₂H₄ via a Synergistic Rhenium-(I) Bipyridine/Copper-Porphyrinic Triazine Framework

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 8261 - 8270

Published: March 28, 2023

The photocatalytic conversion of CO2 into C2+ products such as ethylene is a promising path toward the carbon neutral goal but remains big challenge due to high activation barrier for and similar reduction potentials many possible multi-electron-transfer products. Herein, an effective tandem photocatalysis strategy has been developed support by construction synergistic dual sites in rhenium-(I) bipyridine fac-[ReI(bpy)(CO)3Cl] (Re-bpy) copper-porphyrinic triazine framework [PTF(Cu)]. With these two catalysts, large amount can be produced at rate 73.2 μmol g-1 h-1 under visible light irradiation. However, cannot obtained from use either component Re-bpy or PTF(Cu) catalysts alone; with single catalyst, only monocarbon product CO conditions. In system, generated adsorbed nearby Cu PTF(Cu), this followed C-C coupling process which ultimately produces ethylene. Density functional theory calculations demonstrate that between PTF(Cu)-*CO Re-bpy-*CO form key intermediate Re-bpy-*CO-*CO-PTF(Cu) vital C2H4 production. This work provides new pathway design efficient photocatalysts photoconversion C2 via driven mild

Language: Английский

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Maximizing Electroactive Sites in a Three‐Dimensional Covalent Organic Framework for Significantly Improved Carbon Dioxide Reduction Electrocatalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(1)

Published: Oct. 30, 2021

Synthesis of functional 3D COFs with irreversible bond is challenging. Herein, imide-bonded were constructed via the imidization reaction between phthalocyanine-based tetraanhydride and 1,3,5,7-tetra(4-aminophenyl)adamantine. These two are made up interpenetrated pts networks according to powder X-ray diffraction gas adsorption analyses. CoPc-PI-COF-3 doped carbon black has been employed fabricate electrocatalytic cathode towards CO2 reduction within KHCO3 aqueous solution, displaying Faradaic efficiency 88-96 % for -to-CO conversion at voltage range ca. -0.60 -1.00 V (vs. RHE). In particular, porous structure enables active centers occupying 32.7 total cobalt-phthalocyanine subunits, thus giving a large current density (jCO ) -31.7 mA cm-2 -0.90 V. parameters significantly improved than excellent 2D COF analogue (CoPc-PI-COF-1, 5.1 -21.2 ).

Language: Английский

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Co-catalytic metal–support interactions in single-atom electrocatalysts

Nature Reviews Materials, Journal Year: 2024, Volume and Issue: 9(3), P. 173 - 189

Published: Jan. 10, 2024

Language: Английский

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