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Syngas conversion serves as a gas‐to‐liquid technology to produce liquid fuels and valuable chemicals from coal, natural gas, or biomass. During syngas conversion, sintering is known to deactivate the catalyst owing to the loss of active surface area. However, the growth of nanoparticles might induce the formation of new active sites such as grain boundaries (GBs) which perform differently from the original nanoparticles. Herein, we reported a unique Cu‐based catalyst, Cu nanoparticles with in situ generated GBs confined in zeolite Y (denoted as activated Cu/Y), which exhibited a high selectivity for C5+ hydrocarbons (65.3 C%) during syngas conversion. Such high selectivity for long‐chain products distinguished activated Cu/Y from typical copper‐based catalysts which mainly catalyze methanol synthesis. This unique performance was attributed to the GBs, while the zeolite assisted the stabilization through spatial confinement. Specifically, the GBs enabled H‐assisted dissociation of CO and subsequent hydrogenation into CHx*. CHx* species not only serve as the initiator but also directly polymerize on Cu GBs, known as the carbide mechanism. Meanwhile, the synergy of GBs and their vicinal low‐index facets led to the CO insertion where non‐dissociative adsorbed CO on low‐index facets migrated to GBs and inserted into the metal‐alkyl bond for the chain growth. [ABSTRACT FROM AUTHOR]

The hydrogenation of CO2 by renewable power‐generated hydrogen offers a promising approach to a sustainable carbon cycle. However, the role of water during CO2 hydrogenation is still under debate. Herein, we demonstrated that either too low or too high contents of water hampered the methanol synthesis over Cu/ZnO based catalysts. For Cu single atoms on ZnO supports, the optimal content of water was 0.11 vol. % under 30 bar (CO2 : H2=1 : 3) at 170 °C. Upon the introduction of optimal‐content water, the methanol selectivity immediately became 99.1 %, meanwhile the conversion of CO2 underwent a volcano‐type trend with the maximum of 4.9 %. According to mechanistic studies, water acted as a bridge between H atoms and CO2/intermediates, facilitating the transformation of COOH* and CH2O*. The enhanced activity induced the generation of more water to react with CO via water‐gas shift reaction, resulting in the increase in methanol selectivity. [ABSTRACT FROM AUTHOR]

The conversion of CO2 by renewable power-generated hydrogen is a promising approach to a sustainable production of long-chain olefins (C4+=) which are currently produced from petroleum resources. The decentralized small-scale electrolysis for hydrogen generation requires the operation of CO2 hydrogenation in ambient-pressure units to match the manufacturing scales and flexible on-demand production. Herein, we report a Cu-Fe catalyst which is operated under ambient pressure with comparable C4+= selectivity (66.9%) to that of the state-of-the-art catalysts (66.8%) optimized under high pressure (35 bar). The catalyst is composed of copper, iron oxides, and iron carbides. Iron oxides enable reverse-water-gas-shift to produce CO. The synergy of carbide path over iron carbides and CO insertion path over interfacial sites between copper and iron carbides leads to efficient C-C coupling into C4+=. This work contributes to the development of small-scale low-pressure devices for CO2 hydrogenation compatible with sustainable hydrogen production. The conversion of CO2 by renewable power-generated hydrogen is a promising approach to a sustainable production of long-chain olefins. Here the authors report a Cu-Fe catalyst which achieves the hydrogenation of CO2 into long-chain olefins under ambient pressure via the synergy of carbide mechanism and CO insertion mechanism. [ABSTRACT FROM AUTHOR]

Syngas conversion serves as a gas-to-liquid technology to produce liquid fuels and valuable chemicals from coal, natural gas, or biomass. During syngas conversion, sintering is known to deactivate the catalyst owing to the loss of active surface area. However, the growth of nanoparticles might induce the formation of new active sites such as grain boundaries (GBs) which perform differently from the original nanoparticles. Herein, we reported a unique Cu-based catalyst, Cu nanoparticles with in situ generated GBs confined in zeolite Y (denoted as activated Cu/Y), which exhibited a high selectivity for C 5+ hydrocarbons (65.3 C%) during syngas conversion. Such high selectivity for long-chain products distinguished activated Cu/Y from typical copper-based catalysts which mainly catalyze methanol synthesis. This unique performance was attributed to the GBs, while the zeolite assisted the stabilization through spatial confinement. Specifically, the GBs enabled H-assisted dissociation of CO and subsequent hydrogenation into CH x *. CH x * species not only serve as the initiator but also directly polymerize on Cu GBs, known as the carbide mechanism. Meanwhile, the synergy of GBs and their vicinal low-index facets led to the CO insertion where non-dissociative adsorbed CO on low-index facets migrated to GBs and inserted into the metal-alkyl bond for the chain growth., (© 2024 Wiley-VCH GmbH.)

The hydrogenation of CO 2 by renewable power-generated hydrogen offers a promising approach to a sustainable carbon cycle. However, the role of water during CO 2 hydrogenation is still under debate. Herein, we demonstrated that either too low or too high contents of water hampered the methanol synthesis over Cu/ZnO based catalysts. For Cu single atoms on ZnO supports, the optimal content of water was 0.11 vol. % under 30 bar (CO 2  : H 2 =1 : 3) at 170 °C. Upon the introduction of optimal-content water, the methanol selectivity immediately became 99.1 %, meanwhile the conversion of CO 2 underwent a volcano-type trend with the maximum of 4.9 %. According to mechanistic studies, water acted as a bridge between H atoms and CO 2 /intermediates, facilitating the transformation of COOH* and CH 2 O*. The enhanced activity induced the generation of more water to react with CO via water-gas shift reaction, resulting in the increase in methanol selectivity., (© 2022 Wiley-VCH GmbH.)