Selectivity Control by Relay Catalysis in CO and CO₂ Hydrogenation to Multicarbon Compounds

Accounts of Chemical Research, Год журнала: 2024, Номер 57(5), С. 714 - 725

Опубликована: Фев. 13, 2024

ConspectusThe hydrogenative conversion of both CO and CO2 into high-value multicarbon (C2+) compounds, such as olefins, aromatic hydrocarbons, ethanol, liquid fuels, has attracted much recent attention. The hydrogenation is related to the chemical utilization various carbon resources including shale gas, biomass, coal, carbon-containing wastes via syngas (a mixture H2 CO), while by green chemicals fuels would contribute recycling for neutrality. state-of-the-art technologies CO/CO2 C2+ compounds primarily rely on a direct route Fischer–Tropsch (FT) synthesis an indirect two methanol-mediated processes, i.e., methanol from compounds. be more energy- cost-efficient owing reduced operation units, but product selectivity FT limited Anderson–Schulz–Flory (ASF) distribution. Selectivity control compound one most challenging goals in field C1 chemistry, chemistry transformation one-carbon (C1) molecules.We have developed relay-catalysis strategy solve challenge arising complicated reaction network involving multiple intermediates channels, which inevitably lead side reactions byproducts over conventional heterogeneous catalyst. core relay catalysis design single tandem-reaction channel, can target controllably, choosing appropriate (or intermediate products) steps connecting these intermediates, arranging optimized yet matched catalysts implement like relay. This Account showcases representative systems our group past decade lower (C2–C4) aromatics, oxygenates with breaking limitation catalysts. These are typically composed metal or oxide CO/CO2/H2 activation zeolite C–C coupling reconstruction, well third even fourth catalyst component other functions if necessary. mechanisms oxides, distinct that transition noble surfaces, discussed emphasis role oxygen vacancies. Zeolites catalyze (including hydrocracking/isomerization heavier methanol-to-hydrocarbon reactions, carbonylation methanol/dimethyl ether) system, mainly controlled Brønsted acidity shape-selectivity confinement effect zeolites. We demonstrate thermodynamic/kinetic matching steps, proximity spatial arrangement components, transportation intermediates/products sequence key issues guiding selection each construction efficient system. Our methodology also useful molecules coupling, inspiring efforts toward precision catalysis.

Язык: Английский

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Steam methane reforming using a regenerable antenna–reactor plasmonic photocatalyst

Nature Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 1, 2024

Язык: Английский

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Design of catalysts for selective CO2 hydrogenation

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

Язык: Английский

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Atomic-Scale Visualization of Heterolytic H₂ Dissociation and CO_x Hydrogenation on ZnO under Ambient Conditions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(41), С. 22697 - 22707

Опубликована: Окт. 6, 2023

Studying catalytic hydrogenation reactions on oxide surfaces at the atomic scale has been challenging because of typical occurrence these processes ambient or elevated pressures, rendering them less accessible to atomic-scale techniques. Here, we report an study H2 dissociation and CO CO2 ZnO using pressure scanning tunneling microscopy, X-ray photoelectron spectroscopy, density functional theory (DFT) calculations. We directly visualized heterolytic ZnO(101̅0) under found that reaction does not require assistance surface defects. The presence 300 K impede availability sites for dissociation; instead, can even enhance stability coadsorbed hydride species, thereby facilitating their dissociative adsorption. Our results show is active species hydrogenation, while hydroxyl cannot hydrogenate CO/CO2 ZnO. Both AP studies DFT calculations showed thermodynamically kinetically more favorable compared hydrogenation. point toward a two-step mechanism involving initial oxidation step followed by with form formate. These findings provide molecular insights into deepen our understanding syngas conversion catalysis in general.

Язык: Английский

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Boosting the Catalytic Activity of Nitrogen Sites by Spin Polarization Engineering for Oxygen Reduction and Wide‐Temperature Ranged Quasi‐Solid Zn–Air Batteries

Advanced Energy Materials, Год журнала: 2023, Номер 14(4)

Опубликована: Дек. 3, 2023

Abstract The oxygen reduction reaction (ORR) is a crucial cathode for developing quasi‐solid zinc–air batteries (QZABs) with high energy density. However, the activity and stability of catalysts under extreme conditions have not been fully explore. Herein, series systematic experiments theoretical calculations conducted to investigate potential introducing Fe x Co y into nitrogen (N)‐doped porous carbon (NPC) via one‐step pyrolysis form core–shell structure that can effectively enhance catalysts, particularly at low temperatures. Due difference in work function 5.12, 5.11, 5.06 eV, spin‐polarized charge transferred pyridinic‐N site on surface transfer. Consequently, exhibits varying degrees magnetic moment 0.024 µ B , which forming OOH* enhances ORR activity. 5 @NPC catalyst evaluated QZABs −40 °C achieved power density up 117.6 mW cm −2 only 18.7% lower than normal temperature, cycle life 300 h. This study provides means realize design environments explore their application potential.

Язык: Английский

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Promotion of Anatase/Rutile Junction to Direct Conversion of Syngas to Ethanol on the Rh/TiO₂ Catalysts

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1874 - 1881

Опубликована: Янв. 20, 2024

Although significant efforts have been made for the direct syngas conversion to ethanol, ethanol yield remains low. Herein, we studied on Rh/TiO2 catalysts with different TiO2 phase compositions. The selectivity and reached 34.9 19.4%, respectively, at a 55.7% CO Rh/P25 catalyst. Among supported single Rh catalysts, this is currently highest reported yield. catalyst also shows good stability. mixture of anatase–rutile phases in P25 promotes electron transfer from species because strong metal–support interaction. It boosts Rh0 active site generation, dissociation, CHx formation, which intermediate formation. In contrast, pure anatase or rutile presents poor yield, mainly produces Rh+ species. This study provides an effective method improve conversion.

Язык: Английский

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Natural Sunlight‐Driven CO₂ Hydrogenation into Light Olefins at Ambient Pressure over Bifunctional Cu‐Promoted CoFe Alloy Catalyst

Advanced Functional Materials, Год журнала: 2024, Номер 34(30)

Опубликована: Фев. 23, 2024

Abstract The natural sunlight‐driven conversion of CO 2 into valuable C 2+ products is urgently being pursued at ambient pressure, yet it poses a substantial challenge. Herein, bifunctional Cu‐promoted CoFe alloy catalyst designed for the light‐driven hydrogenation light olefins. Under weak solar‐irradiation intensity 0.45 kW m −2 (0.45 sun), optimal exhibits excellent activity and selectivity, with an impressive 73.7% selectivity hydrocarbons outstanding 56.5% 2‐4 olefins, which best photosynthesis from sunlight to date. design combines advantages both metallic Cu components, providing synergistic effect that enhances performance. promoter plays crucial role in enhancing adsorption hydrogen spillover, while provides stable coupling site 1 intermediate promoting This study new insights catalysts opens up possibilities sustainable production olefins renewable resources.

Язык: Английский

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Recent progress on surface chemistry I: Assembly and reaction

Chinese Chemical Letters, Год журнала: 2024, Номер 35(12), С. 110055 - 110055

Опубликована: Май 27, 2024

Язык: Английский

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Regulating Atomically‐Precise Pt Sites for Boosting Light‐Driven Dry Reforming of Methane

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(46)

Опубликована: Авг. 12, 2024

Abstract Light‐driven dry reforming of methane is a promising and mild route to convert two greenhouse gas into valuable syngas. However, developing facile strategy atomically‐precise regulate the active sites realize balanced stable syngas production still challenging. Herein, we developed spatial confinement approach precisely control over platinum species on TiO 2 surfaces, from single atoms nanoclusters. The configuration comprising sub‐nanoclusters engenders pronounced electronic metal‐support interactions, with resultant interfacial states prompting surface charge rearrangement. unique geometric properties these atom‐cluster assemblies facilitate effective activation CH 4 CO , accelerating intermediate coupling minimizing side reactions. Our catalyst exhibits an outstanding generation rate 34.41 mol g Pt −1 h superior durability, displaying high apparent quantum yield 9.1 % at 365 nm turnover frequency 1289 . This work provides insightful understanding for exploring more multi‐molecule systems atomic scale.

Язык: Английский

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Mass Transfer Modulation by Hollow Multi‐Shelled Structures for High Space‐Time Yield Synthesis of Light Olefins from Syngas

Advanced Functional Materials, Год журнала: 2024, Номер 34(27)

Опубликована: Март 1, 2024

Abstract The separation of CO activation and C─C coupling enables oxide–zeolite catalyzed tandem reaction toward direct conversion syngas into light olefins to be a promising alternative for the traditional Fischer–Tropsch process with elevated selectivity. Utilizing controlled mass transfer match reactants intermediates presents an appealing strategy break limitation on space‐time yield in this process. In work, ZnCrO x hollow multi‐shelled structures (HoMS) are fabricated enhance adsorption enrichment ability syngas, thereby strengthening rate‐determining step resulting accelerated generation intermediates. When coupled SAPO zeolite, quintuple‐shelled HoMS‐based catalysts exhibit record high C 2 = ‐C 4 559 mg·g cat −1 ·h selectivity 90%. This work demonstrates advantages precise nanostructure sculpturing behavior microenvironment provides new highly selective olefins, based efficient sufficient feeding through effects within HoMS.

Язык: Английский

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