Photocatalytic and electrocatalytic transformations of C1 molecules involving C–C coupling

Energy & Environmental Science, Journal Year: 2020, Volume and Issue: 14(1), P. 37 - 89

Published: Oct. 31, 2020

Selective transformation of one-carbon (C1) molecules, which are abundant or easily available and inexpensive carbon feedstocks, into value-added multi-carbon (C2+) compounds is a very attractive but highly challenging research target. Photocatalysis electrocatalysis have offered great opportunities for the activation controllable C–C coupling C1 molecules under mild environmentally benign conditions. This article provides critical review on recent advances in photocatalytic electrocatalytic conversions major including CO, CO2, CH4, CH3OH HCHO, C2+ compounds, such as C2H4, C3H6, ethanol ethylene glycol, play essential roles current chemical energy industry. Besides photocatalysts electrocatalysts reported these conversions, structure–performance relationships key factors that control activity product selectivity analysed to provide insights rational design more efficient catalysts synthesis from feedstocks. The active species, reaction intermediates catalyst-functioning mechanism discussed deepen understanding chemistry selective presence solar electrical energy.

Language: Английский

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Aromatics Production via Methanol-Mediated Transformation Routes

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(13), P. 7780 - 7819

Published: June 14, 2021

The methanol-to-aromatics (MTA) process is regarded as a promising route to produce aromatic commodities through non-petroleum carbon resources, such biomass, waste, coal, natural gas, and CO2. In contrast with the industrially implemented methanol-to-olefin (MTO) process, most MTA studies are still in laboratory-scale stage. Recently, few demonstration plants of have been successfully launched, indicating importance gradual industrial maturity this technology. However, there many fundamental questions technological challenges that must be addressed. Review, we summarize recent advances mechanistic understanding on reaction catalyst deactivation during MTA, elaborate available strategies improve catalytic performance, correlate other important aromatization processes. With knowledge hand, share our views future research directions field.

Language: Английский

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Interfacing with Carbonaceous Potassium Promoters Boosts Catalytic CO₂ Hydrogenation of Iron

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(20), P. 12098 - 12108

Published: Aug. 26, 2020

Directly converting carbon dioxide into high-valued olefins (ethylene, propylene, and linear α-olefins) with regenerative hydrogen could be a way of reducing CO2 emissions replacing fossil fuels. However, precise control C–O activation subsequent C–C coupling toward those remain challenge, due to the unclear catalytic mechanism on active sites surrounding promoters. Herein, we demonstrate that carbonaceous series K-promoters from K2CO3, CH3COOK, KHCO3, KOH can induce Fe/C catalysts form more distinct Fe5C2–K2CO3 interface in nanoscale via hydrogenation, which boosts production by facilitating electron transfer potassium iron species. A high olefin selectivity near 75% hydrocarbons is realized at conversion than 32%. The maximum yield reaches up 20.1%, record-breaking highest value among all Fe based hydrogenation literature. More interestingly, appropriate proximity between catalyst endow system an outstanding stability. These findings enrich chemistry provide strategy design highly selective for chemicals.

Language: Английский

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Neighboring Zn–Zr Sites in a Metal–Organic Framework for CO₂ Hydrogenation

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(23), P. 8829 - 8837

Published: June 7, 2021

ZrZnOx is active in catalyzing carbon dioxide (CO2) hydrogenation to methanol (MeOH) via a synergy between ZnOx and ZrOx. Here we report the construction of Zn2+–O–Zr4+ sites metal–organic framework (MOF) reveal insights into structural requirement for MeOH production. The are obtained by postsynthetic treatment Zr6(μ3-O)4(μ3-OH)4 nodes MOF-808 ZnEt2 mild thermal remove capping ligands afford exposed metal catalysis. resultant MOF-808-Zn catalyst exhibits >99% selectivity CO2 at 250 °C high space-time yield up 190.7 mgMeOH gZn–1 h–1. catalytic activity stable least 100 h. X-ray absorption spectroscopy (XAS) analyses indicate presence centers instead ZnmOn clusters. Temperature-programmed desorption (TPD) hydrogen H/D exchange tests show activation H2 Zn2+ centers. Open Zr4+ also critical, as supported on Zr-based other MOFs without open fail produce MeOH. TPD reveals importance bicarbonate decomposition under reaction conditions generating activation. well-defined local structures metal-oxo provide unique opportunity elucidate details bifunctional

Language: Английский

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Uncovering the reaction mechanism behind CoO as active phase for CO2 hydrogenation

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

Published: Jan. 14, 2022

Abstract Transforming carbon dioxide into valuable chemicals and fuels, is a promising tool for environmental industrial purposes. Here, we present catalysts comprising of cobalt (oxide) nanoparticles stabilized on various support oxides hydrocarbon production from dioxide. We demonstrate that the activity selectivity can be tuned by selection oxide oxidation state. Modulated excitation (ME) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals follows hydrogen-assisted pathway, whereas metallic mainly direct dissociation pathway. Contrary to commonly considered active phase cobalt-based catalysts, titania most catalyst in this study produces 11% C 2+ hydrocarbons. The increases 39% (yielding 104 mmol h −1 g cat hydrocarbons) upon co-feeding CO 2 at ratio 1:2 250 °C 20 bar, thus outperforming majority typical catalysts.

Language: Английский

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ZnZrOx integrated with chain-like nanocrystal HZSM-5 as efficient catalysts for aromatics synthesis from CO2 hydrogenation

Applied Catalysis B Environment and Energy, Journal Year: 2021, Volume and Issue: 286, P. 119929 - 119929

Published: Jan. 24, 2021

Language: Английский

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Highly stable and selective layered Co-Al-O catalysts for low-temperature CO2 methanation

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 310, P. 121303 - 121303

Published: March 12, 2022

Language: Английский

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Porous framework materials for energy & environment relevant applications: A systematic review

Green Energy & Environment, Journal Year: 2023, Volume and Issue: 9(2), P. 217 - 310

Published: Jan. 3, 2023

Carbon peaking and carbon neutralization trigger a technical revolution in energy & environment related fields. Development of new technologies for green production storage, industrial saving efficiency reinforcement, capture, pollutant gas treatment is highly imperious demand. The emerging porous framework materials such as metal–organic frameworks (MOFs), covalent organic (COFs) hydrogen-bonded (HOFs), owing to the permanent porosity, tremendous specific surface area, designable structure customizable functionality, have shown great potential major energy-consuming processes, including sustainable catalytic conversion, energy-efficient separation storage. Herein, this manuscript presents systematic review global comprehensive applications, from macroscopic application perspective.

Language: Английский

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Modulating Electronic Interaction over Zr–ZnO Catalysts to Enhance CO₂ Hydrogenation to Methanol

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 508 - 521

Published: Dec. 22, 2023

ZnZrOx catalysts have been widely used to catalyze CO2 hydrogenation methanol, the catalytic characteristics of active sites being closely related electronic interaction between components. However, Zn and Zr for is not clear. Herein, we investigate impact on behavior catalysts. XPS results DFT calculations demonstrate that there an with electron transfer from Zn, resulting in formation electron-rich sites. Combined H2-TPD, propylene reaction, H2–D2 exchange experiments, situ DRIFTS, solid-state 1H NMR results, it evident more conductive accelerate H2 dissociation form hydride species, likely due Meanwhile, such transfers can promote adsorption bidentate bicarbonate carbonate species also boost their formate methoxy assistance species. The experimental show favorable enhance CH3OH selectivity yield, indicating dominant enhancing CH3OH. This work reveals pivotal role hydrogenation, which beneficial rationally design optimize required

Language: Английский

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

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(5), P. 714 - 725

Published: Feb. 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.

Language: Английский

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