Insights into the Influence of CeO₂Crystal Facet on CO₂Hydrogenation to Methanol over Pd/CeO₂Catalysts

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(19), P. 11493 - 11509

Published: Sept. 10, 2020

CeO2 is an excellent potential material for CO2 hydrogenation attributed to the highly tunable properties including metal–support interaction and abundant oxygen vacancy. In this work, four supports with structurally well-defined different shapes crystal facets are hydrothermally prepared, their effects on composition of Pd species vacancy over Pd/CeO2 catalysts have been intensively investigated in reduction methanol. The 2Pd/CeO2-R (rods) shows highest concentration number vacancies, where (110) facet high surface mobility low formation energy exposed CeO2-R surface. at interface (111) (100) mainly observed 2Pd/CeO2-P (polyhedrons) higher than single 2Pd/CeO2-O (octahedrons) 2Pd/CeO2-C (cubs), respectively. presence promotes vacancies by providing dissociated H atoms facilitate removal O ceria support under a H2 atmosphere. Both PdxCe1–xOδ solid solution dominated PdO CeO2-O reduced metallic after 6–10 nm average particle size. As revealed density functional theory (DFT) calculations, contrast Pd0 atom thermodynamically most unstable PdxCe1−xOδ solution, nanoparticles stable realistic reaction conditions. catalytic activity as abundantly available function adsorption activation sites. Moreover, reactivity correlated its energy. lower facilitates vacancy; however, each TOFoxygen 15 times that 2Pd/CeO2-R. Thus, suitable likely favorable enhancing reactivity. DFT calculations indicate CH3OH probably from formate (HCOO*) pathway via C–O bond cleavage H2COOH*, HCOO* HCOOH* rate-limiting step. These results would provide experimental theoretical insights into rational design effective catalyst hydrogenation.

Language: Английский

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Highlights and challenges in the selective reduction of carbon dioxide to methanol

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(8), P. 564 - 579

Published: June 24, 2021

Language: Английский

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Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 385 - 441

Published: Nov. 2, 2021

As the world pledges to significantly cut carbon emissions, demand for sustainable and clean energy has now become more important than ever. This includes both production storage of carriers, a majority which involve catalytic reactions. article reviews recent developments homogeneous catalysts in emerging applications energy. The most focus been on hydrogen as several efficient have reported recently (de)hydrogenative transformations promising economy. Another direction that extensively covered this review is methanol Homogeneous investigated from CO

Language: Английский

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CO₂ Hydrogenation to Methanol over In₂O₃-Based Catalysts: From Mechanism to Catalyst Development

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(3), P. 1406 - 1423

Published: Jan. 14, 2021

Carbon dioxide (CO2) hydrogenation to methanol with H2 produced renewable energy represents a promising path for the effective utilization of major anthropogenic greenhouse gas, in which catalysts play key role CO2 conversion and selectivity. Although still under development, indium oxide (In2O3)-based have attracted great attention recent years due excellent selectivity along high activity conversion. In this review, we discuss advances In2O3-based based on both experimental computational studies. Various strategies been adopted improve catalytic performance by facilitating formation surface oxygen vacancies (In2O3–x) as active sites, activation toward mitigate reverse water–gas shift reaction, stabilization intermediates. Mechanistic insights are gained from combining kinetic studies, situ characterization, theoretical investigations involving via formate HCOO* pathway versus carboxyl COOH* pathway. Strategies further promote selective include adding metal component such Pd or Ni In2O3 (which may also involve bimetallic In–M catalysts) vacancy formation, an promoter ZrO2 enhance adsorption activation, controlling concentration CO H2O adopting second other desired products olefins aromatics acid catalyst zeolites. Through comprehensive overview In2O3-related catalysts, present review paves way future development methanol.

Language: Английский

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Metal Sites in Zeolites: Synthesis, Characterization, and Catalysis

Chemical Reviews, Journal Year: 2022, Volume and Issue: 123(9), P. 6039 - 6106

Published: Sept. 1, 2022

Zeolites with ordered microporous systems, distinct framework topologies, good spatial nanoconfinement effects, and superior (hydro)thermal stability are an ideal scaffold for planting diverse active metal species, including single sites, clusters, nanoparticles in the framework-associated sites extra-framework positions, thus affording metal-in-zeolite catalysts outstanding activity, unique shape selectivity, enhanced recyclability processes of Brønsted acid-, Lewis metal-catalyzed reactions. Especially, thanks to advances zeolite synthesis characterization techniques recent years, zeolite-confined (denoted as metal@zeolite composites) have experienced rapid development heterogeneous catalysis, owing combination merits both intrinsic properties. In this review, we will present developments strategies incorporating tailoring zeolites advanced identification location, distribution, coordination environment species zeolites. Furthermore, catalytic applications demonstrated, emphasis on composites hydrogenation, dehydrogenation, oxidation Finally, point out current challenges future perspectives precise synthesis, atomic level identification, practical application catalyst system.

Language: Английский

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Recycling Carbon Dioxide through Catalytic Hydrogenation: Recent Key Developments and Perspectives

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(19), P. 11318 - 11345

Published: Aug. 21, 2020

Recycling CO2 as a renewable carbon source for the production of high-value fuels and chemicals has drawn global attention lately promising method to mitigate climate change lessen dependence on fossil fuels. Among available CO2-recycling options, catalytic hydrogenation is most realistic attractive choice if hydrogen produced using energy source. Depending nature catalyst, distinct reaction pathways, various value-added hydrocarbons can be produced. Intense research recently developed high-performance catalysts, identified clear deepened understanding mechanisms. In this review, we present an overview recent key advances in oxygenates that have large market sizes, such formic acid, methanol, methane, light olefins, well liquid fuels, terms catalyst design, performance, mechanism. addition, current technical challenges perspectives conversion processes are discussed with regard mitigation.

Language: Английский

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Advances in the Design of Heterogeneous Catalysts and Thermocatalytic Processes for CO₂ Utilization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 14147 - 14185

Published: Nov. 20, 2020

Utilization of CO2 as feedstock to produce fine chemicals and renewable fuels is a highly promising field, which presents unique challenges in its implementation at scale. Heterogeneous catalysis with simple operation industrial compatibility can be an effective means achieving this challenging task. This review summarizes the current developments heterogeneous thermal for production carbon monoxide, alcohols, hydrocarbons from CO2. A detailed discussion provided regarding structure–activity correlations between catalyst surface intermediate species aid rational design future generation catalysts. Effects active metal components, supports, promoters are discussed each section, will guide researchers synthesize new catalysts improved selectivity stability. Additionally, brief overview process considerations has been provided. Future research directions proposed special emphasis on application scope catalytic materials possible approaches increase performance.

Language: Английский

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Architectural Design for Enhanced C₂ Product Selectivity in Electrochemical CO₂ Reduction Using Cu-Based Catalysts: A Review

ACS Nano, Journal Year: 2021, Volume and Issue: 15(5), P. 7975 - 8000

Published: May 6, 2021

Electrochemical CO2 reduction to value-added chemicals and fuels is a promising approach mitigate the greenhouse effect arising from anthropogenic emission energy shortage caused by depletion of nonrenewable fossil fuels. The generation multicarbon (C2+) products, especially hydrocarbons oxygenates, great interest for industrial applications. To date, Cu only metal known catalyze C–C coupling in electrochemical reaction (eCO2RR) with appreciable efficiency kinetic viability produce wide range C2 products aqueous solutions. Nonetheless, poor product selectivity associated main technical problem application eCO2RR technology on global scale. Based extensive research efforts, delicate rational design electrocatalyst architecture using principles nanotechnology likely significantly affect adsorption energetics some key intermediates hence inherent pathways. In this review, we summarize recent progress that has been achieved tailoring efficient conversion target products. By considering experimental computational results, further analyze underlying correlations between catalyst its toward Finally, major challenges are outlined, directions future development suggested.

Language: Английский

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Towards the development of the emerging process of CO₂heterogenous hydrogenation into high-value unsaturated heavy hydrocarbons

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10764 - 10805

Published: Jan. 1, 2021

This review covers recent developments in the synthesis of α-olefins and aromatics from CO 2 hydrogenation via direct indirect routes.

Language: Английский

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Novel Heterogeneous Catalysts for CO₂ Hydrogenation to Liquid Fuels

ACS Central Science, Journal Year: 2020, Volume and Issue: 6(10), P. 1657 - 1670

Published: Sept. 18, 2020

Carbon dioxide (CO2) hydrogenation to liquid fuels including gasoline, jet fuel, diesel, methanol, ethanol, and other higher alcohols via heterogeneous catalysis, using renewable energy, not only effectively alleviates environmental problems caused by massive CO2 emissions, but also reduces our excessive dependence on fossil fuels. In this Outlook, we review the latest development in design of novel very promising catalysts for direct hydrocarbons, alcohols. Compared with methanol production, synthesis products two or more carbons (C2+) faces greater challenges. Highly efficient C2+ from can be achieved a reaction coupling strategy that first converts carbon monoxide then conducts C–C over bifunctional/multifunctional catalyst. Apart catalytic performance, unique catalyst ideas, structure–performance relationship, discuss current challenges perspectives industrial applications.

Language: Английский

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