Cocatalysts for Selective Photoreduction of CO₂into Solar Fuels

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(6), P. 3962 - 4179

Published: Feb. 14, 2019

Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution simultaneously overcome both environmental problems energy crisis. The low selectivity challenging multi-electron photoreduction reactions makes it one the holy grails in heterogeneous photocatalysis. This Review highlights important roles cocatalysts selective photocatalytic reduction using semiconductor catalysts. A special emphasis this review placed on key role, design considerations modification strategies for photoreduction. Various cocatalysts, such as biomimetic, metal-based, metal-free, multifunctional ones, their are summarized discussed, along with recent advances area. provides useful information highly photo(electro)reduction electroreduction complements existing reviews various photocatalysts.

Language: Английский

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Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products

Nature Catalysis, Journal Year: 2019, Volume and Issue: 2(3), P. 198 - 210

Published: March 4, 2019

Language: Английский

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Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C–C coupling over fluorine-modified copper

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(6), P. 478 - 487

Published: April 20, 2020

Language: Английский

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Core–shell structured catalysts for thermocatalytic, photocatalytic, and electrocatalytic conversion of CO₂

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(10), P. 2937 - 3004

Published: Jan. 1, 2020

Catalytic conversion of CO2 to produce fuels and chemicals is attractive in prospect because it provides an alternative fossil feedstocks the benefit converting cycling greenhouse gas on a large scale. In today's technology, converted into hydrocarbon Fischer-Tropsch synthesis via water shift reaction, but processes for direct such as methane, methanol, C2+ hydrocarbons or syngas are still far from large-scale applications processing challenges that may be best addressed by discovery improved catalysts-those with enhanced activity, selectivity, stability. Core-shell structured catalysts relatively new class nanomaterials allow controlled integration functions complementary materials optimised compositions morphologies. For conversion, core-shell can provide distinctive advantages addressing catalyst sintering activity loss reforming processes, insufficient product selectivity thermocatalytic hydrogenation, low efficiency photocatalytic electrocatalytic hydrogenation. preceding decade, substantial progress has been made synthesis, characterization, evaluation potential applications. Nonetheless, remain inexpensive, robust, regenerable this class. This review in-depth assessment these thermocatalytic, photocatalytic, valuable hydrocarbons.

Language: Английский

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Promoting electrocatalytic CO2 reduction to formate via sulfur-boosting water activation on indium surfaces

Nature Communications, Journal Year: 2019, Volume and Issue: 10(1)

Published: Feb. 21, 2019

Electrocatalytic reduction of CO2 to fuels and chemicals is one the most attractive routes for utilization. Current catalysts suffer from low faradaic efficiency a CO2-reduction product at high current density (or reaction rate). Here, we report that sulfur-doped indium catalyst exhibits formate (>85%) in broad range (25-100 mA cm-2) electrocatalytic aqueous media. The formation rate reaches 1449 μmol h-1 cm-2 with 93% efficiency, highest value reported date. Our studies suggest sulfur accelerates by unique mechanism. Sulfur enhances activation water, forming hydrogen species can readily react produce formate. promoting effect chalcogen modifiers be extended other metal catalysts. This work offers simple useful strategy designing both active selective electrocatalysts reduction.

Language: Английский

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Protecting Copper Oxidation State via Intermediate Confinement for Selective CO₂ Electroreduction to C₂₊ Fuels

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(13), P. 6400 - 6408

Published: March 16, 2020

Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment enabling deep CO2 reduction oxygenates hydrocarbons (e.g., C2+ compounds) is the difficulty coupling carbon-carbon bonds efficiently. Copper in +1 oxidation state has been thought be active for catalyzing formation, whereas it prone being reduced Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine intermediates formed situ, which turn covers local catalyst surface thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide exhibit a Faradaic efficiency 75.2 ± 2.7% partial current density 267 13 mA cm-2 large C2+-to-C1 ratio ∼7.2. Operando Raman spectra, conjunction X-ray absorption studies, confirm species as-designed are well retained during reduction, leads marked selectivity rate.

Language: Английский

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CO₂ Reduction: From Homogeneous to Heterogeneous Electrocatalysis

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 53(1), P. 255 - 264

Published: Jan. 8, 2020

Due to increasing worldwide fossil fuel consumption, carbon dioxide levels have increased in the atmosphere with increasingly important impacts on environment. Renewable and clean sources of energy been proposed, including wind solar, but they are intermittent require efficient scalable storage technologies. Electrochemical CO2 reduction reaction (CO2RR) provides a valuable approach this area. It combines solar- or wind-generated electrical production chemical bonds carbon-based fuels. can provide ways integrate capture, utilization, cycles while maintaining controlled atmospheric CO2. Electrochemistry allows for utilization an input drive reactions. Because is kinetically inert, highly active catalysts required decrease barriers sufficiently so that rates be achieved sufficient electrochemical reduction. Given associated multiple electron-proton CO, formaldehyde (HC(O)H), formic acid, formate (HC(O)OH, HC(O)O-), more reduced forms carbon, there also demand high selectivity catalysis. Catalysts explored include homogeneous solution, immobilized surfaces, heterogeneous catalysts. In catalysis, occurs following diffusion catalyst electrode where proton coupled electron transfer occurs. Useful area typically transition-metal complexes organic ligands properties utilize combinations metal ligand redox levels. As way limit amount catalyst, device-like configurations, added surfaces conductive substrates by surface binding, polymeric films, molecular structures electronic configurations related solution. Immobilized, suffer from performance losses even decomposition during long-term cycles, amenable detailed mechanistic investigations. parallel efforts, nanocatalysts detail development facile synthetic procedures offer catalytic areas. Their activity stability attracted significant level investigation, possible exploitation large-scale applications. However, translation reactivity creates new environment complicates elucidation details identification site exploring pathways. Here, results previous studies based complex electroreduction summarized. Early showed Ru, Ir, Rh, Os, well-defined structures, all capable catalyzing CO formate. Derivatives were attached conducting electrodes bonding, noncovalent polymerization. The concept binding has extended preparation chemically deposition nanostructured such as nano tin, copper, which shown selectivities activities toward our presentation, we end Account recent advances perspective about application electrocatalysis

Language: Английский

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Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO₂ Reduction to Formate

Advanced Energy Materials, Journal Year: 2019, Volume and Issue: 10(11)

Published: Dec. 13, 2019

Abstract Selective CO 2 reduction to formic acid or formate is the most technologically and economically viable approach realize electrochemical valorization. Main group metal–based (Sn, Bi, In, Pb, Sb) nanostructured materials hold great promise, but are still confronted with several challenges. Here, current status, challenges, future opportunities of main for reviewed. Firstly, fundamentals presented, including technoeconomic viability different products, possible reaction pathways, standard experimental procedure, performance figures merit. This then followed by detailed discussions about types electrocatalyst materials, an emphasis on underlying material design principles promoting activity, selectivity, stability. Subsequently, recent efforts flow cells membrane electrode assembly reviewed so as promote density well mechanistic studies using in situ characterization techniques. To conclude a short perspective offered directions this exciting field.

Language: Английский

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Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: March 16, 2020

Abstract Highly effective electrocatalysts promoting CO 2 reduction reaction (CO RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c -MOF) with copper-phthalocyanine as ligand (CuN 4 ) and zinc-bis(dihydroxy) complex (ZnO linkage (PcCu-O 8 -Zn). The PcCu-O -Zn exhibits high selectivity of 88%, turnover frequency 0.39 s −1 long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. molar H /CO ratio (1:7 4:1) can be tuned varying metal centers applied potential, making 2D -MOFs highly relevant for syngas industry applications. contrast experiments combined operando spectroelectrochemistry theoretical calculation unveil synergistic catalytic mechanism; ZnO complexes act RR sites CuN promote the protonation adsorbed during RR. This work offers strategy on developing MOF synergistically catalyzing toward synthesis.

Language: Английский

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Transition metal-based catalysts for the electrochemical CO₂reduction: from atoms and molecules to nanostructured materials

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(19), P. 6884 - 6946

Published: Jan. 1, 2020

An overview of the main strategies for rational design transition metal-based catalysts electrochemical conversion CO₂, ranging from molecular systems to single-atom and nanostructured catalysts.

Language: Английский

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