Carbon capture and conversion using metal–organic frameworks and MOF-based materials

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(10), P. 2783 - 2828

Published: Jan. 1, 2019

Rapidly increasing atmospheric CO2 concentrations threaten human society, the natural environment, and synergy between two. In order to ameliorate problem, carbon capture conversion techniques have been proposed. Metal-organic framework (MOF)-based materials, a relatively new class of porous materials with unique structural features, high surface areas, chemical tunability stability, extensively studied respect their applicability such techniques. Recently, it has become apparent that capabilities MOF-based significantly boost potential toward conversion. Furthermore, materials' well-defined structures greatly facilitate understanding structure-property relationships roles in this review, we provide comprehensive account significant progress design synthesis including MOFs, MOF composites derivatives, application Special emphases on capacities catalytic performances are discussed.

Language: Английский

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Ionic Exchange of Metal–Organic Frameworks to Access Single Nickel Sites for Efficient Electroreduction of CO₂

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(24), P. 8078 - 8081

Published: June 8, 2017

Single-atom catalysts often exhibit unexpected catalytic activity for many important chemical reactions because of their unique electronic and geometric structures with respect to bulk counterparts. Herein we adopt metal–organic frameworks (MOFs) assist the preparation a catalyst containing single Ni sites efficient electroreduction CO2. The synthesis is based on ionic exchange between Zn nodes adsorbed ions within cavities MOF. This single-atom exhibited an excellent turnover frequency CO2 (5273 h–1), Faradaic efficiency CO production over 71.9% current density 10.48 mA cm–2 at overpotential 0.89 V. Our findings present some guidelines rational design accurate modulation nanostructured atomic scale.

Language: Английский

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Metal–Organic Framework-Based Catalysts with Single Metal Sites

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(21), P. 12089 - 12174

Published: May 1, 2020

Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, high surface area, different types MOF-based single sites well exploited, including coordinately unsaturated from nodes metallolinkers, as active species immobilized MOFs. Furthermore, controllable thermal transformation MOFs can upgrade them nanomaterials functionalized with single-atom catalysts (SACs). These unique features derivatives enable serve highly versatile platform for catalysis, which has actually been becoming rapidly developing interdisciplinary research area. In this review, we overview the recent developments catalysis at in emphasis on structures applications thermocatalysis, electrocatalysis, photocatalysis. We also compare results summarize major insights gained works providing challenges prospects emerging field.

Language: Английский

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Scalable Production of Efficient Single-Atom Copper Decorated Carbon Membranes for CO₂ Electroreduction to Methanol

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(32), P. 12717 - 12723

Published: July 26, 2019

Electrocatalytic reduction reaction of CO2 (CO2RR) is an effective way to mitigate energy and environmental issues. However, very limited catalysts are capable converting resources into high-value products such as hydrocarbons or alcohols. Herein, we first propose a facile strategy for the large-scale synthesis isolated Cu decorated through-hole carbon nanofibers (CuSAs/TCNFs). This CuSAs/TCNFs membrane has excellent mechanical properties can be directly used cathode CO2RR, which could generate nearly pure methanol with 44% Faradaic efficiency in liquid phase. The self-supporting structure greatly reduces embedded metal atoms produces abundant efficient single atoms, actually participate eventually causing -93 mA cm-2 partial current density C1 more than 50 h stability aqueous solution. According DFT calculations, possess relatively higher binding *CO intermediate. Therefore, further reduced like methanol, instead being easily released from catalyst surface CO product. report may benefit design high-yield single-atom other electrocatalytic reactions.

Language: Английский

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Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction

Nature Communications, Journal Year: 2018, Volume and Issue: 9(1)

Published: Jan. 23, 2018

Restructuring-induced catalytic activity is an intriguing phenomenon of fundamental importance to rational design high-performance catalyst materials. We study three copper-complex materials for electrocatalytic carbon dioxide reduction. Among them, the copper(II) phthalocyanine exhibits by far highest yielding methane with a Faradaic efficiency 66% and partial current density 13 mA cm−2 at potential – 1.06 V versus reversible hydrogen electrode. Utilizing in-situ operando X-ray absorption spectroscopy, we find that under working conditions undergoes structural oxidation state changes form ~ 2 nm metallic copper clusters, which catalyzes dioxide-to-methane conversion. Density functional calculations rationalize restructuring behavior attribute reversibility strong divalent metal ion–ligand coordination in molecular structure small size generated clusters reaction conditions. The conversion into value-added products requires understanding active species present Here, authors discover copper-containing complexes reversibly transform during electrocatalysis methane-producing nanoclusters.

Language: Английский

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Metal-organic frameworks for catalysis: State of the art, challenges, and opportunities

EnergyChem, Journal Year: 2019, Volume and Issue: 1(1), P. 100005 - 100005

Published: June 27, 2019

Language: Английский

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Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities

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

Published: Jan. 30, 2020

Abstract Carbon dioxide electroreduction provides a useful source of carbon monoxide, but comparatively few catalysts could be sustained at current densities industry level. Herein, we construct high-yield, flexible and self-supported single-atom nickel-decorated porous membrane catalyst. This possesses interconnected nanofibers hierarchical pores, affording abundant effective nickel single atoms that participate in reduction. Moreover, the excellent mechanical strength well-distributed this combines gas-diffusion catalyst layers into one architecture. integrated directly used as gas diffusion electrode to establish an extremely stable three-phase interface for high-performance electroreduction, producing monoxide with 308.4 mA cm −2 partial density 88% Faradaic efficiency up 120 h. We hope work will provide guidance design application electro-catalysts potential industrial scale.

Language: Английский

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Oriented electron transmission in polyoxometalate-metalloporphyrin organic framework for highly selective electroreduction of CO2

Nature Communications, Journal Year: 2018, Volume and Issue: 9(1)

Published: Oct. 22, 2018

The design of highly stable, selective and efficient electrocatalysts for CO2 reduction reaction is desirable while largely unmet. In this work, a series precisely designed polyoxometalate-metalloporphyrin organic frameworks are developed. Noted that the integration {ε-PMo8VMo4VIO40Zn4} cluster metalloporphyrin endows these greatly advantages in terms electron collecting donating, migration electrocatalytic active component reaction. Thus-obtained catalysts finally present excellent performances mechanisms catalysis processes discussed revealed by density functional theory calculations. Most importantly, Co-PMOF exhibits remarkable faradaic efficiency ( > 94%) over wide potential range (-0.8 to -1.0 V). Its best can reach up 99% (highest reported metal-organic frameworks) it high turnover frequency 1656 h-1 stability 36 h).

Language: Английский

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Metal–organic frameworks for electrocatalysis

Coordination Chemistry Reviews, Journal Year: 2017, Volume and Issue: 373, P. 22 - 48

Published: Sept. 21, 2017

Language: Английский

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Metal–Organic Frameworks Mediate Cu Coordination for Selective CO₂ Electroreduction

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(36), P. 11378 - 11386

Published: Aug. 16, 2018

The electrochemical carbon dioxide reduction reaction (CO2RR) produces diverse chemical species. Cu clusters with a judiciously controlled surface coordination number (CN) provide active sites that simultaneously optimize selectivity, activity, and efficiency for CO2RR. Here we report strategy involving metal-organic framework (MOF)-regulated cluster formation shifts CO2 electroreduction toward multiple-carbon product generation. Specifically, promoted undercoordinated during the of by controlling structure dimer, precursor clusters. We distorted symmetric paddle-wheel dimer secondary building block HKUST-1 to an asymmetric motif separating adjacent benzene tricarboxylate moieties using thermal treatment. By varying materials processing conditions, modulated local atomic structure, oxidation state bonding strain dimers. Using electron paramagnetic resonance (EPR) in situ X-ray absorption spectroscopy (XAS) experiments, observed low CN from dimers electroreduction. These exhibited 45% C2H4 faradaic (FE), record MOF-derived catalysts. A structure-activity relationship was established wherein tuning Cu-Cu determines CO2RR selectivity.

Language: Английский

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