Efficient electrocatalytic CO2 reduction to CO with high selectivity using a N-doped carbonized wood membrane

Abstract Photocatalytic CO2 reduction into energy carriers is of utmost importance due to the rising concentrations of carbon dioxide and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH4), from CO2 remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ε-Keggin clusters and photosensitive TCPP linkers, exhibiting high selectivity (> 96%) for CH4 formation in photocatalytic CO2 reduction system. To our knowledge, the high CH4 selectivity of POMCFs has surpassed all of the reported coordiantion framework-based heterogeneous photocatalysts for CO2-to-CH4 conversion. Significantly, the introduction of Zn-ε-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH4 formation, considering that eight MoV atoms can theoretically donate eight electrons to fulfill the multi-electrons reduction process of CO2 to CH4 transformation.

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A Z-scheme photocatalyst constructed with an yttrium–tantalum oxynitride and a binuclear Ru(ii) complex for visible-light CO2 reduction

Chemical Communications ◽

10.1039/c6cc03627a ◽

2016 ◽

Vol 52 (50) ◽

pp. 7886-7889 ◽

Cited By ~ 40

Author(s):

Kanemichi Muraoka ◽

Hiromu Kumagai ◽

Miharu Eguchi ◽

Osamu Ishitani ◽

Kazuhiko Maeda

Keyword(s):

Visible Light ◽

Band Gap ◽

High Selectivity ◽

Co2 Reduction ◽

Very High ◽

Hybrid Photocatalyst

A hybrid photocatalyst composed of an yttrium–tantalum oxynitride (with a 2.1 eV band gap) and a binuclear Ru(ii) complex containing both photosensitizing and catalytic units was capable of reducing CO2 to HCOOH with very high selectivity (>99%) under visible light (>400 nm) irradiation.

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Unexpected High Selectivity for Acetate Formation from CO2 Reduction with Copper Based 2D Hybrid Catalysts at Ultralow Potentials

Chemical Science ◽

10.1039/d1sc05441d ◽

2021 ◽

Author(s):

Rongming Cai ◽

Mingzi Sun ◽

Jiazheng Ren ◽

Min Ju ◽

Xia Long ◽

...

Keyword(s):

High Selectivity ◽

Co2 Reduction ◽

Catalytic Performance ◽

Active Species ◽

Rapid Decay ◽

Hybrid Catalysts ◽

Commodity Chemicals ◽

Acetate Formation

Copper-based catalysts are efficient for CO2 reduction affording commodity chemicals. However, the Cu(I) active species are easily reduced to Cu(0) during CO2RR, leading to rapid decay of catalytic performance. Herein,...

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Selective photocatalytic CO2 reduction on copper–titanium dioxide: a study of the relationship between CO production and H2 suppression

Chemical Communications ◽

10.1039/c9cc02891a ◽

2019 ◽

Vol 55 (56) ◽

pp. 8068-8071 ◽

Cited By ~ 15

Author(s):

Yangchun Lan ◽

Yongzhi Xie ◽

Jiaxi Chen ◽

Zhuofeng Hu ◽

Dehu Cui

Keyword(s):

Titanium Dioxide ◽

High Selectivity ◽

Co2 Reduction ◽

The Relationship

High selectivity of CO2 reduction and suppression of H2 evolution on a Cu/TiO2 photocatalyst.

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Immobilizing cobalt phthalocyanine into a porous carbonized wood membrane as a self-supported heterogenous electrode for selective and stable CO2 electroreduction in water

Dalton Transactions ◽

10.1039/d0dt03304a ◽

2020 ◽

Vol 49 (44) ◽

pp. 15607-15611

Author(s):

Haidong Zhang ◽

Shixiong Min ◽

Fang Wang ◽

Zhengguo Zhang

Keyword(s):

Cobalt Phthalocyanine ◽

Co2 Electroreduction ◽

Wood Membrane ◽

Carbonized Wood

Immobilizing CoPc into a porous carbonized wood membrane (CoPc/CWM) leads to a self-supported heterogenous electrode for efficient CO2 electroreduction in water.

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Directing the reactivity of metal hydrides for selective CO2 reduction

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1811396115 ◽

2018 ◽

Vol 115 (50) ◽

pp. 12686-12691 ◽

Cited By ~ 29

Author(s):

Bianca M. Ceballos ◽

Jenny Y. Yang

Keyword(s):

High Selectivity ◽

Co2 Reduction ◽

Metal Hydrides ◽

Product Formation ◽

Proton Reduction ◽

Efficient Catalyst ◽

Faradaic Efficiency ◽

Catalytic Intermediates ◽

Proton Activity ◽

Selection Of

A critical challenge in electrocatalytic CO2 reduction to renewable fuels is product selectivity. Desirable products of CO2 reduction require proton equivalents, but key catalytic intermediates can also be competent for direct proton reduction to H2. Understanding how to manage divergent reaction pathways at these shared intermediates is essential to achieving high selectivity. Both proton reduction to hydrogen and CO2 reduction to formate generally proceed through a metal hydride intermediate. We apply thermodynamic relationships that describe the reactivity of metal hydrides with H+ and CO2 to generate a thermodynamic product diagram, which outlines the free energy of product formation as a function of proton activity and hydricity (∆GH−), or hydride donor strength. The diagram outlines a region of metal hydricity and proton activity in which CO2 reduction is favorable and H+ reduction is suppressed. We apply our diagram to inform our selection of [Pt(dmpe)2](PF6)2 as a potential catalyst, because the corresponding hydride [HPt(dmpe)2]+ has the correct hydricity to access the region where selective CO2 reduction is possible. We validate our choice experimentally; [Pt(dmpe)2](PF6)2 is a highly selective electrocatalyst for CO2 reduction to formate (>90% Faradaic efficiency) at an overpotential of less than 100 mV in acetonitrile with no evidence of catalyst degradation after electrolysis. Our report of a selective catalyst for CO2 reduction illustrates how our thermodynamic diagrams can guide selective and efficient catalyst discovery.

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