Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4

Li, Jian; Huang, Hongliang; Xue, Wenjuan; Sun, Kang; Song, Xiaohui; Wu, Chunrui; Nie, Lei; Li, Yang; Liu, Chengyuan; Pan, Yang; Jiang, Hai‐Long; Mei, Donghai; Zhong, Chongli

doi:10.1038/s41929-021-00665-3

Cited by 558 publications

(369 citation statements)

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“…[157,158] Considering the synergistic effect of a single metal site on the reaction mechanism, dual-metal sites in carbon-based, metal complexes, and other inorganic materials have been proposed as rational for inducing high selectivity for hydrocarbon products in photocatalytic processes. Li et al [31] incorporated Ni and Cu into MOF-808 to construct a photocatalyst with flexible dual-metal-site pairs (DMSPs), where each metal exists in its single-site form, embedded into porous matrices. The synergetic effects within dual-metalsite pairs dramatically boosted the maximal CH 4 selectivity of electron-based 99.4% and product-based 97.5%, confirming the promise of dual single-atom catalysis as a paradigm for photocatalyst development.…”

Section: Single-atom Catalystsmentioning

confidence: 99%

“…[ 22 ] However, widespread adoption of CO 2 ‐to‐CH 4 photoreduction is hampered by the poor activity, [ 23 ] selectivity, [ 24 ] and stability [ 25 ] of presently available photocatalysts, motivating an exhaustive search for active and selective yet stable materials. Experimental catalyst engineering approaches for improving activity and selectivity include heterojunctions, [ 26 ] defect engineering, [ 27 ] cocatalysts, [ 28 ] surface modification, [ 29 ] facet engineering, [ 30 ] and single‐atom catalysis, [ 31 ] among which the former two have received the majority of attention in recent years (Figure 1b). However, it is also worth noting that single‐atom catalysis has very recently emerged as a new frontier in photocatalysis research.…”

Section: Introductionmentioning

confidence: 99%

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Emerging Strategies for CO₂ Photoreduction to CH₄: From Experimental to Data‐Driven Design

Cheng

Sun

Lim

et al. 2022

Advanced Energy Materials

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been described as a key metric for understanding the effects of global warming due to its direct impact on climate change. [2] Extensive modeling with energy-economyenvironment scenarios or projections to keep the global temperature from rising above 1.5 °C by the year 2100 shows that such a positive outlook is only possible if the global energy system is completely decarbonized (i.e., net-zero global CO 2 emissions) by mid-century, followed by active CO 2 removal (i.e., carbon-negative) in the second half of the century. [3] The catalytic conversion of CO 2 to valuable energy-related products (e.g., syngas, CH 4 , CH 3 OH, and longer-chain hydrocarbons) [4] by thermal reforming and hydrogenation, [5][6][7][8][9][10][11] electrocatalysis, [12][13][14] or photocatalysis [15] could occupy an important position in a future carbon-negative economy by directly replacing nonrenewable sources of these molecules, provided that the energy inputs to these processes are themselves derived from renewable sources. [16,17] In this regard, photocatalytic strategies stand out by not requiring a secondary medium of energy storage, and being able to realize the CO 2 conversion into high value-added fuels directly via renewable solar energy without external energy input. [18] Indeed, photocatalytic CO 2 reduction has been considered to be a "kill two birds with one stone" approach for sustainable energy production and greenhouse gas reduction. [19] In contrast, thermocatalytic approachesThe solar-energy-driven photoreduction of CO 2 has recently emerged as a promising approach to directly transform CO 2 into valuable energy sources under mild conditions. As a clean-burning fuel and drop-in replacement for natural gas, CH 4 is an ideal product of CO 2 photoreduction, but the development of highly active and selective semiconductor-based photocatalysts for this important transformation remains challenging. Hence, significant efforts have been made in the search for active, selective, stable, and sustainable photocatalysts. In this review, recent applications of cutting-edge experimental and computational materials design strategies toward the discovery of novel catalysts for CO 2 photocatalytic conversion to CH 4 are systematically summarized. First, insights into effective experimental catalyst engineering strategies, including heterojunctions, defect engineering, cocatalysts, surface modification, facet engineering, and single atoms, are presented. Then, datadriven photocatalyst design spanning density functional theory (DFT) simulations, high-throughput computational screening, and machine learning (ML) is presented through a step-by-step introduction. The combination of DFT, ML, and experiments is emphasized as a powerful solution for accelerating the discovery of novel catalysts for photocatalytic reduction of CO 2 . Last, challenges and perspectives concerning the interplay between experiments and data-driven rational design strategies for the industrialization of large-scale CO 2 photoreduction technologies are described.

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Section: Single-atom Catalystsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Emerging Strategies for CO₂ Photoreduction to CH₄: From Experimental to Data‐Driven Design

Cheng

Sun

Lim

et al. 2022

Advanced Energy Materials

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“…Inspired by nature, in a flexible microenvironment, Cu and Ni DMSPs are incorporated into the metal organic framework (MOF) in the form of monodisperse sites, and an MOF‐808‐CuNi photocatalyst has been developed by a wet‐chemical method (Figure 8i). [ 71 ] It realizes the adaptively catalytic process of active sites accompanying the reaction process, thereby stabilizing the C1 intermediate in the process of photoreduction of CO 2 , and exhibiting high selectivity and high yield from CO 2 to CH 4 . The above reports provide new ideas for artificially constructing bioinspired photocatalysts for CO 2 photoreduction with bionic catalytic active sites.…”

Section: Biomimetic Photocatalysts With Artificial Photocatalytic Act...mentioning

confidence: 99%

mentioning

confidence: 99%

A Review on the Bioinspired Photocatalysts and Photocatalytic Systems

Yang

Fan

et al. 2022

Advanced Sustainable Systems

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After long‐term evolution, organisms in nature have achieved optimal structure, organization, and function to adapt to the environment. Some ingenious biological structures have highly efficient solar light absorption, matter transmission, and natural photocatalytic properties, such as leaves, sunflowers, seaweeds, algae, bacteria. Artificial photocatalysis, which involves CO2 reduction and water splitting to obtain green renewable energy or oxygen, is of great significance for solving the problem of energy shortages, achieving carbon neutrality, and building a sustainable society. In order to improve the efficiency of artificial photocatalysis, it is necessary to develop highly efficient photocatalysts by expanding ideas and drawing innovative inspiration from nature. Artificially constructed photocatalysts with bionic structures achieved by simulating natural organisms have gradually become an exciting research field with great potential in recent years. This article reviews bioinspired photocatalysts and photocatalytic systems from the aspects of principle, composition, construction method, and the achieved performance. It is expected that this review will help researchers develop a systematic and in‐depth understanding for the biomimetic design of photocatalysts and photocatalytic systems.

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“…Recently, CO 2 photoreduction into high‐value chemicals has aroused widespread attention as a promising strategy to alleviate the energy shortage and air pollution problems. [ 1–4 ] Therefore, many efforts have been devoted to investigating effective photocatalysts for CO 2 reduction, for which several types of photocatalysts including metal oxides, [ 5–7 ] carbon nitrides, [ 8–10 ] and sulfides [ 11,12 ] have proved suitable. For example, Collado et al.…”

Section: Introductionmentioning

confidence: 99%

Novel Cerium‐Based Sulfide Nano‐Photocatalyst for Highly Efficient CO₂Reduction

Zhang

Wang

et al. 2022

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To address the environmental crisis caused by excessive emissions of CO2, the development of effective photocatalysts for the conversion of CO2 into chemicals has emerged as one of the most promising strategies. Herein, beyond those well‐studied materials, a rare‐earth sulfide‐based nanocrystal NaCeS2 is fabricated and investigated for efficient and selective conversion of CO2 into CO, where the role of Ce ions is crucial. Firstly, the hybridization of Ce 4f and Ce 5d orbitals contributes to the photoresponsive band structure of NaCeS2. Secondly, due to the charge rearrangement supplied by the incompletely filled 4f orbitals of Ce ions, NaCeS2 exhibits excellent charge separation efficiency and CO2 adsorption affinity, reducing the energy barrier for the conversion from CO2 to CO. Moreover, a NaCeS2‐MoS2 heterostructure is also designed to further boost the electron transfer from the Mo site to the Ce site, which results in an improvement of the catalytic reduction yield from 7.24 to 23.42 µmol g−1 within 9 h (both better than TiO2 controls). This work offers a platform for the development of rare‐earth‐based photocatalysts for CO2 conversion.

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Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4

Cited by 558 publications

References 63 publications

Emerging Strategies for CO₂ Photoreduction to CH₄: From Experimental to Data‐Driven Design

Emerging Strategies for CO₂ Photoreduction to CH₄: From Experimental to Data‐Driven Design

A Review on the Bioinspired Photocatalysts and Photocatalytic Systems

Novel Cerium‐Based Sulfide Nano‐Photocatalyst for Highly Efficient CO₂Reduction

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Self-adaptive dual-metal-site pairs in metal-organic frameworks for selective CO2 photoreduction to CH4

Cited by 558 publications

References 63 publications

Emerging Strategies for CO2 Photoreduction to CH4: From Experimental to Data‐Driven Design

Emerging Strategies for CO2 Photoreduction to CH4: From Experimental to Data‐Driven Design

A Review on the Bioinspired Photocatalysts and Photocatalytic Systems

Novel Cerium‐Based Sulfide Nano‐Photocatalyst for Highly Efficient CO2Reduction

Contact Info

Product

Resources

About

Emerging Strategies for CO₂ Photoreduction to CH₄: From Experimental to Data‐Driven Design

Emerging Strategies for CO₂ Photoreduction to CH₄: From Experimental to Data‐Driven Design

Novel Cerium‐Based Sulfide Nano‐Photocatalyst for Highly Efficient CO₂Reduction