Photosensitizing single-site metal−organic framework enabling visible-light-driven CO2 reduction for syngas production

Li, Meng; Mu, Yan‐Fei; Yao, Shuang; Guo, Song; Guo, Xiangwei; Zhang, Zhi‐Ming; Lu, Tong‐Bu

doi:10.1016/j.apcatb.2019.01.014

Cited by 141 publications

(77 citation statements)

References 42 publications

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“…However, the conventional methane dry reforming suffers from high operating temperatures (>600 °C) and many of catalysts inevitably undergo severe deactivation due to carbon deposition. As an alternative, the syngas production via photocatalysis is an emerging and attractive technique because the catalytic process can be conducted at ambient temperature and use the clean and inexhaustible solar energy [3–9] …”

Section: Introductionmentioning

confidence: 99%

Light‐Driven Syngas Production over Defective ZnIn₂S₄ Nanosheets

Wang

Chen

et al. 2021

Chemistry A European J

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Photocatalytic syngas (CO and H2) production with CO2 as gas source not only ameliorates greenhouse effect, but also produces valuable chemical feedstocks. However, traditional photocatalytic systems require noble metal or suffers from low yield. Here, we demonstrate that S vacancies ZnIn2S4 (VS‐ZnIn2S4) nanosheets are an ideal photocatalyst to drive CO2 reduction into syngas. It is found that building S vacancies can endow ZnIn2S4 with stronger photoabsorption, efficient electron–hole separation, and larger CO2 adsorption, finally promoting both hydrogen evolution reaction (HER) and CO2 reduction reaction (CO2RR). The syngas yield of CO and H2 is therefore significantly increased. In contrast to pristine ZnIn2S4, the syngas yield over VS‐ZnIn2S4 can be improved by roughly ≈4.73 times and the CO/H2 ratio is modified from 1:4.18 to 1:1. Total amount of syngas after 12 h photocatalysis is as high as 63.20 mmol g−1 without use of any noble metals, which is even higher than those of traditional noble metal‐based catalysts in the reported literatures. This work demonstrates the critical role of S vacancies in mediating catalytic activity and selectivity, and highlights the attractive ability of defective ZnIn2S4 for light‐driven syngas production.

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Section: Introductionmentioning

confidence: 99%

Light‐Driven Syngas Production over Defective ZnIn₂S₄ Nanosheets

Wang

Chen

et al. 2021

Chemistry A European J

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“…[16] Ru II complexes (e.g.,e specially [Ru(bpy) 3 ]Cl 2 ,b py = bipyridine) with accessible redox states, high quantum efficiency, and long-lived excited states, are some of the most widely used metal complexes in CO 2 photoreduction. [17][18][19][20][21] The combination of thesec omplexes and semiconductors is considered as an efficient way to enhance photocatalytic reactivity and stabilityu nder visible-light irradiation. [22,23] Also, the heterogeneous process will facilitate catalystr e-use and liquid product separation.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Photoreduction of Low‐Concentration CO₂to Syngas by Using a Polyoxometalates/Ru^IIComposite

You

Lang

et al. 2020

Chemistry A European J

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At present, the fixation of CO2 always requires it to be extracted from the atmosphere first, which leads to more energy consumption. Thus, direct photoreduction of low‐concentration CO2 to useful chemicals (e.g., syngas) under sunlight is significant from an energy‐saving and environmentally friendly perspective. Here, the design and fabrication of a [Ru(bpy)3]/[Co20Mo16P24] composite is demonstrated for visible‐light‐driven syngas production from diluted CO2 (3–20 %) gas with a high yield of approximately 1000 TONs (turnover number of syngas). This activity is an order of magnitude higher than the reported system with [Ru(bpy)3]2+ participation. With evidence from ultrafast transient absorption, GC‐MS, 1H NMR spectroscopy and in situ transient photovoltage tests, a clear and fundamental understanding of the highly efficient photoreduction of CO2 by the [Ru(bpy)3]/[Co20Mo16P24] composite is achieved. Making use of the structure and property designable polyoxometalates towards the photo‐fixation of CO2 is a conceptually distinct and commercially interesting strategy for making useful chemicals and environmental protection.

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“…Accordingly, the CO/H 2 ratios could be effectively manipulated in a wide range from 1:19 to 9:1 by adjusting the Fe/Ni ratio of catalyst in the low‐concentration CO 2 photoreduction system. The obtained tunable range for CO/H 2 ratio is obviously wider than the reported CO 2 photoreduction systems and (photo)electrocatalytic systems, [ 23 ] as shown in Table S3 (Supporting Information). Notably, the total catalytic performances (H 2 +CO) of a series of Fe/Ni bimetals‐COFs are similar but the ratio is obviously different, indicating that the ratio of metal sites shows great effects on adjusting the selectivity of the products.…”

Section: Resultsmentioning

confidence: 80%

Rational Design of FeNi Bimetal Modified Covalent Organic Frameworks for Photoconversion of Anthropogenic CO₂ into Widely Tunable Syngas

Han

Zhong

et al. 2020

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Direct photoconversion of low‐concentration CO2 into a widely tunable syngas (i.e., CO/H2 mixture) provides a feasible outlet for the high value‐added utilization of anthropogenic CO2. However, in the low‐concentration CO2 photoreduction system, it remains a huge challenge to screen appropriate catalysts for efficient CO and H2 production, respectively, and provide a facile parameter to tune the CO/H2 ratio in a wide range. Herein, by engineering the metal sites on the covalent organic frameworks matrix, low‐concentration CO2 can be efficiently photoconverted into tunable syngas, whose CO/H2 ratio (1:19–9:1) is obviously wider than reported systems. Experiments and density functional theory calculations indicate that Fe sites serve as the H2 evolution sites due to the much stronger binding affinity to H2O, while Ni sites act as the CO production sites for the higher affinity to CO2. Notably, the widely tunable syngas can also be produced over other Fe/Ni‐based bimetal catalysts, regardless of their structures and supporting materials, confirming the significant role of the metal sites in regulating the selectivity of CO2 photoreduction and providing a modular design strategy for syngas production.

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Photosensitizing single-site metal−organic framework enabling visible-light-driven CO2 reduction for syngas production

Cited by 141 publications

References 42 publications

Light‐Driven Syngas Production over Defective ZnIn₂S₄ Nanosheets

Light‐Driven Syngas Production over Defective ZnIn₂S₄ Nanosheets

Highly Efficient Photoreduction of Low‐Concentration CO₂to Syngas by Using a Polyoxometalates/Ru^IIComposite

Rational Design of FeNi Bimetal Modified Covalent Organic Frameworks for Photoconversion of Anthropogenic CO₂ into Widely Tunable Syngas

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Photosensitizing single-site metal−organic framework enabling visible-light-driven CO2 reduction for syngas production

Cited by 141 publications

References 42 publications

Light‐Driven Syngas Production over Defective ZnIn2S4 Nanosheets

Light‐Driven Syngas Production over Defective ZnIn2S4 Nanosheets

Highly Efficient Photoreduction of Low‐Concentration CO2to Syngas by Using a Polyoxometalates/RuIIComposite

Rational Design of FeNi Bimetal Modified Covalent Organic Frameworks for Photoconversion of Anthropogenic CO2 into Widely Tunable Syngas

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Light‐Driven Syngas Production over Defective ZnIn₂S₄ Nanosheets

Light‐Driven Syngas Production over Defective ZnIn₂S₄ Nanosheets

Highly Efficient Photoreduction of Low‐Concentration CO₂to Syngas by Using a Polyoxometalates/Ru^IIComposite

Rational Design of FeNi Bimetal Modified Covalent Organic Frameworks for Photoconversion of Anthropogenic CO₂ into Widely Tunable Syngas