Targeted H2O activation to manipulate the selective photocatalytic reduction of CO2 to CH3OH over carbon nitride-supported cobalt sulfide†

IF 9.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Green Chemistry Pub Date : 2022-01-01 DOI:10.1039/d2gc03226k
Minzhi Ma , Zeai Huang , Rui Wang , Ruiyang Zhang , Tian Yang , Zhiqiang Rao , Wenjun Fa , Fengying Zhang , Yuehan Cao , Shan Yu , Ying Zhou
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引用次数: 5

Abstract

The selective photocatalytic reduction of CO2 by H2O to methanol is a desirable solution for solar energy storage with the production of abundant chemicals. However, this is a formidable challenge because the conversion of CO2 to CH3OH is a 6-electron transfer reaction that needs 4 protons, while other products requiring less electrons and protons, such as CO, HCOOH, and HCHO, are much easier to form than CH3OH, leading to lower selectivity for the production CH3OH. Herein, we propose a novel concept of targeting activated H2O to provide ample protons without the generation of strong oxidative free radicals for the highly selective photocatalytic reduction of CO2 to CH3OH with H2O. Carbon nitride (CN)-supported cobalt sulfide (CS) was fabricated as the desired prototype photocatalyst (CS/CN). Cobalt sulfide was confirmed to promote the generation of protons without the formation of strong oxidative free radicals (such as ˙OH and ˙O2) by significantly weakening the overpotential of the H2O oxidation half-reaction. This targeted H2O activation contributed to the continuous coupling of multi-protons/electrons and CO2 to form the key intermediates CHO* and CH3O*, which were necessary for the generation of CH3OH. Accordingly, the CH3OH selectivity by the optimized CS/CN (87.2%) photocatalyst was 2.3 times higher than that of CN (38.6%) with an increase in the CH3OH production rate from 22.0 μmol g−1 h−1 to 97.3 μmol g−1 h−1. This work provides an elegant solution to achieve the highly selective photocatalytic conversion of CO2 to CH3OH by modulating the H2O activation process.

Abstract Image

目标水活化,以操纵选择性光催化还原CO2到CH3OH在碳氮负载的硫化钴†
水选择性光催化还原CO2制甲醇是一种理想的太阳能储能解决方案,可产生丰富的化学物质。然而,这是一个艰巨的挑战,因为CO2转化为CH3OH是一个需要4个质子的6个电子转移反应,而其他需要更少电子和质子的产物,如CO、HCOOH和HCHO,比CH3OH更容易形成,导致生成CH3OH的选择性较低。在此,我们提出了一种新的概念,即靶向活化的H2O,在不产生强氧化自由基的情况下提供充足的质子,用于用H2O高选择性光催化将CO2还原为CH3OH。制备了氮化碳(CN)负载的硫化钴(CS)作为期望的原型光催化剂(CS/CN)。硫化钴通过显著减弱H2O氧化半反应的过电位,在不形成强氧化自由基(如˙OH和˙O2−)的情况下促进质子的生成。这种有针对性的H2O活化有助于多质子/电子与CO2连续耦合形成关键中间体CHO*和ch30 *,这是生成CH3OH所必需的。因此,优化后的CS/CN光催化剂对CH3OH的选择性(87.2%)比CN(38.6%)提高了2.3倍,CH3OH产率从22.0 μmol g−1 h−1提高到97.3 μmol g−1 h−1。这项工作提供了一种优雅的解决方案,通过调节水的活化过程来实现CO2到CH3OH的高选择性光催化转化。
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来源期刊
Green Chemistry
Green Chemistry 化学-化学综合
CiteScore
16.10
自引率
7.10%
发文量
677
审稿时长
1.4 months
期刊介绍: Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.
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