热增强的光催化二氧化碳还原技术

doi:10.16085/j.issn.1000-6613.2021-0632

摘要/Abstract

摘要：

利用太阳光驱动二氧化碳（CO₂）催化转化合成燃料是缓解能源危机和降低温室效应的理想途径。然而，当前面临的主要挑战在于CO₂固有的化学稳定性使得光催化反应的转化效率低下。热量被认为是促进催化转化反应过程的重要推动力，可以有效提升光催化转化的效率。本文综述了不同形式的热增强光催化在CO₂还原生产燃料方面的应用，包括外加热源的光催化CO₂还原、光热效应促进的光催化CO₂还原以及等离激元增强的光催化CO₂还原体系。文章指出：热增强的光催化技术继承了光催化的高选择性和热催化的高反应活性的优势，实现了CO₂还原反应的高效进行。具体分析如下：外加热源主要通过直接加热装置或者聚焦太阳光能实现，产物的生成效率明显增强，选择性影响不大；光热效应发挥着局部提高催化剂反应温度的作用，使能量利用效率更高，大幅度降低CO₂还原反应所需的能量；等离激元效应除了发挥光热效应的作用，同时兼备增强光吸收、促进载流子分离和加速表面反应动力学的作用。文章最后指出，通过对反应机理进行深度研究，合理调控反应体系的反应条件，将极大促进热增强的光催化CO₂还原技术发展，为CO₂利用提供有效手段。

关键词: CO₂转化, 热增强, 光催化, 等离激元效应, 光吸收

Abstract:

Directly utilizing sunlight to drive catalytic carbon dioxide (CO₂) reduction into synthetic chemical fuels is one of the most promising approaches to alleviate the energy crisis and reduce the greenhouse effect. However, the inherent chemical stability of CO₂ results in low photocatalytic conversion efficiency, forming a great challenge. Thermal energy is considered to be an important driving force to improve the catalytic conversion rate during the reaction process. Taking advantages of the high selectivity by photocatalysis and the high reaction activity by thermal catalysis, the thermal-enhanced photocatalysis CO₂ reduction exhibits high conversion efficiency. This article summarized the different forms of thermal-enhanced photocatalysis CO₂ reduction, including external heating sources, photothermal effect and plasmonic effect. The external heating source was mainly realized by direct heating device or focused solar energy, which could remarkably increase the production efficiency. The photothermal effect was exerting to increase the local reaction temperature of catalyst, which greatly enhanced the energy utilization efficiency in CO₂ reduction. In addition to the same effect as the photothermal effect, plasmonic effect also played a role in enhancing light absorption, promoting carrier separation and accelerating surface reaction kinetics. In-depth research on the reaction mechanism and rational control of the reaction conditions would greatly promote the development of thermal-enhanced photocatalytic CO₂ reduction technology and provide effective means for CO₂ utilization.

Key words: CO₂ conversion, thermal enhanced, photocatalytic, plasmonic effect, light absorption

中图分类号:

TQ034

罗志斌, 龙冉, 王小博, 裴爱国, 熊宇杰. 热增强的光催化二氧化碳还原技术[J]. 化工进展, 2021, 40(9): 5156-5165.

LUO Zhibin, LONG Ran, WANG Xiaobo, PEI Aiguo, XIONG Yujie. Thermal-enhanced photocatalytic carbon dioxide reduction[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 5156-5165.

图/表 10

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表1

热增强光催化CO2还原技术的代表性研究工作"

催化材料	反应物	产物	能量来源	催化性能	参考文献
AuCu/g-C₃N₄	CO₂	CH₃CH₂OH	300W氙灯（λ>420nm）+外热120℃	产率为0.89mmol · g $c a t - 1$ · h^-1（选择性为93.1%），分别是光催化和热催化的4.2倍和7.6倍	［9］
Bi₄TaO₈Cl/W₁₈O₄₉异质结	CO₂	CO	模拟光源20mW · cm^-2+外热120℃	产率为23.42μmol · g $c a t - 1$ · h^-1，达到Bi₄TaO₈Cl光催化的167倍	［10］
Pt/TiO_2-_x	CO₂	CH₄	模拟光源AM 1.5G+外热120℃	产率为0.3412μmol · g $c a t - 1$ · h^-1（选择性为87.5%），达到室温TiO_2-_x光催化的155倍	［11］
In₂O_3-_x(OH)_y	CO₂+H₂	CO	聚焦氙灯光源约20kW · m^-2	产率为22.0μmol · g $c a t - 1$ · h^-1，是光催化的6倍	［21］
VIII族金属纳米颗粒	CO₂	CH₄	300W氙灯光源	相对于光催化方法，光热催化CO₂还原产率级别提升了几个数量级，从μmol · g $c a t - 1$ · h^-1提升到了mol · g $c a t - 1$ · h^-1	［12］
B纳米颗粒	CO₂	CO、CH₄	300W氙灯光源	CO和CH₄的产率分别为1.0μmol · g $c a t - 1$ · h^-1和2.5μmol · g $c a t - 1$ · h^-1，是当前报道的B基材料的最优性能	［22］
TiO₂光子晶体	CO₂	CH₄	300W氙灯光源	CH₄产率达到35.0μmol · h^-1 · m^-2，分别达到商用P25和TiO₂纳米管的15.9倍和4.7倍	［23］
Ni/Ce_xTi_yO₂	CO₂+H₂	CH₄	300W氙灯光源	CH₄产率达到17.0mmol · g $c a t - 1$ · h^-1	［25］
TiO₂-石墨烯复合材料	CO₂	CO、CH₄	300W氙灯光源 4.38kW · m^-2	CO的产率达到了5.2μmol · g^-1_cat · h^-1，CH₄的产率达到了26.7μmol · g $c a t - 1$ · h^-1，分别是纯TiO₂的5.1倍和2.8倍	［28］
Pd-TiO₂	CO₂	CO	500W汞灯光源	CO产率11.05μmol · g $c a t - 1$ · h^-1，是商业化TiO₂（P25）的8.27倍	［13］
Ni-CeO₂/SiO₂复合材料	CO₂+CH₄	H₂、CO	500W氙灯光源	H₂和CO的产率分别达到了33.42mmol · min^-1 · g^-1_cat和41.53mmol · min^-1 · g $c a t - 1$ ，光制燃料转化效率达到了27.4%	［34］
MoO_3-_x	CO₂	CO、CH₄	模拟太阳光能	CO产率达到10.3μmol · g $c a t - 1$ · h^-1，是MoO₃（0.52μmol · g $c a t - 1$ · h^-1）的20倍；CH₄产率达到2.08μmol · g $c a t - 1$ · h^-1，是MoO₃（0.04μmol · g $c a t - 1$ · h^-1）的52倍	［35］

表1

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