李洋洋,黄思懿,田鑫,许狄,定明月
LI Yangyang,HUANG Siyi,TIAN Xin,XU Di,DING Mingyue

• 1:武汉大学动力与机械学院
• 2:武汉大学碳中和研究院碳中和感知与效能评估教育部工程研究中心

摘要(Abstract)：

耦合绿氢将CO_2催化转化为高值化学品是实现大规模CO_2减排、绿氢储运的重要途径，对于推动“双碳”目标和绿色能源转型具有重要意义。但传统热催化CO_2加氢技术通常依赖高温条件，存在反应条件苛刻、能耗高、催化剂易失活，产物选择性难以调控的问题。近年来，光热催化CO_2加氢发展迅速，与热催化技术相比，光热催化能够耦合可再生太阳能资源，减少化石能源的使用，同时能够实现温和条件下的CO_2加氢反应，一定程度提升催化剂运行稳定性，引起学术界和工业界的广泛关注。然而，由于CO_2分子的化学惰性和反应路径复杂，不同产物的生成涉及竞争反应路径，实现CO_2高效和定向的光热催化转化极具挑战。近年来，研究者通过设计高效光热催化剂、优化反应体系、探究光热协同机制等策略，在提升CO_2转化率和优化目标产物选择性方面取得了显著进展。基于此，系统总结了光热催化CO_2加氢的研究进展。首先对光热催化CO_2加氢反应和催化剂体系进行了介绍，围绕光热催化CO_2加氢制备CO、CH_4、甲醇和C_(2+)产物的新型催化剂体系进行了总结，研究了光热材料（金属纳米颗粒、半导体、MOF材料等）在光照条件下产生的光生电子效应或光热转换效应，激发光生载流子和促进反应体系的快速升温参与催化过程，并探讨了催化剂的组成、结构（如粒径、缺陷、界面）与反应性能之间的关系。其次总结了光热催化CO_2加氢反应机制，介绍了光热催化对产物选择性和反应性能的调控机制；一方面，通过降低关键反应路径能垒，使反应更倾向于生成特定产物，显著提高目标产物选择性，另一方面，电子转移可优化CO_2、*CO和*HCOO等反应物和关键中间物种的吸附和转化动力学，从而加速反应进程。最后，对光热催化CO_2加氢反应的发展前景进行总结和展望。目前光热催化技术发展仍面临反应机制不明、催化剂光能利用率低和长期稳定性差等挑战，未来需开发全光谱响应材料，调控特定产物的选择性（如C_(2+)），提升催化剂稳定性，开发具有高稳定性催化剂并深入研究光热协同机制以实现产业化应用。
CO_2 catalytic conversion with green hydrogen into high value-added chemicals is an important approach to achieve large-scale CO_2 emission reduction,green hydrogen storage and transportation,which is great significance for advancing the “Dual Carbon” goals and facilitating the transition to green energy. However,traditional thermal catalytic CO_2 hydrogenation technologies usually rely on hightemperature conditions,which have problems such as harsh reaction conditions,high energy consumption,easy deactivation of catalysts,and difficulty in regulating product selectivity. In recent years, photothermal catalysis for CO_2 hydrogenation has developed rapidly.Compared with thermal catalysis technology,photothermal catalysis can couple renewable solar energy resources,reduce the use of fossil energy, and at the same time achieve CO_2 hydrogenation reactions under mild conditions, improving the operational stability of the catalyst to a certain extent,which has attracted extensive attention from both the academic and industrial communities. However,due to the chemical inertness of CO_2 molecules and the complexity of reaction pathways,the generation of different products involves competing reaction pathways,making it extremely challenging to achieve efficient and targeted photothermal catalytic conversion of CO_2. In recent years,researchers have made significant progress in improving the CO_2 conversion rate and optimizing the selectivity of target products through strategies such as designing efficient photothermal catalysts,optimizing reaction systems,and exploring the photothermal synergy mechanism. Based on this, this paper systematically summarizes the research progress of photothermal catalytic CO_2 hydrogenation.Firstly,the photothermal catalytic CO_2 hydrogenation reaction and catalyst systems are introduced. The new catalyst system for preparing CO, CH_4, methanol and C_(2+) products by photothermal catalytic CO_2 hydrogenation was summarized. The photoelectronic effect or photothermal conversion effect produced by photothermal materials(such as metal nanoparticles, semiconductors, MOF materials,etc.) under light conditions was studied. The photogenerated carriers are excited and the rapid temperature rise of the reaction system is promoted to participate in the catalytic process, and the structure-activity relationship between the composition, structure(such as particle size,defects,interfaces) of the catalyst and the reaction performance is explored. Secondly,the mechanism of photothermal catalytic CO_2 hydrogenation reaction was summarized,and the regulation mechanism of photothermal catalysis on product selectivity and reaction performance was introduced. On the one hand,by lowering the energy barrier of the key reaction path,the reaction is more inclined to generate specific products,significantly enhancing the selectivity of the target products. On the other hand,electron transfer can optimize the adsorption and conversion kinetics of reactants such as CO_2,*CO,and *HCOO,as well as key intermediate species,thereby accelerating the reaction process. Finally,the development prospects of photothermal catalytic CO_2 hydrogenation are prospected.At present, the development of photothermal catalysis technology still faces challenges such as unclear reaction mechanisms, low utilization rate of catalyst light energy, and poor long-term stability. In the future, it is necessary to develop full-spectrum response materials,regulate and achieve the selectivity of specific products(such as C_(2+)),improve the stability of the catalyst,develop highly stable catalysts,and conduct in-depth research on the photothermal synergy mechanism to achieve industrial application.

关键词(KeyWords)： 光热催化;CO_2加氢;高值化学品;催化剂;构效关系;反应机理
photothermal catalysis;CO_2 hydrogenation;high va.lue-added chemicals;catalyst;structure-performance relationship;reaction mechanism

Abstract:

Keywords:

基金项目(Foundation): 国家重点研发计划催化科学重点专项资助项目（2022YFA1504700）;; 国家自然科学基金资助项目（22308266,U21A20317）;; 湖北省自然科学基金创新群体资助项目（2022CFA017）

作者(Author): 李洋洋,黄思懿,田鑫,许狄,定明月
LI Yangyang,HUANG Siyi,TIAN Xin,XU Di,DING Mingyue

DOI: 10.13226/j.issn.1006-6772.GPF25052901

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