Research progress on the reaction pathway of CO2 methanation
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摘要:
CO2甲烷化反应是一个复杂的多相催化过程,在反应过程中会产生各种各样的中间体,其反应路径目前还存在许多争议和矛盾。深入系统地研究CO2甲烷化反应中催化剂表面中间体的演变过程,可以进一步从机理的角度优化催化剂的设计方案,提高催化性能。本工作主要基于原位红外光谱表征技术,总结梳理了最近关于CO2甲烷化反应路径研究的相关工作,着重探讨了负载型催化剂的活性金属、载体、助剂、合成方法等因素对CO2甲烷化反应路径的影响以及由此对催化剂性能所产生的积极效果。同时针对现阶段所面临的争论点,即反应气CO2与H2的活化位点、催化剂的活性位点以及未来可行的研究方法进行了详细论述。
Abstract:CO2 methanation is a very complex heterogeneous catalytic process, in which a variety of intermediates are produced. There are still many controversies and contradictions in the exploration of the reaction pathway of CO2 methanation. In-depth and systematic study of the evolution process of the intermediates formed on the catalyst surface in CO2 methanation will help to further optimize the design of catalyst from the perspective of mechanism, thereby improving the catalytic performance. This paper summarises recent work on the CO2 methanation reaction pathway based on in situ infrared spectroscopy, focusing on the influence of the active metal, carrier, additives and synthesis method of the supported catalyst on the CO2 methanation reaction pathway and the resulting positive effects on catalyst performance. In addition, the controversial points faced at the current stage, such as the activation sites of reaction gases CO2 and H2, the active sites of catalysts and the feasible research methods in the future are discussed in detail.
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图 8 (a)流动反应器/DRIFT池流出气体质谱中CH4和H2O质量碎片信号强度和甲酸盐(1570−1590 cm−1)、甲氧基(1160 cm−1)的红外吸收峰强度变化曲线,甲酸(a1)和甲醇(a2)加氢过程红外采样;(b)甲酸(b1)和甲醇(b2)加氢过程中催化剂Ni/ZrO2的红外谱图[12]
Figure 8 (a) Correlation between the signal intensities of the mass fragments of CH4 and H2O in mass spectra of the effluent gases from the flow reactor/DRIFT cell,Infrared absorption peak intensity change curve of formate (1570−1590 cm−1), methoxy (1160 cm−1), infrared sampling during formic acid hydrogenation process (a1), and methanol hydrogenation process (a2), (b) Infrared spectra of catalyst Ni/ZrO2 during hydrogenation of formic acid (b1) and hydrogenation of methanol (b2)12](with permission from Elsevier Publications)
图 9 513 K下原料气CO2 + H2与CO2交替切换时催化剂5%Pd/Al2O3上随时间变化的(a)红外谱图,(b)在DRIFT池出口处收集的相应质谱信号曲线图(左)513 K下,原料气CO2 + H2与CO2交替切换时还原的催化剂0.5%Pd/Al2O3上随时间变化的(a)红外谱图(b)在DRIFT池出口处收集的相应质谱信号曲线图(右)[54]
Figure 9 (a) DRIFT spectra and (b) the corresponding MS signals collected at the exit of the DRIFT cell as a function of time when the feed gas was switched alternately between CO2 + H2 and CO2 over 5% Pd/Al2O3 at 513 K (left) (a) DRIFT spectra and (b) the corresponding MS signals at the exit of the DRIFT cell collected at 513 K as a function of time when the feed gas was switched alternately between CO2 + H2 and CO2 over a reduced 0.5% Pd/Al2O3 sample[54](with permission from ACS Publications)
图 11 催化剂Ni/ZrO2-P(a)与Ni/ZrO2-C(b)在2.5%H2,0.5%CO2和Ar作为载体组成的混合气体(40 mL/min)下进行程序升温反应时的原位红外光谱谱图[69]
双齿碳酸氢盐(♣), 单齿碳酸盐(♦), 双齿甲酸盐( + )、单齿甲酸盐(*)、线性CO或桥连CO (△) 以及气态CH4 (●)
Figure 11 Operando DRIFT spectra during temperature-programmed reaction of a gas mixture (40 mL/min) containing 2.5% H2, 0.5% CO2 with Ar as carrier gas over Ni/ZrO2-P (a) and Ni/ZrO2-C (b)69]
bidentate bicarbonate (♣), monodentate carbonates (♦), bidentate formate ( + ), monodentate formate (*), linear CO or bridge CO (△) and gaseous CH4 (●) (with permission from Elsevier Publications)
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