Electrochemical reduction of CO_(2)into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO_(2)capture and utilization,resulting from their high catalytic a...Electrochemical reduction of CO_(2)into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO_(2)capture and utilization,resulting from their high catalytic activity and selectivity.The mobility and accessibility of active sites in Cubased catalysts significantly hinder the development of efficient Cu-based catalysts for CO_(2)electrochemical reduction reaction(CO_(2)RR).Herein,a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride(g-C_(3)N_(4))as the active sites for CO_(2)-to-CH_(4)conversion in CO_(2)RR.By regulating the coordination and density of Cu sites in g-C_(3)N_(4),an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH_(4)Faraday efficiency of 49.04%and produces the products with a high CH_(4)/C_(2)H_(4)ratio over 9.This work provides the first experimental study on g-C_(3)N_(4)-supported single Cu atom catalyst for efficient CH_(4)production from CO_(2)RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO_(2)RR by engineering Cu active sites in 2D materials with porous crystal structures.展开更多
二氧化碳(CO_(2))捕集与封存技术有利于减少CO_(2)的排放量,近年来针对CO_(2)地质封存形成了从纳米尺度到油气藏尺度的大量研究成果,大多数研究只针对单一维度多孔介质中流动行为开展研究,且物理实验方法受许多不确定性因素影响,十分耗...二氧化碳(CO_(2))捕集与封存技术有利于减少CO_(2)的排放量,近年来针对CO_(2)地质封存形成了从纳米尺度到油气藏尺度的大量研究成果,大多数研究只针对单一维度多孔介质中流动行为开展研究,且物理实验方法受许多不确定性因素影响,十分耗费时间和成本。为了从微观角度深入理解CO_(2)地质封存过程中的渗流行为,提高CO_(2)地质埋存量,基于追踪两相界面动态变化的VOF(Volume of Fluid)方法,分别建立了2D和3D模型,开展了超临界CO_(2)-水两相流动数值模拟研究,对比了不同润湿性、毛细管数、黏度比条件下的CO_(2)团簇分布特征、CO_(2)饱和度变化规律,揭示了孔隙尺度CO_(2)埋存的内在机理。研究结果表明:①随着岩石对CO_(2)润湿性增加,CO_(2)波及范围扩大,同时CO_(2)团簇的卡断频率减少,CO_(2)埋存量增加;②随着毛细管数的增加,驱替模式由毛细指进转变为稳定驱替,CO_(2)埋存量增加;③随着注入超临界CO_(2)黏度逐渐接近水的黏度,两相流体之间的流动阻力降低,促进了“润滑效应”,CO_(2)相的渗流能力提高,CO_(2)埋存量增加;④润湿性、毛细管数、黏度比在不同维度多孔介质模型中对CO_(2)饱和度的影响程度不同。结论认为,基于VOF方法的CO_(2)-水两相渗流模拟研究在孔隙尺度上揭示了CO_(2)地质封存过程中的渗流机理,对CCUS技术的发展有指导意义,也为更大尺度的CO_(2)地质封存研究提供了理论指导和技术支撑。展开更多
基金This work was supported by the Fundamental Research Funds for the Central Universities(2232021A-02 and 2232023Y-01)the National Natural Science Foundation of China(Nos.52122312,22209024 and 22202183).
文摘Electrochemical reduction of CO_(2)into high-value hydrocarbons and alcohols by using Cu-based catalysts is a promising and attractive technology for CO_(2)capture and utilization,resulting from their high catalytic activity and selectivity.The mobility and accessibility of active sites in Cubased catalysts significantly hinder the development of efficient Cu-based catalysts for CO_(2)electrochemical reduction reaction(CO_(2)RR).Herein,a facile and effective strategy is developed to engineer accessible and structural stable Cu sites by incorporating single atomic Cu into the nitrogen cavities of the host graphitic carbon nitride(g-C_(3)N_(4))as the active sites for CO_(2)-to-CH_(4)conversion in CO_(2)RR.By regulating the coordination and density of Cu sites in g-C_(3)N_(4),an optimal catalyst corresponding to a one Cu atom in one nitrogen cavity reaches the highest CH_(4)Faraday efficiency of 49.04%and produces the products with a high CH_(4)/C_(2)H_(4)ratio over 9.This work provides the first experimental study on g-C_(3)N_(4)-supported single Cu atom catalyst for efficient CH_(4)production from CO_(2)RR and suggests a principle in designing highly stable and selective high-efficiency Cu-based catalysts for CO_(2)RR by engineering Cu active sites in 2D materials with porous crystal structures.
文摘二氧化碳(CO_(2))捕集与封存技术有利于减少CO_(2)的排放量,近年来针对CO_(2)地质封存形成了从纳米尺度到油气藏尺度的大量研究成果,大多数研究只针对单一维度多孔介质中流动行为开展研究,且物理实验方法受许多不确定性因素影响,十分耗费时间和成本。为了从微观角度深入理解CO_(2)地质封存过程中的渗流行为,提高CO_(2)地质埋存量,基于追踪两相界面动态变化的VOF(Volume of Fluid)方法,分别建立了2D和3D模型,开展了超临界CO_(2)-水两相流动数值模拟研究,对比了不同润湿性、毛细管数、黏度比条件下的CO_(2)团簇分布特征、CO_(2)饱和度变化规律,揭示了孔隙尺度CO_(2)埋存的内在机理。研究结果表明:①随着岩石对CO_(2)润湿性增加,CO_(2)波及范围扩大,同时CO_(2)团簇的卡断频率减少,CO_(2)埋存量增加;②随着毛细管数的增加,驱替模式由毛细指进转变为稳定驱替,CO_(2)埋存量增加;③随着注入超临界CO_(2)黏度逐渐接近水的黏度,两相流体之间的流动阻力降低,促进了“润滑效应”,CO_(2)相的渗流能力提高,CO_(2)埋存量增加;④润湿性、毛细管数、黏度比在不同维度多孔介质模型中对CO_(2)饱和度的影响程度不同。结论认为,基于VOF方法的CO_(2)-水两相渗流模拟研究在孔隙尺度上揭示了CO_(2)地质封存过程中的渗流机理,对CCUS技术的发展有指导意义,也为更大尺度的CO_(2)地质封存研究提供了理论指导和技术支撑。
