Microstructure Induced Thermodynamic and Kinetic Modulation to Enhance CO2 Photothermal Reduction: A Case of Atomic-Scale Dispersed Co-N Species Anchored Co@C Hybrid
Microstructure Induced Thermodynamic and Kinetic Modulation to Enhance CO2 Photothermal Reduction: A Case of Atomic-Scale Dispersed Co-N Species Anchored Co@C Hybrid
复制标题
微结构诱导热力学和动力学调节增强 CO2 光热还原：原子级分散 Co-N 物种锚定 Co@C 杂化物的案例
DOI：
10.1021/acscatal.9b04963
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发表时间：
2020-04-17
期刊：
影响因子：
12.9
通讯作者：
Ye, Jinhua
中科院分区：
文献类型：
--
作者：
Ning, Shangbo;Xu, Hua;Ye, Jinhua
将CO2转化为单一产品是一项关键的科学挑战，因为通过非均相催化剂进行CO2的靶向活化和转化存在困难。在此，我们提出了一种原子级分散的Co-N物种锚定的Co@C混合结构（标题为Co@ CoN&C），它可以调节热力学和动力学过程中的催化性能，以在光热CO2还原中实现活性和高选择性的CO产率。最佳样品提供了132 mmol g（cat）（-1）h（-1）的最大产率和显著的CO选择性（91.1%），而与典型的Co纳米颗粒（NPs）相比，不期望的甲烷化活性被抑制。机理研究表明，CO2在石墨碳和钴纳米颗粒上的吸附-强光子-物质相互作用可以提高光热转换效率，从而诱导高的工作温度，这对CO2的活化有利，从而提高了催化剂的活性。此外，碳层提高了CO2的吸附能力，表面原子分散的Co-N物种削弱了加氢能力，从动力学上控制了反应路径，从而获得了高的CO选择性。本研究证实微结构设计可以调控光化学反应的热力学和动力学因素，从而实现潜在的太阳能-化学能转换。
The transformation of CO2 into a single product is a critical scientific challenge because of the difficulty associated with targeted activation and conversion of CO2 by heterogeneous catalysts. Herein, we present an atomic-scale dispersed Co-N species anchored Co@C hybrid structure (entitled as Co@ CoN&C) that regulates catalytic properties in thermodynamic and kinetic processes to achieve active and highly selective CO yield in the photothermal CO2 reduction. An optimal sample delivers the maximum yield rate of 132 mmol g(cat)(-1)h(-1) and remarkable CO selectivity (91.1%), while the undesirable methanation activity, compared with typical Co nanoparticles (NPs), was suppressed. The mechanism study suggests that the CO2 Adsorption- strong photon-matter interaction over graphitic-carbon and Co NPs can enhance the light-to-heat conversion efficiency and thus induce the high work temperature, which is thermodynamically beneficial for CO2 activation and subsequently promoted the catalytic activity. Furthermore, the carbon layers improve the adsorption of CO2, and the surface atomically dispersed Co-N species weakens hydrogenation capability, which kinetically controls the reaction pathway and therefore attains the high selectivity for CO production. This study exemplifies that the microstructure design can modulate the thermodynamic and kinetic factors of photochemical reaction and thereby achieve potential solar-to-chemical energy conversion.