Xiaofeng Kang, Zhizhong He, Feng Wang, Ya Liu, Liejin Guo
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引用次数: 0
Abstract
Efficiently regulating reaction pathways for photoreduction CO2 to achieve required products is enormously strenuous. The design of active sites for CO2 adsorption, activation, and tuning of reaction pathways is pivotal to address this grand challenge. Herein, highly selective sites are developed for photoreduction CO2 to HCOOH and CO based on asymmetrically coupling different ratios of Ni and Co loaded on crystalline carbon nitride (CCN) by an alloying synthesis strategy, which is confirmed by high‐resolution transmission electron microscopy (HRTEM) imaging, X‐ray diffraction (XRD) patterns, and X‐ray photoelectron spectroscopy (XPS) spectra. In situ Fourier transform infrared spectra suggest that the key intermediate *OCHO to HCOOH pathway prefers to form on Ni sites, while *COOH to CO pathway tends to generate on Co sites, and the characteristic peaks intensity of the two key intermediates are stronger with the synergistic effects of NiCo bimetallic, further verified by the theory calculations. Accordingly, HCOOH with a selectivity of 98.5% (194.5 µmol g⁻1 h⁻1) or CO with a selectivity of 85.4% (144.8 µmol g−1 h−1) can be achieved on the optimized NixCoy alloy, under sacrificial agent‐free conditions.
有效地调节光还原CO2的反应途径以获得所需的产物是非常艰苦的。设计二氧化碳吸附、活化和调整反应途径的活性位点是解决这一重大挑战的关键。本文采用合金化合成策略,通过不对称耦合不同比例的Ni和CO负载在晶体氮化碳(CCN)上,开发了光还原CO2为HCOOH和CO的高选择性位点,并通过高分辨率透射电子显微镜(HRTEM)成像、X射线衍射(XRD)图和X射线光电子能谱(XPS)谱证实了这一点。原位傅里叶变换红外光谱表明,关键中间体*OCHO - HCOOH通路倾向于在Ni位点上生成,而*COOH - CO通路倾向于在CO位点上生成,并且随着NiCo双金属的协同作用,两个关键中间体的特征峰强度更强,理论计算进一步验证了这一点。因此,在无牺牲剂的条件下,在优化的NixCoy合金上,HCOOH的选择性为98.5%(194.5µmol g - 1 h - 1), CO的选择性为85.4%(144.8µmol g - 1 h - 1)。
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