Spin polarization regulates photocatalytic CO2 into hydrocarbons by Co doped BiOCl

Wenjuan Li, Yipin Zhang, Weiguang Ran, Yuhua Wang, Fu Tian, Fuzhi Zhang, Min Xu, Dapeng Zhang, Na Li, Tingjiang Yan
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Abstract

Doping magnetic elements into semiconductors is an effective strategy for manipulating spin-polarized electrons in photocatalysis. This work indicates that the introduction of spin-polarized electrons into BiOCl ultrathin sheets remarkably boosts the efficiency of photocatalytic CO reduction by doping BiOCl with magnetic Co. The Co-doped BiOCl (Co-BiOCl) photocatalyst selectively converts CO into CH and C products with a hydrocarbon selectivity of 76.9 %, which is not available for pristine BiOCl. The spin-polarized electrons generated from Co-BiOCl promote CO adsorption, stabilize the key CO* intermediate, and significantly reduce the kinetic barrier to CH* formation, tuning the subsequent hydrogenation and C−C coupling into hydrocarbons. The regulatory effect of spin polarization on photocatalytic CO reduction can also be observed for Fe-, Ni- or non-magnetic element Cu- doped BiOCl. Hence, this work provides new insight into the regulation of the photoreduction of CO to hydrocarbon products by spin-polarized electrons.
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自旋极化调节掺杂 Co 的 BiOCl 光催化二氧化碳转化为碳氢化合物的过程
在半导体中掺入磁性元素是在光催化过程中操纵自旋极化电子的一种有效策略。这项研究表明,通过在 BiOCl 超薄片中掺杂磁性 Co,将自旋极化电子引入 BiOCl 超薄片,可显著提高光催化还原 CO 的效率。掺杂 Co 的 BiOCl(Co-BiOCl)光催化剂可选择性地将 CO 转化为 CH 和 C 产物,其碳氢化合物选择性高达 76.9%,这是原始 BiOCl 所不具备的。Co-BiOCl 产生的自旋极化电子促进了 CO 的吸附,稳定了关键的 CO* 中间体,并显著降低了 CH* 形成的动力学障碍,从而调整了随后的氢化和 C-C 耦合成碳氢化合物的过程。对于掺杂铁、镍或非磁性元素铜的 BiOCl,也能观察到自旋极化对光催化 CO 还原的调节作用。因此,这项工作为自旋极化电子调节 CO 光还原成烃类产物提供了新的见解。
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