Amphiphilic heterojunctions with atomically dispersed copper–alkynyl active units for highly efficient CO2 photoreduction

Fangjie Xu, Baoxin Ge, Pengyang Jiang, Xinlin Cai, Fangshu Xing, Caijin Huang
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Abstract

The efficiency of CO photoreduction is limited by slow charge kinetics and the mass transfer of hydrophobic CO and HO over the photocatalyst. Herein, we present a copper–alkynyl bond coordination polymer (CA-CP) with atomically-dispersed copper–alkynyl units (ADCAUs). By incorporating hydrophobic CA-CP with hydrophilic iodine vacancy-rich bismuth oxyhalides (I-BX), we construct amphiphilic heterojunction photocatalysts (CA-CP/I-BX) for visible-light-driven CO photoreduction. CA-CP/I-BX achieves excellent stability, 100 % CO selectivity and a CO-evolution rate of 157.6 μmol g h coupled with O releasing. Experimental and theoretical calculations elucidate that the ADCAUs favor adsorption and activation of CO, and have high CO selectivity. Moreover, the amphiphilic janus structure not only ensures the spatial synergy effect of CO reduction and HO oxidation, but also promotes charge separation and proton feeding, boosting CO photoreduction activity. This work develops Cu–alkynyl coordination polymer photocatalysts with ADCAUs and provides insights into hydrophobic–hydrophilic biphasic photocatalysts for synergistic CO reduction and HO oxidation.
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具有原子分散铜-炔基活性单元的两性异质结,可实现高效的二氧化碳光还原
光催化剂上缓慢的电荷动力学和疏水性 CO 和 HO 的传质限制了 CO 光还原的效率。在此,我们提出了一种具有原子分散铜-炔基单元(ADCAUs)的铜-炔基键配位聚合物(CA-CP)。通过将疏水性的 CA-CP 与亲水性的富碘空位氧卤化铋(I-BX)结合在一起,我们构建了两亲异质结光催化剂(CA-CP/I-BX),用于可见光驱动的 CO 光还原。CA-CP/I-BX 具有出色的稳定性、100% 的一氧化碳选择性以及 157.6 μmol g h 的一氧化碳转化率,同时还能释放 O。实验和理论计算表明,ADCAUs 有利于 CO 的吸附和活化,并具有较高的 CO 选择性。此外,两亲破环结构不仅确保了 CO 还原和 HO 氧化的空间协同效应,还促进了电荷分离和质子馈入,提高了 CO 光还原活性。这项研究开发了具有 ADCAUs 的铜-炔基配位聚合物光催化剂,为协同 CO 还原和 HO 氧化的疏水-亲水双相光催化剂提供了新的见解。
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