Microchemical environmental regulation of POMs@MIL-101(Cr) promote photocatalytic nitrogen to ammonia

Senda Su; Xiaoman Li; Zhenyu Liu; Wenming Ding; Yue Cao; Yang Yang; Qin Su; Min Luo

doi:10.1016/j.jcis.2023.05.069

Microchemical environmental regulation of POMs@MIL-101(Cr) promote photocatalytic nitrogen to ammonia

J Colloid Interface Sci. 2023 Sep 15:646:547-554. doi: 10.1016/j.jcis.2023.05.069. Epub 2023 May 15.

Authors

Senda Su¹, Xiaoman Li², Zhenyu Liu¹, Wenming Ding¹, Yue Cao¹, Yang Yang¹, Qin Su¹, Min Luo³

Affiliations

¹ State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021, China.
² State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021, China. Electronic address: lixm2017@nxu.edu.cn.
³ State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan, Ningxia 750021, China. Electronic address: luominjy@nxu.edu.cn.

PMID: 37210902
DOI: 10.1016/j.jcis.2023.05.069

Abstract

The polyoxometalates (POMs) have been shown to be highly effective as reactive sites for photocatalytic nitrogen fixation reactions. However, the effect of POMs regulation on catalytic performance has not been reported yet. Herein, a series of composites (SiW₉M₃@MIL-101(Cr) (M = Fe, Co, V, Mo) and D-SiW₉Mo₃@MIL-101(Cr), D, Disordered) were obtained by regulating transition metal compositions and arrangement in the POMs. The ammonia production rate of SiW₉Mo₃@MIL-101(Cr) is much higher than that of other composites, reaching 185.67 μmol·h^-1·g^-1_cat in N₂ without sacrificial agents. The structural characterization of composites reveals that the increase of the electron cloud density of W atom in composites is the key to improve the photocatalytic performance. In this paper, the microchemical environment of POMs was regulated by transition metal doping method, thereby promoting the efficiency of photocatalytic ammonia synthesis for the composites, which provides new insights into the design of POM-based photocatalysts with high catalytic activity.

Keywords: MOFs; Microchemical environmental; Nitrogen fixation; POMs.