Proton-coupled electron transfer activation of peroxydisulfate with phosphorylated zero-valent iron

被引：16

作者：

Liang, Chuan ^{[1
]}

Liu, Xiufan ^{[2
]}

Ling, Cancan ^{[3
]}

Guo, Furong ^{[1
]}

Li, Meiqi ^{[3
]}

Zhang, Xiang ^{[1
]}

She, Yiyi ^{[1
]}

Sun, Hongwei ^{[1
]}

Ai, Zhihui ^{[1
]}

Zhang, Lizhi ^{[1
,3
]}

机构：

[1] Cent China Normal Univ, Coll Chem, Inst Environm & Appl Chem, Key Lab Pesticide & Chem Biol,Minist Educ, Wuhan 430079, Peoples R China

[2] Hubei Normal Univ, Coll Chem & Chem Engn, Hubei Key Lab Pollutant Anal & Reuse Technol, Huangshi 435002, Hubei, Peoples R China

[3] Shanghai Jiao Tong Univ, Sch Environm Sci & Engn, Shanghai 200240, Peoples R China

来源：

APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2024年 / 352卷

基金：

中国国家自然科学基金;

关键词：

Peroxydisulfate activation; Zero-valent iron; Proton-coupled electron transfer; Phosphate proton relays; CORE-SHELL NANOWIRES; WATER OXIDATION; REDUCTION; PERSULFATE; CHEMISTRY; MECHANISM; EVOLUTION; KINETICS;

D O I：

10.1016/j.apcatb.2024.124025

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Heterogeneous peroxydisulfate (PDS) activation driven by conventional electron transfer (ET) is often frustrated by low thermodynamic driving force and sluggish kinetics. Herein, we propose a proton-coupled electron transfer (PCET) strategy of PDS activation, by utilizing ball-milled phosphorylated zero-valent iron (P-ZVI(bm)) as a PCET platform. P-ZVI(bm) efficiently activated PDS to produce SO4 center dot- and (OH)-O-center dot for rapid degradation of 4-chlorophenol in a wide pH range of 3.5-10.5, with rate constants 3-62 times those of the ZVI(bm)/PDS counterpart. PCET mechanism was evidenced by the pH dependent kinetics, kinetic isotope effect, and proton inventory study. The surface-bound phosphates offer flexible pendant protons (P-O-H) through hydrogen bonds, delocalizing electrons of peroxide O to polarize the O-O bond, thereby facilitating the ET from ZVI for O-O bond cleavage. The work demonstrates the superiority of PCET strategy for heterogeneous PDS activation, and shall guide the design of high-performance Fenton-like catalysts.

引用

页数：9

共 48 条

[1] Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications [J].