壳聚糖钴配合物的合成及光催化产氢性能

doi:10.7503/cjcu20190593

摘要/Abstract

摘要：

通过一锅法合成了壳聚糖钴配合物(Cs-Co)催化剂. 电感耦合等离子体质谱与X光电子能谱测试结果表明, Cs-Co中Co元素的含量为1.1 mmol/g, Co为正二价. 在优化条件下, 18 mg Cs-Co催化剂的总催化产氢量达到12.7 mL(80 min), 催化产氢速率为30258 μmol·g ^-1·h ^-1. 通过研究Cs-Co的光催化并结合电化学方法, 提出了可能的光催化机理.

关键词: 壳聚糖, 钴肟配合物, 一锅法, 光催化产氢

Abstract:

Chitosan-cobalt complex(Cs-Co) was synthesized by one-pot method. The content of Co in Cs-Co is 1.1 mmol/g and Co is positive bivalent. Under the optimized conditions, the total hydrogen production of 18 mg catalyst Cs-Co was 12.7 mL within 80 min, the hydrogen evolution rate was 30258 μmol·g ^-1·h ^-1. By studying the photocatalytic process of Cs-Co and combining with electrochemical method, a possible photocatalytic process and mechanism were proposed.

Key words: Chitosan, Cobalt oxime complex, One-pot method, Photocatalytic hydrogen evolution

中图分类号:

O644
O643.3

TrendMD:

曹锰, 柳阳, 张尚玺, 王振希, 徐胜. 壳聚糖钴配合物的合成及光催化产氢性能. 高等学校化学学报, 2020, 41(4): 735.

CAO Meng, LIU Yang, ZHANG Shangxi, WANG Zhenxi, XU Sheng. Synthesis and Photocatalytic Hydrogen Evolution Properties of Chitosan Cobalt Complex ^†. Chem. J. Chinese Universities, 2020, 41(4): 735.

图/表 10

Scheme 1 Some [FeFe] hydrogenase models reported in the literature(TON=Tamover number)

Scheme 2 Synthesis of chitosan cobalt oxime complexes

Fig.1 1H NMR spectra of chitosan and Cs-Co

Fig.2 FTIR(A) and UV-Vis(B) spectra of chitosan(a) and Cs-Co(b)

Fig.3 XPS Survy spectrum(A) and XPS spetrum of Co element(B) of Cs-Co

Fig.4 TG analysis curve of Cs-Co

Fig.5 Effect of pH value(A) and catalyst dosage(B) on catalytic hydrogen production(A) Catalytic conditions: Cs-Co, (18 mg) dry weight; [Ru(bpy)3]Cl2·H2O, 15 mg; ascorbic acid, 176 mg; H2O, 10 mL; illumination for 1 h. (B) Catalytic conditions: pH 4.5; [Ru(bpy)3]Cl2·H2O, 15 mg; ascorbic acid, 176 mg; H2O, 10 mL; illumination for 1 h.

Fig.6 Hydrogen production versus time of Cs-CoCatalytic conditions: Cs-Co, 18 mg; pH=4.5; [Ru(bpy)3]Cl2·6H2O, 15 mg; ascorbic acid, 176 mg; H2O, 10 mL. * [Ru(bpy)3]Cl2·6H2O(15 mg) and ascorbic acid(176 mg) were added again.

Fig.7 Cyclic voltammetric curve of Cs-Co in 0.1 mol/L HAc/NaOAc(pH=4.5) with a scan rate of 0.1 V/s

Scheme 3 Possible photocatalytic by drogen evolution mechanism of Cs-Co

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