利用钴-氨基硫脲类配合物作为氧化还原催化剂光分解水制备氢气

引用本文: 景旭, 杨林林, 常智舵, 何成, 段春迎. 利用钴-氨基硫脲类配合物作为氧化还原催化剂光分解水制备氢气[J]. 无机化学学报, 2015, (5): 975-980. doi: 10.11862/CJIC.2015.090 shu

Citation: JING Xu, YANG Lin-Lin, CHANG Zhi-Duo, HE Cheng, DUAN Chun-Ying. Photocatalytic Hydrogen Production from Water Using Cobalt-Thiosemicarbazone Complex as Redox Catalyst[J]. Chinese Journal of Inorganic Chemistry, 2015, (5): 975-980. doi: 10.11862/CJIC.2015.090 shu

利用钴-氨基硫脲类配合物作为氧化还原催化剂光分解水制备氢气

1.
大连理工大学精细化工国家重点实验室, 大连 116024

通讯作者: 段春迎 hbdu@nju.edu.cn

基金项目:
国家自然科学基金(No.21471075) (No.21471075)

973项目(No.2011CB808704)资助。 (No.2011CB808704)

摘要: 通过将磷配体与氨基硫脲结合进一步增加螯合配体的配位能力,并引入磺酸根增强其水溶性,合成了一个钴配合物Co-NSP(配体HNSP:4-[2-(2-二苯基膦-苯烯基)-氨基硫脲腙]苯甲酸),利用其氧化还原特性开展均相体系的光驱动从水中制备氢气的研究。新的NSP三齿配体能够稳定低价的金属中心,有助于提升催化剂的催化性能。利用其与荧光素所构筑的光催化体系,在电子牺牲剂三乙胺存在下显示出良好的性能,光照6h其TON(turnover number)可达2000molH₂每摩尔催化剂。为了研究和比较其性能特点,对这一光催化体系的荧光滴定和氧化还原性能也进行了较细致的研究。

关键词:

氨基硫脲;金属钴配合物;光催化制备氢气;氮硫磷三齿配体

English

Photocatalytic Hydrogen Production from Water Using Cobalt-Thiosemicarbazone Complex as Redox Catalyst

1.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, Liaoning 116024, China

Corresponding author: 段春迎 hbdu@nju.edu.cn

Received Date: 30 October 2014
Fund Project:
国家自然科学基金(No.21471075)

973项目(No.2011CB808704)资助。

Abstract: By incorporating a phosphine donor within a thiosemicarbazone moiety to enhance the coordinated ability of the chelators, a cobalt complex Co-NSP (HNSP: 4-[2-(2-diphenylphosphino-benzylidene) thiosemicar-bohydrazone]benzenesulfonate) was obtained as the proton reduction catalyst for light driven H₂ evolution in homogeneous environment with fluorescein as the photosensitizer. The presence of NSP tridentate chelator benefits the formation of low oxidized species to increase the catalytic efficiency, and the incorporation of a sulfonate group enhances the water solubility of the catalyst. The amount of H₂ generation in 12 h photolysis maximizes in the presence of sacrificial reagent NEt₃ at pHvalue of 11.0. The initial TOF (turnover frequency) is about 200 mol H₂ per mole catalyst per hour with the turnover number (TON) about 2000 mol H₂ per mole of catalyst.

Key words:

thiosemicarbazone;cobalt complex;photocatalytic hydrogen ecolution;nsp tridentate chelator

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

利用钴-氨基硫脲类配合物作为氧化还原催化剂光分解水制备氢气

通讯作者: 段春迎 hbdu@nju.edu.cn

English

Photocatalytic Hydrogen Production from Water Using Cobalt-Thiosemicarbazone Complex as Redox Catalyst

Corresponding author: 段春迎 hbdu@nju.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

利用钴-氨基硫脲类配合物作为氧化还原催化剂光分解水制备氢气

通讯作者: 段春迎 hbdu@nju.edu.cn

English

Photocatalytic Hydrogen Production from Water Using Cobalt-Thiosemicarbazone Complex as Redox Catalyst

Corresponding author: 段春迎 hbdu@nju.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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