金属碳化钨与液相染料光敏剂协同促进光催化制氢  

Metallic Tungsten Carbide Coupled with Liquid-Phase Dye Photosensitizer for Efficient Photocatalytic Hydrogen Production

作　　者：雷永刚 赵天宇[3] 黄锦鸿 张颖贞 臧雪瑞 李晓 蔡伟龙 黄剑莹 胡军[3] 赖跃坤 Yonggang Lei;Tianyu Zhao;Kim Hoong Ng;Yingzhen Zhang;Xuerui Zang;Xiao Li;Weilong Cai;Jianying Huang;Jun Hu;Yuekun Lai(National Engineering Research Center of Chemical Fertilizer Catalyst(NERC-CFC),College of Chemical Engineering,Fuzhou University,Fuzhou 350116,China;Qingyuan Innovation Laboratory,Quanzhou 362801,Fujian Province,China;School of Chemical Engineering,Northwest University,Xi'an,710069,China;R&D Center of Biochemical Engineering Technology,Ming Chi University of Technology,New Taipei 24301,Taiwan,China;College of Pipeline and Civil Engineering,China University of Petroleum(East China),Qingdao 266580,Shandong Province,China)

机构地区：[1]福州大学石油化工学院,化肥催化剂国家工程研究中心(NERC-CFC),福州350116 [2]清源创新实验室,福建泉州362801 [3]西北大学化工学院,西安710069 [4]明志科技大学生化工程技术研发中心,中国台湾新北243015 [5]中国石油大学(华东)储运与建筑工程学院,山东青岛266580

出　　处：《物理化学学报》2023年第4期58-66,共9页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(22075046,51972063,21676216,21501127,51502185);国家重点研发计划(2019YFE0111200);福建省杰出青年基金(2020J06038);福建省自然科学基金(2019J01256);111项目(D17005);中国博士后科学基金(前期站,2019TQ0061);陕西省教育厅专项(20JC034);Kim Hoong Ng感谢中国台湾科技部(MOST)和明志科技大学(MCUT)的财政支持(MOST-110-2222-E-131-004-);Kim Hoong Ng感谢中国台湾科技部(MOST)和明志科技大学(MCUT)的财政支持(VK000-1300-111)。

摘　　要：使用WC作为光催化材料通过水还原制氢很常见,但它通常需要与有效的光吸收剂协同才能产生有意义的光催化活性。这可归因于WC的窄带隙,导致水的氧化还原能力不足。有趣的是,我们的研究通过一种新型固液光催化体系克服了这种限制,该体系将裸WC光催化剂与液相光敏赤藓红B(Er B)相结合。这种概念的提出消除了将WC耦合到光吸收半导体的需要,这通常需要繁琐的程序来获得适当的功能化光催化复合材料。实验结果表明,在可见光(λ=520 nm)照射下,所提出的固液光催化体系产生了显著的氢气,然而,只有在三乙醇胺(TEOA)作为牺牲试剂的共同存在下。显然,仅加入WC和Er B的空白实验在典型的光催化条件下表现出几乎为零的光催化活性和无法测量的H_(2)生成。在光照TEOA溶液中仅存在Er B或WC的光反应中也观察到类似的活性。这些空白实验证实了所有三种成分的重要性,即WC、Er B和TEOA,它们分别作为光催化剂、光吸收剂和牺牲试剂,在我们提出的体系中产生有意义的H_(2)。值得注意的是,在我们的调查中系统地研究了三个关键参数,即p H值、Er B和WC浓度的影响。发现H_(2)生成的最佳p H值为8,稍微改变到更碱性或酸性条件会降低体系的光催化活性。在p H<8时,部分TEOA将发生部分质子化,从而失去其在光催化体系中作为牺牲试剂的活性。当p H值增加到超过8时,反应介质中的低质子浓度也会扰乱热力学驱动,导致体系产生的H_(2)受到抑制。同时,发现最佳Er B浓度为1mmol·L^(-1),从最佳点降低或增加Er B浓度均不利于H_(2)的产生。Er B浓度较低的体系(<1mmol·L^(-1)),在吸光上不足以满足体系的礼用,而较高浓度(>1 mmol·L^(-1)Er B)的体系,会引起明显的散射效应,组织光穿透反应溶液。相反,WC的浓度与H_(2)的生成呈稳定的正相关,在加入12 mmol·L^(-1)WC的体系中,H_(2)的生成量最高。在最佳条件�Tungsten carbide(WC)is commonly used as a photocatalytic material for hydrogen production via water reduction.However,it is often combined with an effective photoabsorber to provide sufficient photoactivity.This is attributed to the narrow band gap of WC,which leads to an inadequate redox capability for water reduction.Notably,this limitation was overcome using a novel solid-liquid photocatalytic system that compliments bare WC photocatalysts with liquid-phase photosensitizing erythrosine B(ErB).The proposed concept eliminates the need to couple WC with photoabsorbing semiconductors,which often requires tedious procedures for the proper functionalization of photocatalytic composites.The experimental results indicated significant hydrogen production from the proposed solid-liquid photocatalytic system under irradiation with visible light(λ=520 nm);however,only in the presence of triethanolamine(TEOA)as a sacrificial reagent.Evidently,a blank experiment with only WC and ErB under typical photoreaction conditions exhibited nearly zero photoactivity and the production of H_(2)was undetected.Similarly,nonactivity was observed for the photoreaction in the presence of ErB or WC in the irradiated TEOA solution.These blank experiments confirmed the significance of all three components,namely WC,ErB,and TEOA,which functioned as the photocatalyst,photoabsorber,and sacrificial reagent,respectively,for suitable H_(2)production in the proposed system.The effects of three critical parameters,such as pH,ErB concentration,and WC concentration,were systematically investigated.The optimum pH for H_(2)production was 8,with a slight variation to more basic or acidic conditions reducing the photoactivity of the system.At pH<8,part of TEOA undergoes partial protonation,thereby losing its activity as a sacrificial reagent in the photocatalytic system.As the pH increased to>8,the low proton concentration in the reaction medium perturbed the thermodynamic drive,leading to suppressed H_(2)production.The optimum ErB concentration was 1 mmo

关 键 词：液相 WC 赤藓红B 三乙醇胺 光催化 制氢 

分 类 号：O643[理学—物理化学]