Polyoxometalates‐doped Bi_(2)O_(3–x)/Bi photocatalyst for highly efficient visible‐light photodegradation of tetrabromobisphenol A and removal of NO  

多酸掺杂Bi_(2)O_(3–x)/Bi光催化剂用于高效可见光催化降解四溴双酚A和NO去除

作　　者：Yingnan Zhao Xing Qin Xinyu Zhao Xin Wang Huaqiao Tan Huiying Sun Gang Yan Haiwei Li Wingkei Ho Shun‐cheng Lee 赵英男;覃星;赵鑫宇;王馨;谭华桥;孙慧颖;闫刚;李海玮;何咏基;李顺诚(香港教育大学科学与环境研究系,中国香港;东北师范大学化学学院,教育部多金属氧酸盐与网状材料化学重点实验室,吉林长春130024;吉林建筑大学材料科学与工程学院,吉林长春130018;香港理工大学土木与环境工程系,中国香港)

机构地区：[1]Department of Science and Environmental Studies,The Education University of Hong Kong,Hong Kong,China [2]Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education,Faculty of Chemistry,Northeast Normal University,Changchun 130024,Jilin,China [3]College of Material Science and Engineering,Jilin Jianzhu University,Changchun 130018,Jilin,China [4]Department of Civil and Environmental Engineering,The Hong Kong Polytechnic University,Hong Kong,China

出　　处：《Chinese Journal of Catalysis》2022年第3期771-781,共11页催化学报（英文）

基　　金：国家自然科学基金(21771033);中央高校基本科研业务费(2412018BJ001);“香江学者”计划(2018–2019,XJ2018021);香港政府研究资助局一般研究基金(18301117);香港教育学院院长研究基金(04425).

摘　　要：Bismuth‐based photocatalysts are a class of excellent visible‐light photocatalysts;however,their redox activity is relatively poor and the efficiency of photogenerated carrier separation is low,limiting their development and application in the field of photocatalysis.To address these issues,a series of polyoxometalate PW_(12)O_(40)^(3–)‐doped Bi_(2)O_(3–x)/Bi Schottky photocatalysts PW_(12)@Bi_(2)O_(3–x)/Bi‐n(PBOB‐n,where n is the amount of NaBH4,i.e.,6,12,18,24,and 48 mg)were prepared by a simple electrospinning/calcination/in‐situ NaBH4 reduction method.In this composite photocatalyst,the doping of PW_(12) could effectively adjust the electronic structure of Bi_(2)O_(3–x) and improve its redox properties.As a shallow electron trap,PW_(12) promoted the separation of the photogenerated carriers.Furthermore,desirable Schottky junction between the metal Bi nanoparticles and PW_(12)@Bi_(2)O_(3–x) further accelerated the separation of the photogenerated carriers.The synergistic effect of the aforementioned factors endowed PBOB‐n with excellent photocatalytic activity.Among the samples,PBOB‐18 exhibited superior photocatalytic activity.Under visible‐light irradiation,93.7%(20 mg catalyst)of 20 ppm tetrabromobisphenol A(TBBPA,20 mL)was degraded in 60 min.Its activity was 4.4 times higher than that of Bi_(2)O_(3).PBOB‐18 also exhibited an ultrahigh photocatalytic performance for the removal of NO.Its removal rate(600 ppb)reached 83.3%in 30 min,making it one of the most active Bi‐based photocatalysts.Furthermore,the photocatalytic mechanisms of PBOB‐18 for TBBPA and NO have been proposed.This work provides a new direction and reference for the design of low‐cost,efficient,stable,and versatile photocatalysts.四溴双酚A(TBBPA)是一种重要的塑料添加剂和阻燃剂,广泛用于树脂、塑料、胶黏剂以及涂料中.它不仅是持久性的机污染物,还是一种内分泌干扰物,具有免疫毒性、神经毒性和细胞毒性.NO_(x),特别是NO,是主要的大气污染物之一,是形成PM2.5的重要前体,也容易引起酸雨,引发光化学烟雾、臭氧损耗、温室效应等,严重危害生态环境和人类健康.光催化技术以太阳能为驱动力,被认为是高效去除各种环境污染物的有效策略之一.但目前报道的光催化剂,大多仅适用于特定条件下单一污染物的高活性去除,严重限制了其发展,难以满足日益复杂的多功能环境净化需求.因此,设计廉价、高效、稳定的广谱光催化剂对拓展光催化的应用具有重要意义.廉价的铋基半导体光催化剂具有良好的可见光吸收能力,被认为是有前景的高效可见光催化剂之一.其中,Bi_(2)O_(3)作为组成最简单的铋基光催化剂,因其无毒、可见光催化活性好、稳定性好而备受关注.同时,其价带是由O 2p以及Bi 6s轨道杂化而成,有利于光生载流子在体相中的迁移,增强导电性.但Bi_(2)O_(3)在实际应用中仍面临着氧化还原活性不足和光生载流子分离效率低等问题,限制了其应用.因此,对Bi_(2)O_(3)进行修饰和调控,以增强其光催化活性,拓展其应用范围,成为推动Bi_(2)O_(3)光催化剂实用化的关键和挑战.本文通过简单的静电纺丝/煅烧/原位NaBH_(4)还原方法,制备了一系列多阴离子[PW_(12)O_(40)]^(3–)(PW_(12))掺杂的Bi_(2)O_(3–x)/Bi光催化剂PW_(12)@Bi_(2)O_(3–x)/Bi-n(PBOB-n,其中n为NaBH_(4)的用量,n=6,12,18,24和48 mg).在该复合光催化剂中,PW_(12)的掺杂可以有效地调节Bi_(2)O_(3–x)的电子结构,并改善其氧化还原性能.同时,PW_(12)作为电子浅阱,还可以促进光生载流子的分离.此外,金属Bi纳米粒子与PW_(12)@Bi_(2)O_(3–x)之间良好的肖特基结进一步加速了光生

关 键 词：Bismuth‐based photocatalyst POLYOXOMETALATES BI Photocatalytic degradation NO removal 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学] X505[环境科学与工程—环境工程]