Polycondensation of ammonium thiocyanate into novel porous g-C_3N_4 nanosheets as photocatalysts for enhanced hydrogen evolution under visible light irradiation  

热聚合硫氰酸铵制备多孔g-C_3N_4纳米片及其可见光催化分解水制氢性能（英文）

作　　者：崔言娟[1] 王愉雄 王浩[1] 曹福[1] 陈芳艳[1] 

机构地区：[1]江苏科技大学环境与化学工程学院,江苏镇江212003

出　　处：《Chinese Journal of Catalysis》2016年第11期1899-1906,共8页催化学报（英文）

基　　金：supported by the National Natural Science Foundation of China(21503096);the Natural Science Foundation of Jiangsu Province(BK20140507)~~

摘　　要：Porous graphitic carbon nitride（pg-C3N4） nanosheets have been prepared through a one-step ammonia thermopolymerization method.The effects of synthetic temperature on the structural,optical and photocatalytic properties of the samples have been investigated.Characterization results show that the heptazine-based conjugate heterocyclic structure was formed over 500℃,which is attributed to the inhibitory effect of ammonia from the decomposition of NH4SCN.Precise nanosheet morphology and an increased pore distribution with an enlarged surface area are observed for the samples obtained under high temperatures.Optical analysis results show that the bandgap of the samples widens and photoluminescene intensity is gradually quenched as the treating temperature is increased.The results demonstrate that a higher polymerization temperature improves the nanolayer structure,porosity and migration rate of the photo-induced carriers of the samples.The pg-C3N4 nanosheets prepared at 600℃ presents the highest photocatalytic activity for hydrogen evolution from water under visible-light irradiation.This study demonstrates a novel strategy for the synthesis and optimization of polymer semiconductor nanosheets with gratifying photocatalytic performance.二维层状半导体材料与其体相堆积结构相比表现出独特的性质,有望在纳米材料科学领域取得新的突破.基于对太阳能利用的研究,二维半导体光催化材料引起了研究者的广泛关注.诸多半导体材料已被设计合成二维纳米片结构应用于光催化领域,如MoS_2,WS_2,SnS_2和TiO_2等.石墨相氮化碳(g-C_3N_4)是一种典型的非金属二维聚合物半导体.二维层状结构的组成使得g-C_3N_4纳米片能够表现出优异的光电性质.然而,其合成目前仍然存在很大困难.目前已报道的单层或多层g-C_3N_4的制备主要有超声辅助溶剂剥离法、热处理法、插层法和电化学合成法等.但这些方法存在合成复杂和引入结构缺陷等不足.另外,在体相组成中插入孔结构也能够提高g-C_3N_4的光催化活性.目前常用的方法主要是模板法.然而,在这些生孔过程中往往引起聚合度降低,增加长程无序度,不利于光生载流子的传输.因此,如果将多孔结构引入g-C_3N_4纳米片,同时提高其聚合度结构,将在很大程度上提高其光催化性能.本文利用直接氨气热聚合的方法,将硫氰酸铵进行高温热处理,一步法合成出较高聚合度的多孔g-C_3N_4纳米片,在可见光照射下表现出较高的产氢活性和稳定性.采用X射线衍射(XRD)、红外光谱(FTIR)、荧光光谱(PL)和电子顺磁共振(EPR)等方法对多孔g-C_3N_4纳米片结构进行了详细表征.在助催化剂Pt存在下,采用可见光照射(>420 nm)分解水产氢的方法评价了其光催化性能.结果表明,热处理温度对产物结构及性能具有较大影响.XRD结果表明,在450 ℃热处理,硫氰酸铵未完全聚合,与前期氮气热处理的结论不同.当热聚合温度上升至500 ℃,石墨相结构形成.至600 ℃时,石墨相的层间距缩小,且聚合度没有明显下降.这表明氨气气氛抑制了原料分解,提高了分解聚合温度,同时增加了产物的聚合度.FTIR结果表明,热聚合温度对产物C

关 键 词：Carbon nitride NANOSHEET Semiconductor AMMONIA PHOTOCATALYSIS Hydrogen evolution 

分 类 号：O643.36[理学—物理化学] TQ116.2[理学—化学]