硫掺杂氮化碳微球的制备及其光催化还原性能

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1、硫掺杂氮化碳微球的制备及其光催化还原性能崔言娟;李明;赵艺蒙;杨传锋;王浩【摘要】Sulfur doped carbon nitride materials (CNS)were prepared from solvothermal method at low tempera-ture,using thiocyanuric acid as one of the precursors.XRD,FTIR,SEM and XPS technologies were carried out to characterize the catalysts.The photocatalytic reductio

2、n properties of CNS were tested by Cr(VI)reduction and H2 production from water splitting.Results showed that sulfur substituted crystal nitrogen in the carbon ni-tride molecular and formed CS bonds.With the increasing time of polymerization,the content of sulfur in the products increased.The cataly

3、sts showed remarkable visible light absorbance,and the optical absorption band edges red shifted up to about 700 nm with the increasing time of polymerization.Compared to the carbon nitride synthesized from direct calcination,CNS possessed much enhanced photocatalytic reduction activity of Cr(V) und

4、er visible light irradiation.In addition,CNS catalysts had obvious H2production properties from water split-ting.Mechanism analysis showed that photo-generated electrons and O2- were major active species during photocatalytic reduction of Cr(VI)over CNS catalysts.% 以含 硫单体三聚硫氰酸为合成原料之一，低温溶剂热法合成硫掺杂氮化碳材

5、料(CNS) 利 用XRD、FT-IR、SEM、XPS等技术对催化剂进行了表征通过对Cr(V)的还原去 除和光解水制氢性能测试,研究了 CNS的光催化还原性能结果表明,硫元素主要取 代氮化碳分子中晶格氮形成CS键随着聚合反应时间的延长，所得产物中硫含量 升高催化剂具有显著的可见光吸收，随着聚合时间的延长,吸收带边红移，可扩展至约 700 nm.与直接煅烧法制备的氮化碳相比,在可见光照下,CNS对Cr(VI)具有显著增 强的还原去除性同时,CNS催化剂具有明显的光解水制氢性能机理分析表明，光生 电子和Q2-是CNS光催化还原Cr(VI)的主要活性物种.【期刊名称】功能材料年(卷),期】2018(

6、049)005【总页数】6页(P5163-5168) 【关键词】 氮化碳;硫掺杂;溶剂热;光催化;还原【作 者】 崔言娟;李明;赵艺蒙;杨传锋;王浩【作者单位】 江苏科技大学 环境与化学工程学院,江苏 镇江212008;江苏科技大学 环境与化学工程学院,江苏 镇江212008;江苏科技大学 环境与化学工程学院,江苏 镇江212008;江苏科技大学 环境与化学工程学院,江苏 镇江212008;江苏科技大学 环境与化学工程学院,江苏 镇江212008【正文语种】 中 文【中图分类】 O6490引言近年来，可见光光催化剂在环境污染物净化和清洁能源转化方向引起了人们的广泛 关注。氮化碳是一类新型的非金

7、属聚合物半导体光催化剂，在光催化降解有机污染 物、CO2还原，光解水制氢等方面具有广泛的应用前景1-3。尽管如此，常规高 温煅烧法制备的氮化碳由于比表面积小、可见光利用率低(CNS-72CNS-48CNS-24的 顺序递减。图7 CNS-96和CN对Cr(VI)还原去除的紫外-可见吸光度曲线Fig 7 UV-Vis absorbance curves of Cr(V) reduction over CNS-96 and CN图8 CNS光催化剂对Cr(VI)光催化还原去除Fig 8 Photocatalytic reduction of Cr(V) over CNS samples2.2.2

8、光解水制氢理论研究表明，S掺杂引起氮化碳的导带位置上移，还原性增强。因此，除了 Cr(VI)的还原去除性，对CNS催化剂的光解水制氢性能同时进行了考察，结果见 图 9。没有催化剂的反应体系没有 H2 产生。催化剂加入后，随着光照时间的延长， 产H2量呈线性增加。与Cr(VI)还原活性相一致，CNS-96具有最佳的产氢速率。 经过2 h的光照，产H2量为32.1 pmol,是CNS-24产氢量的5倍。2.3 光催化机理分析为了对CNS催化剂光催化还原Cr(V)的机理进行分析，以CNS-48为催化剂，在 反应体系中加入不同的活性物种牺牲剂，通过考察还原速率的变化而研究过程机理， 如图10所示。在体

9、系中通过加入甲醇(CH3OH)作为空穴牺牲剂后,Cr(V)的还原 去除速率显著提高，这是由于空穴的消耗降低了光生电子的复合率。当在反应过程 中通入N2作为O2清除剂后,Cr(V)的还原去除速率有一定的降低。这说明Q2- 在反应过程中也起到一定的作用。因此可以总结为，CNS催化剂对Cr(V)的还原 过程中，e-还原起到主要作用，同时Q2-也参与还原过程，这与文献报道的结果 相一致22。图9 CNS光解水制氢性能Fig 9 Photocatalytic H2 production over CNS catalysts图10不同活性物种对CNS催化剂还原去除Cr(VI)的过程影响Fig 10 The

10、 effect of different active species to photoreduction of Cr(V)over CNS catalyst3结论采用低温溶剂热技术制备了硫掺杂氮化碳微球CNS光催化剂，考察了 CNS在可 见光条件下的光催化还原性能，结果表明：(1) 以三聚硫氰酸为合成单体之一，低温溶剂热条件下能够一步合成出硫掺杂的氮 化碳微球光催化剂，具有高的可见光响应，吸收带边可扩展至近700 nm。(2) 硫元素主要取代氮化碳分子中晶格氮，形成C-S键。随着聚合反应时间的延长， 所合成催化剂中硫含量增加，原子比达到13.6%。(3) 在中性条件下，CNS催化剂具有优异的

11、光催化还原Cr(VI)的性能，经过3h的 光照，去除率可近100%。同时，具有明显的光解水制氢活性。(4) 机理分析表明，在CNS光催化还原Cr(V)的过程中除了光生电子起主要作用 外，Q2-也是重要的活性物种。参考文献：1 Jiang Wenjun, Luo Wenjiao, Wang Jun, et al. Enhancement of catalytic activity and oxidative ability for graphitic J. Journal of Photochemistry and Photobiology C: Photochemistry Reviews,

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