摘要
As a new organic conjugated semiconductor,graphitic carbon nitride(g-C_(3)N_(4))is emerging as a fascinating material for various photocatalytic applications due to its adjustable electronic structure,outstanding thermal endurance,appealing chemical stability,low cost,and environmental friendliness.Nevertheless,unmodified bulk g-C_(3)N_(4) possesses some intrinsic limitations related to poor crystallinity,marginal visible-light harvesting,easy recombination of charge pairs,small surface area,and slow charge migration,which give rise to the low quantum efficiency of photocatalytic reactions.One efficient strategy to overcome these shortcomings is the manipulation of the microstructures of g-C_(3)N_(4).Other than the traditional structure control,mimicking the structures of creatures in nature to design and construct bio-inspired structures is a promising approach to improve the photocatalytic performance of g-C_(3)N_(4) and even g-C_(3)N_(4)-based systems.This review summarizes the recent advances of the traditional structure-control of g-C_(3)N_(4)-based systems,and bio-inspired synthesis of g-C_(3)N_(4)-based systems from two aspects of structural bionics and functional bionics.Furthermore,the fundamentals of bio-inspired design and fabrication of g-C_(3)N_(4)-based systems are introduced in detail.Additionally,the different theoretical calculations,diverse photocatalytic applications and various modification strategies of bio-inspired structured g-C_(3)N_(4)-based systems are recapped.We believe that this work will be a guiding star for future research in the new field of biomimetic photocatalysis.
太阳能的绿色高效利用可减缓化石燃料消耗,有助于“双碳”目标的实现.光催化技术不仅可在温和条件下转化太阳能为化学能,还能实现有机污染物的高效降解,是太阳能开发利用的理想技术.光催化技术的核心在于半导体光催化剂的开发.近年来,由于石墨相氮化碳(g-C_(3)N_(4))具有易调节的电子结构、优异的耐热性和化学稳定性,廉价无毒等优势,成为光催化领域中的明星催化剂.然而,未经改性的块体g-C_(3)N_(4)存在结晶度差、可见光吸收能力弱、表面积小、载流子易复合以及电荷迁移慢等问题,导致其较低的光催化反应活性.g-C_(3)N_(4)微观形貌结构的调控可提升光吸收性能,促进载流子分离与迁移,加快表面反应速率,进而大幅提升g-C_(3)N_(4)光催化活性.除了传统的微观形貌结构调控策略以外,模仿自然界中生物结构来设计和构建仿生结构,是提升g-C_(3)N_(4)光催化性能的有效途径之一.本综述以传统的微观形貌结构调控策略为铺垫,重点介绍了设计构建仿生结构g-C_(3)N_(4)基光催化剂的理论基础,包括仿生体系的设计原则、合成策略、反应机制以及优缺点.从结构仿生学角度,归纳总结了五种仿生结构的g-C_(3)N_(4)基光催化剂在制备方法、形貌结构、光催化活性以及活性提升机制方面的最新进展,包括蜂窝状结构、花状结构、鱼鳞状结构、叶状结构和螺旋状结构.从功能仿生学角度,详细介绍了木状结构和类叶绿体结构的g-C_(3)N_(4)基光催化剂的最新进展.在此基础上,总结了g-C_(3)N_(4)基仿生催化剂在光催化降解有机污染物、光催化分解水制氢、光催化CO_(2)还原、光催化固氮合成氨、光催化制备H2O_(2)等领域的应用.此外,从理论计算层面归纳总结了g-C_(3)N_(4)基仿生光催化剂的构效关系和催化机理研究,同时详细介绍了g-C_(3)N_(4)基仿生光催化剂的改性策略.最后,从仿生催化�
基金
国家自然科学基金(22002014,U1862105,22078256)
秦创原引用高层次创新创业人才项目(2021QCYRC4-24)
陕西省自然科学基础研究计划(2017JZ001,2018KJXX-008,2019TD-039)
中央高校基本研究经费(cxtd2017004)
西安交通大学“青年拔尖人才”支持计划(HG6J021).
