摘要
钛基金属有机框架(Ti-MOFs)因其优异的光电性质和光催化性能、化学稳定性和低毒性以及多样化的结构,被认为是光催化分解水制氢领域中最具吸引力的MOFs之一。综述了近年来Ti-MOFs及其复合材料和衍生多孔材料在光催化制氢领域的进展。通过染料敏化或选择合适的官能团和金属节点会对Ti-MOFs的光响应及光催化活性产生重要影响。为进一步提高光催化析氢性能,可引入金属离子或与其他半导体结合形成多功能复合材料。此外,通过在合适的条件下煅烧Ti-MOFs前驱体可制备更多新颖高效的光催化剂。最后,从关键的角度讨论了Ti-MOFs及其衍生多孔材料未来在光催化分解水制氢领域的机遇和挑战。
Nowadays,it is imperative to promote the green transformation of global energy for meeting the"carbon peaking and carbon neutrality"goals,the energy sustainable development is crucial for social progress and humanity's future.Hydrogen has the advantages of being renewable,pollution-free,and high combustion heat has a wide range of application prospects and is one of the potential candidates to replace traditional fossil energy in the future,therefore,supporting global renewable energy development.Photocatalytic water splitting technology for hydrogen production directly uses unlimited reserves of clean solar energy and converts it into chemical energy,which is an emerging technology with great development prospects and is regarded as an important means to achieve the goal of"carbon neutrality"in the future.In recent years,titanium-based metal-organic frameworks(Ti-MOFs)have attracted much attention in the field of photocatalytic water splitting for hydrogen production due to their highly ordered structure,large specific surface area,high porosity,numerous active sites,strong compatibility with various materials,and an ideal template for the preparation of various carbon-and metal-based porous materials as well as their derived porous materials.However,in practical applications,similar to most one-component photocatalysts,Ti-MOFs have a low visible light response and rapid recombination of photogenerated-electron-hole pairs.In addition,most Ti-MOFs also have challenges such as poor stability and low electron conductivity,which hinder their further application in the field of photocatalytic water splitting to hydrogen.Thus,the measures to overcome the above shortcomings and thus further improve the photocatalytic performance of Ti-MOFs are the focus of current research fields.Based on this,this paper systematically summarized the latest progress of Ti-MOFs photocatalysts and their derived porous materials in the field of photocatalytic water splitting to hydrogen production.In response to Ti-MOFs’major problems including low light response,fast carrier recombination,poor stability,and low conductivity,plenty of work aiming at modifying Ti-MOFs photocatalysts and their derived porous materials had been made in recent years.First,this work described the main advantages of Ti-MOFs,including their controllable and variable structure,high as well as controllable porosity,and large specific surface area,together with excellent optical properties.Based on these characteristics,the probability of photogenerated electron-hole recombination center formation of Ti-MOFs could be reduced,and more reactive sites could be exposed.Besides,Ti-MOFs had excellent photo-response characteristics,making Ti-MOFs have broad prospects in the field of photocatalytic hydrogen production.Secondly,this work summarized some strategies and research progress in improving the photocatalytic hydrogen evolution performance of Ti-MOFs,including photosensitizers introduction,functional group,and nano-metal modification.Although these methods could effectively improve the activity of Ti-MOFs photocatalysts,their hydrogen evolution performance was still low.To further improve the activity and hydrogen production rate,the design of new high-efficiency Ti-MOFs photocatalysts by metal doping or combination with narrow bandgap semiconductor modification had become a hot spot.This strategycouldnot only made full use of the advantages of Ti-MOFs but also effectively combined the advantages of other narrow bandgap semiconductors or metals to design brand-new photocatalysts with enhanced efficiency.Subsequently,the research progress of Ti-MOFs-derived metal oxides(Ti_(x)O_(y))and their high-performance porous composites in the field of photocatalytic hydrogen production was reviewed.Ti-MOFs-derived metal oxides could not only maintain the original high specific surface area and good porosity of the precursor but also have the photocatalytic activity of semiconductors,which could effectively promote the photocatalytic reaction rate and improve their photocatalytic performance.Finally,the challenges and opportunities of Ti-MOFs in the field of photocatalytic water splitting to hydrogen were summarized.Compared with other types of MOFs(such as Zr-MOFs,Fe-MOFs,etc.),there were relatively few Ti-MOFs and their derivatives that could be used for the photocatalytic decomposition of water to produce hydrogen.Therefore,more new Ti-MOFs that could be applied to the field of photocatalytic hydrogen production still waited to be explored.Secondly,the crystallization process of Ti-MOFs was hindered due to the easy hydrolysis of Ti-MOFs,thus the development of Ti-MOFs in the field of photocatalytic water splitting to hydrogen production was limited.It was necessary to design more feasible schemes to improve the water stability of Ti-MOFs.By modifying the hydrophobic group of the ligand or using other inorganic materials as the titanium source,such as Ti_(3)C_(2)T_(x) or TiC_(2)T_(x) which was a two-dimensional layered MXene,it could be used as a titanium source to effectively solve the problem of titanium source hydrolysis and prepare more Ti-MOFs with new topology.In addition,the mechanism of Ti-MOFs photocatalytic separation of water to hydrogen production remained unclear.By combining advanced characterization methods and density function theory(DFT)calculations,more details of the mechanism ccould be revealed,which was of great significance for the design of Ti-MOFs photocatalysts with more novel structures and outstanding performance.
作者
吴鹏
李绍元
席风硕
李秀凤
吕国强
马文会
Wu Peng;Li Shaoyuan;Xi Fengshuo;Li Xiufeng;Lv Guoqiang;Ma Wenhui(National Engineering Laboratory of Vacuum Metallurgy,School of Metallurgical and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China)
出处
《稀有金属》
EI
CAS
CSCD
北大核心
2023年第12期1624-1641,共18页
Chinese Journal of Rare Metals
基金
国家自然科学基金项目(52274408,52264056)
云南省重大科技专项项目(202102AB080016,202103AA080004,202202AB080010,202202AG050012)
云南省优秀青年基金项目(202201AW070014)资助
作者简介
吴鹏(1998-),男,江西上饶人,硕士研究生,研究方向:金属有机框架光催化剂,E-mail:wp18779399593@163.com;通信作者:李绍元,教授,电话:15198907664,E-mail:lsy415808550@163.com
