金属卤化物钙钛矿量子点的制备及其光催化应用研究进展

doi:10.19964/j.issn.1006-4990.2022-0109

摘要/Abstract

摘要：

利用太阳能光催化技术生产清洁燃料、降解污染物及转化高附加值产品，是解决当前能源短缺和环境污染问题的有效途径。随着对金属卤化物钙钛矿的深入研究，成功开发出一系列能够制备出成分和形貌控制精确、产物均匀性好、结晶度高的钙钛矿量子点的合成方法，使钙钛矿量子点应用到光催化领域中。综述了热注入法、配体辅助再沉淀法、溶剂热法、微波辅助法等金属卤化物钙钛矿量子点的合成方法及金属卤化物钙钛矿量子点在光催化析氢、光催化还原二氧化碳、光催化合成有机物以及光催化降解有机物等方面的研究进展，最后对金属卤化物钙钛矿光催化剂的发展前景进行了展望。

关键词: 金属卤化物钙钛矿, 量子点, 光催化

Abstract:

Solar driven photocatalysis is an effective method to prepare clean fuels，degrade pollutants and convert high value-added products to solve the problems of energy shortage and environmental pollution.With the further study of metal halide perovskite，researchers have successfully developed a series of synthesis methods which can prepare perovskite quantum dots with precise composition and morphology control，good product uniformity and high crystallinity，so that perovskite quantum dots can be applied to the field of photocatalysis.The synthesis methods of metal halide perovskite quantum dots by thermal injection，ligand-assisted reprecipitation，solvothermal method and microwave assisted method were reviewed，and the research progress of metal halide perovskite in the aspects of photocatalytic hydrogen evolution，photocatalytic reduction of CO₂，photocatalytic synthesis of organic matter and photocatalytic degradation of organic matter were discussed.Finally，the development prospect of metal halide perovskite photocatalyst was prospected.

Key words: metal halide perovskites, quantum dots, photocatalytic

中图分类号:

TQ034

李宏渊,孟哈日巴拉. 金属卤化物钙钛矿量子点的制备及其光催化应用研究进展[J]. 无机盐工业, 2023, 55(2): 36-44.

LI Hongyuan,HARI Bala. Research progress of preparation and photocatalytic application of metal halide perovskite quantum dots[J]. Inorganic Chemicals Industry, 2023, 55(2): 36-44.

图/表 5

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参考文献 57

1	FUJISHIMA A， HONDA K.Electrochemical photolysis of water at a semiconductor electrode[J].Nature，1972，238（5358）：37-38.
2	HISATOMI T， DOMEN K.Reaction systems for solar hydrogen production via water splitting with particulate semiconductor photocatalysts[J].Nature Catalysis，2019，2（5）：387-399.
3	LI Xubing， TUNG C H， WU Lizhu.Semiconducting quantum dots for artificial photosynthesis[J].Nature Reviews Chemistry，2018，2（8）：160-173.
4	LIAO Guangfu， GONG Yan， ZHANG Li，et al.Semiconductor polymeric graphitic carbon nitride photocatalysts：The “holy grail” for the photocatalytic hydrogen evolution reaction under visible li-ght[J].Energy & Environmental Science，2019，12（7）：2080-2147.
5	郭宇，李燕瑞，王成名，等.TiO₂/石墨烯复合材料的光生电荷分离调控与光催化产氢性能研究[J].化学学报，2019，77（6）：520-524.
	GUO Yu， LI Yanrui， WANG Chengming，et al.Photogenerated charge separation and photocatalytic hydrogen production of TiO₂/graphene composite materials[J].Acta Chimica Sinica，2019，77（6）：520-524.
6	WINNERL J， KRAUT M， ARTMEIER S，et al.Selectively grown GaN nanowalls and nanogrids for photocatalysis：Growth and optical properties[J].Nanoscale，2019，11（10）：4578-4584.
7	YU Shan， FAN Xiangbing， WANG Xian，et al.Efficient photocatalytic hydrogen evolution with ligand engineered all-inorganic InP and InP/ZnS colloidal quantum dots[J].Nature Communications，2018，9.Doi：10.1038/s41467-018-06294-y .
8	SUBUDHI S， RATH D， PARIDA K M.A mechanistic approach towards the photocatalytic organic transformations over functionalised metal organic frameworks：A review[J].Catalysis Science & Technology，2018，8（3）：679-696.
9	刘玉成，郑啸，黄培强.光催化氧化还原体系中硝酮与芳香叔胺的自由基偶联反应[J].化学学报，2019，77（9）：850-855.
	LIU Yucheng， ZHENG Xiao， HUANG PeiQiang.Photoredox catalysis for the coupling reaction of nitrones with aromatic tertiary amines[J].Acta Chimica Sinica，2019，77（9）：850-855.
10	CHENG Ziyong， LIN Jun.Layered organic-inorganic hybrid pero-vskites：Structure，optical properties，film preparation，patterning and templating engineering[J].CrystEngComm，2010，12（10）：2646-2662.
11	ABDI-JALEBI M， PAZOKI M， PHILIPPE B，et al.Dedoping of lead halide perovskites incorporating monovalent cations[J].ACS Nano，2018，12（7）：7301-7311.
12	D′INNOCENZO V， GRANCINI G， ALCOCER M J P，et al.Excitons versus free charges in organo-lead tri-halide perovskites[J].Nature Communications，2014，5.Doi：10.1038/ncomms4586 .
13	CHEN Zhaolai， DONG Qingfeng， LIU Ye，et al.Thin single crystal perovskite solar cells to harvest below-bandgap light absorption[J].Nature Communications，2017，8.Doi：10.1038/s41467-017-02039-5 .
14	JIANG Qi， ZHANG Liuqi， WANG Haolin，et al.Enhanced electron extraction using SnO₂ for high-efficiency planar-structure HC（NH₂）₂PbI₃-based perovskite solar cells[J].Nature Energy， 2017，2.Doi：10.1038/nenergy.2016.177 .
15	LI Sijia， DING Huaiyi， CAI Hongbing，et al.Realizing CsPbBr₃ light-emitting diode arrays based on PDMS template confined solution growth of single-crystalline perovskite[J].The Journal of Physical Chemistry Letters，2020，11（19）：8275-8282.
16	FERNANDEZ-IZQUIERDO L， REYES-BANDA M G，MATHEWX，et al.Cesium lead bromide（CsPbBr₃） thin-film-based solid-state neutron detector developed by a solution-free sublimation process[J].Advanced Materials Technologies，2020，5（12）.Doi：10.1002/admt.202000534 .
17	JIANG Linlin， PENG Yong， XIANG Tianxing，et al.A counter electrode modified with renewable carbonized biomass for an all-inorganic CsPbBr₃ perovskite solar cell[J].Journal of Alloys and Compounds，2022，902.Doi：10.1016/j.jallcom.2022.163725 .
18	ZHANG Canran， DUAN Junjie， QIN Feifei，et al.CsPbBr₃ interconnected microwire structure：Temperature-related photoluminescence properties and its lasing action[J].Journal of Materials Chemistry C，2019，7（34）：10454-10459.
19	KOJIMA A， TESHIMA K， SHIRAI Y，et al.Organometal halide perovskites as visible-light sensitizers for photovoltaic cells[J].Journal of the American Chemical Society，2009，131（17）：6050-6051.
20	MIN H， LEE D Y， KIM J，et al.Perovskite solar cells with atomically coherent interlayers on SnO₂ electrodes[J].Nature，2021，598（7881）：444-450.
21	MACEICZYK R M， DÜMBGEN K， LIGNOS I，et al.Microfluidic reactors provide preparative and mechanistic insights into the synthesis of formamidinium lead halide perovskite nanocryst-als[J].Chemistry of Materials，2017，29（19）：8433-8439.
22	PROTESESCU L， YAKUNIN S， BODNARCHUK M I，et al.Nanocrystals of cesium lead halide perovskites（CsPbX₃，X=Cl，Br，and I）：Novel optoelectronic materials showing bright emission with wide color gamut[J].Nano Letters，2015，15（6）：3692-3696.
23	ZHANG Feng， ZHONG Haizheng， CHEN Cheng，et al.Brightly luminescent and color-tunable colloidal CH₃NH₃PbX₃（X=Br，I，Cl） quantum dots：Potential alternatives for display technolo- gy[J].ACS Nano，2015，9（4）：4533-4542.
24	LI Xiaoming， WU Ye， ZHANG Shengli，et al.CsPbX₃ quantum dots for lighting and displays：Room-temperature synthesis，photoluminescence superiorities，underlying origins and white light-emitting diodes[J].Advanced Functional Materials，2016，26（15）：2435-2445.
25	SHAMSI J， RASTOGI P， CALIGIURI V，et al.Bright-emitting perovskite films by large-scale synthesis and photoinduced solid-state transformation of CsPbBr₃ nanoplatelets[J].ACS Nano，2017，11（10）：10206-10213.
26	CHEN Min， ZOU Yatao， WU Linzhong，et al.Solvothermal synthesis of high-quality all-inorganic cesium lead halide perovskite nanocrystals：From nanocube to ultrathin nanowire[J].Advanced Functional Materials，2017，27（23）.Doi：10.1002/adfm. 201701121 .
27	CHEN Daqin， FANG Gaoliang， CHEN Xiao，et al.Mn-Doped CsPbCl₃ perovskite nanocrystals：Solvothermal synthesis，dual-color luminescence and improved stability[J].Journal of Materials Chemistry C，2018，6（33）：8990-8998.
28	LONG Zi， REN Hong， SUN Jianghui，et al.High-throughput and tunable synthesis of colloidal CsPbX₃ perovskite nanocrystals in a heterogeneous system by microwave irradiation[J].Chemical Communications，2017，53（71）：9914-9917.
29	PAN Qi， HU Huicheng， ZOU Yatao，et al.Microwave-assisted synthesis of high-quality “all-inorganic”CsPbX₃（X=Cl，Br，I） perovskite nanocrystals and their application in light emitting diodes[J].Journal of Materials Chemistry C，2017，5（42）：10947-10954.
30	TONG Yu， BLADT E， AYGÜLER M F，et al.Highly luminescent cesium lead halide perovskite nanocrystals with tunable composition and thickness by ultrasonication[J].Angewandte Chemie International Edition，2016，55（44）：13887-13892.
31	TONG Yu， BOHN B J， BLADT E，et al.From precursor powders to CsPbX₃ perovskite nanowires：One-pot synthesis，growth mech-anism，and oriented self-assembly[J].Angewandte Chemie International Edition，2017，56（44）：13887-13892.
32	NEDELCU G， PROTESESCU L， YAKUNIN S，et al.Fast anion-exchange in highly luminescent nanocrystals of cesium lead halide perovskites（CsPbX₃，X=Cl，Br，I）[J].Nano Letters，2015，15（8）：5635-5640.
33	LIGNOS I， STAVRAKIS S， NEDELCU G，et al.Synthesis of cesium lead halide perovskite nanocrystals in a droplet-based microfluidic platform：Fast parametric space mapping[J].Nano Letters，2016，16（3）：1869-1877.
34	ZHANG Dandan， YANG Yiming， BEKENSTEIN Y，et al.Synthesis of composition tunable and highly luminescent cesium lead halide nanowires through anion-exchange reactions[J].Journal of the American Chemical Society，2016，138（23）：7236-7239.
35	PARK S， CHANG W J， LEE C W，et al.Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution[J].Nature Energy，2017，2.Doi：10.1038/nenergy.2016.185 .
36	XIAO Mu， HAO Mengmeng， Miaoqiang LYU，et al.Surface ligands stabilized lead halide perovskite quantum dot photocatalyst for visible light-driven hydrogen generation[J].Advanced Functional Materials，2019，29（48）.Doi：10.1002/adfm.201905683 .
37	WU Yaqiang， WANG Peng， ZHU Xianglin，et al.Composite of CH₃NH₃PbI₃ with reduced graphene oxide as a highly efficient and stable visible-light photocatalyst for hydrogen evolution in aqueous HI solution[J].Advanced Materials，2018，30（7）.Doi：10.1002/adma.201704342 .
38	SONG Wentao， WANG Yiming， WANG Cheng，et al.Photocatalytic hydrogen production by stable CsPbBr₃@PANI nanoparticles in aqueous solution[J].ChemCatChem，2021，13（7）：1711-1716.
39	DING Ling， SHEN Chenyang， ZHAO Yi，et al.CsPbBr₃ nanocrystals glass facilitated with Zn ions for photocatalytic hydrogen production via H₂O splitting[J].Molecular Catalysis，2020，483.Doi：10.1016/j.mcat.2020.110764 .
40	XU Yangfan， YANG Muzi， CHEN Baixue，et al.A CsPbBr₃ perovskite quantum dot/graphene oxide composite for photocatalytic CO₂ reduction[J].Journal of the American Chemical Society，2017，139（16）：5660-5663.
41	HOU Jungang， CAO Shuyan， WU Yunzhen，et al.Inorganic colloidal perovskite quantum dots for robust solar CO₂ reduction[J].Chemistry-A European Journal，2017，23（40）：9481-9485.
42	XU Yangfan， YANG Muzi， CHEN Hongyan，et al.Enhanced solar-driven gaseous CO₂ conversion by CsPbBr₃ nanocrystal/Pd nano-sheet Schottky-junction photocatalyst[J].ACS Applied Energy Materials，2018，1（9）：5083-5089.
43	JIANG Yong， LIAO Jinfeng， XU Yangfan，et al.Hierarchical CsPbBr₃ nanocrystal-decorated ZnO nanowire/macroporous graphene hybrids for enhancing charge separation and photocatalytic CO₂ reduction[J].Journal of Materials Chemistry A，2019，7（22）：13762-13769.
44	Man OU， TU Wenguang， YIN Shengming，et al.Amino-assisted anchoring of CsPbBr₃ perovskite quantum dots on porous g-C₃N₄ for enhanced photocatalytic CO₂ reduction[J].Angewandte Chemie，2018，130（41）：13758-13762.
45	PAN Aizhao， MA Xiaoqin， HUANG Shengying，et al.CsPbBr₃ perovskite nanocrystal grown on MXene nanosheets for enhanced photoelectric detection and photocatalytic CO₂ reduction[J].The Journal of Physical Chemistry Letters，2019，10（21）：6590-6597.
46	XU Yangfan， WANG Xudong， LIAO Jinfeng，et al.Amorphous-TiO₂-encapsulated CsPbBr₃ nanocrystal composite photocatalyst with enhanced charge separation and CO₂ fixation[J].Advanced Materials Interfaces，2018，5（22）.Doi：10.1002/admi.201801015 .
47	WAN Shipeng， Man OU， ZHONG Qin，et al.Perovskite-type CsPbBr₃ quantum dots/UiO-66（NH₂） nanojunction as efficient visible-light-driven photocatalyst for CO₂ reduction[J].Chemical Engineering Journal，2019，358：1287-1295.
48	KONG Zicheng， LIAO Jinfeng， DONG Yujie，et al.Core@Shell CsPbBr₃@Zeolitic imidazolate framework nanocomposite for efficient photocatalytic CO₂ reduction[J].ACS Energy Letters， 2018，3（11）：2656-2662.
49	WU Liyuan， MU Yanfei， GUO Xiaoxuan，et al.Encapsulating perovskite quantum dots in iron-based metal-organic frameworks（MOFs） for efficient photocatalytic CO₂ reduction[J].Angewandte Chemie International Edition，2019，58（28）：9491-9495.
50	FAN Qiangwen， ZHU Longwei， LI Xuhuai，et al.Visible-light pho-tocatalytic selective oxidation of amine and sulfide with CsPbBr 3 as photocatalyst[J].New Journal of Chemistry，2021，45（30）：13317-13322.
51	HUANG Haowei， YUAN Haifeng， JANSSEN K P F，et al.Efficient and selective photocatalytic oxidation of benzylic alcohols with hybrid organic-inorganic perovskite materials[J].ACS Energy Letters，2018，3（4）：755-759.
52	LI Xin， ZHANG Taiyang， WANG Tian，et al.Recent progress of photocatalysis based on metal halide perovskites[J].Acta Chimica Sinica，2019，77（11）.Doi：10.6023/a19080292 .
53	WU Wenbin， WONG Y C， TAN Zhikuang，et al.Photo-induced thiol coupling and C-H activation using nanocrystalline lead-halide perovskite catalysts[J].Catalysis Science & Technology，2018，8（16）：4257-4263.
54	CARDENAS-MORCOSO D， GUALDRÓN-REYES A F， FERREIRA VITORETI A B，et al.Photocatalytic and photoelectrochemical degradation of organic compounds with all-inorganic metal halide perovskite quantum dots[J].The Journal of Physical Chemistry Letters，2019，10（3）：630-636.
55	ZHAO Yanyan， SHI Huanxian， HU Xiaoyun，et al.Fabricating CsPbX₃/CN heterostructures with enhanced photocatalytic activity for penicillins 6-APA degradation[J].Chemical Engineering Journal，2020，381.Doi：10.1016/j.cej.2019.122692 .
56	GAO Ge， XI Qiaoyue， ZHOU Hua，et al.Novel inorganic perovs-kite quantum dots for photocatalysis[J].Nanoscale，2017，9（33）：12032-12038.
57	ZHAO Yanyan， WANG Yongbo， LIANG Xuhua，et al.Enhanced photocatalytic activity of Ag-CsPbBr₃/CN composite for broad spectrum photocatalytic degradation of cephalosporin antibiotics 7-ACA[J].Applied Catalysis B：Environmental，2019，247：57-69.

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