增强钒酸铟基材料光催化清洁能源生产和环境污染修复性能研究进展

1成果简介

近日，江西农业大学赵国庆博士、卢丽敏教授团队和中南大学焦飞鹏教授课题组合作在Separation and Purification Technology上发表了题为“Recent intensification strategies of Indium vanadate-based materials for photocatalytic application”的综述论文（10.1016/j.seppur.2024. 127462）。

钒酸铟（InVO4）基材料因具有合适的能带结构、优异的化学稳定性和出色的光催化活性，使其在清洁能源生产和环境污染物修复领域展现出良好的应用前景。然而，传统的InVO4半导体由于其不可避免的固有弊端限制了其广泛应用。基于此，为提高目标催化剂的光催化活性，本论文从形貌调控、掺杂工程、缺陷调控、共催化剂改性、晶面工程、异质结构建和外部能量场等方面对提高InVO4催化剂光催化活性的举措和机制进行了总结和评述。随后，对InVO4基光催化材料在清洁能源生产（如析氢、析氧、N2固定、H2O2合成、有机化学品合成）以及环境修复（有机污染物去除、重金属离子修复、VOCs净化、抗菌）等领域的应用进展进行了总结。最后，对InVO4光催化剂的研究现状进行了总结并对可能的研究方向进行了展望。

近年来，随着社会飞速发展和人们物质生活水平的提高，能源短缺和环境污染成为非常棘手的两大难题。作为一种有着广阔前景的绿色无污染的能源转化和环境修复技术，半导体光催化技术既能实现从太阳能的化学能的催化转化，还可以通过产生活性氧物种实现目标污染物的矿化分解，因而成为国内外研究的热点方向之一。InVO4作为一种重要的三元金属氧化物半导体，由于其具有窄带隙（约2.0 eV），结构稳定、生物相容性好、易合成等优势备受关注，在光催化领域得到广泛使用。

然而，其光生载流子复合严重等不足严重阻碍其光催化性能的进一步提高。因此，如何通过各种有效的调控策略进一步增强InVO4光催化剂的活性一直是该领域研究者们所关注的焦点。基于此，本论文从催化剂材料的调控策略出发，总结了形貌控制、掺杂工程、缺陷裁剪、助催化剂改性、晶面工程、异质结构建以及外加能量场等策略增强InVO4光催化剂催化活性的方法特点和活性增强机制。最后，进一步总结了InVO4光催化剂在清洁能源生产和环境污染物修复领域的研究进展，分析了目前所面临的挑战，并对未来可能研究发展趋势进行了展望。

2图文导读

Fig. 1 The band gap distribution of various metal vanadate photocatalysts

Fig. 3 (a) TEM image of the molecularly thin InVO4 nanosheet, (b) partial enlarged detail, (c) HRTEM images of the flat-laying and (d) the corresponding FFT patterns, (e) lateral HRTEM image, (f) crystalline model of the nanosheet. [J. Am. Chem. Soc., 2019, 141, 4209-4213.].

Fig. 4 SEM images of InVO4 samples obtained using different concentration of CTAB solution: (a) C0, (b) C0.1, (c) C0.5, (d) C1, and (e) C2. The insets are the corresponding images of low magnification. TEM image of C1. (f) The inset is the corresponding image of high resolution. [J. Mater. Sci., 2013, 48, 7574-7580.].

Fig. 5 XPS spectra of (a) In 3d, (b) O 1s, (c) V 2p3/2, (d) EPR spectra of InVO4and EG 10 h-InVO4, (e) In K-edge EXAFS spectra of InVO4, EG 10 h-InVO4 and In2O3, (f) UV-vis diffuse reflectance spectra of InVO4 and EG 10 h-InVO4, (g) charge density difference of a N2 molecule adsorbed on InVO4(left) and Vo-InVO4 (right) surfaces. Calculated Gibbs free energy diagram of N2 fixation on the surface of InVO4 and Vo-InVO4 through (h) alternating and (i) distal mechanisms at U = 0 V. [Environ. Sci. Nano, 2022, 9, 1996-2005.].

Fig. 6 (a) Photocatalytic H2 evolution rates over different MoS2/InVO4 composite photocatalysts, (b) plots of photocatalytic H2 production amount versus irradiation time over 3 wt% MoS2/InVO4 and 3 wt% Pt/InVO4 photocatalysts, (c) cyclic H2 evolution over 3 wt% MoS2/InVO4 photocatalyst, (d) proposed photocatalytic process for H2 evolution over the MoS2/InVO4 photocatalyst. [Dalton Trans., 2017, 46, 2072-2076.]. (e) H2 generation rate and (f) STH of various photocatalyst. [Mater. Sci. Eng. B, 2023, 297, 116682.].

Fig. 7 (a) The photocatalytic activity of the as-prepared samples, (b) the cycling tests for the photocatalytic CO2 reduction over 40 % IVO/LTO. [J. Alloy. Compound., 2023, 168086.]. Typical time course of (c) CO and (d) CH4 production catalyzed by various photocatalysts, (e) photocatalytic CO and CH4 evolution rates on these samples in the first 4 h, (f) cyclic tests of photocatalytic CO and CH4 production on the p-C3N4/InVO4-5 sample. [Chem. Eng. J., 2022, 434, 133867]. (g) Yields of CO after 2 h of reaction with various catalysts, and (h) cycling yield for CO production of CoAl-LDH/InVO4-30. [J. Colloid Interf. Sci., 2023, 629, 92-102.]. (i) Z-scheme mechanism of CO2 photoreduction using rGO/InVO4/Fe2O3. [ACS Sustain. Chem. Eng., 2018, 6, 8201-8211.].

Fig. 8 (a) RhB concentration versus irradiation time for the degradation of RhB aqueous solution over various photocatalysts, (b) MB (solid lines) and RhB (dotted lines) concentrations versus irradiation time over various photocatalysts for the degradation of MB and RhB (C0 = 15 mg/L) aqueous solution (c) RhB (dotted lines) + MB (solid lines) concentration versus irradiation time for the degradation of the RhB + MB aqueous solution over various photocatalysts. The “Mix” means the RhB + MB mixture. [Appl. Catal. B: Environ., 2015, 165, 285-295.]. (d) The photodegradation of TC solution, (e) the corresponding pseudo-first-order kinetics, (f) illustration of the possible mechanism of TC degradation over InVO4/CeVO4 heterojunction under simulated sunlight irradiation. [J. Environ. Chem. Eng., 2020, 8, 104588.]. (g) Photocatalytic degradation efficiency of as-prepared samples, (h) kinetic rate constants of the as-prepared catalysts, (i) photocatalytic mechanism for tetracycline degradation by InVO4/ZnWO4 composite. [Environ. Res., 2023, 227, 115735.].

Fig. 9 (a) Photocatalytic reduction of Cr6+ with various photocatalysts, (b) kinetics plots for photocatalytic reduction of Cr6+ with various photocatalysts. Photocatalytic reduction of Cr6+ to Cr3+ in the presence of 0.75 BiVO4/0.25 InVO4 samples, (c) schematic illustration for the possible photocatalytic mechanism of the 0.75 BiVO4/0.25 InVO4 composite for Cr6+ reduction under visible light irradiation. [Sep. Purif. Technol., 2023, 310, 123143.]. (d) Effect of different pH, (e) effect of dosage, (f) removal efficiency after different regeneration cycles, (g) XRD patterns of IAS-2 before and after adsorption/ photocatalytic reaction, (h) FTIR spectra of IAS-2 before and after U(Ⅵ) adsorption experiment, (i) XPS spectra of U 4f for IAS-2 after U(Ⅵ) photoreduction experiment. [Chemosphere, 2020, 260, 127548.].

Fig. 10 (a) E. coli survival curves, (b) photo-catalytic disinfection rate histogram ofE. coli,S. aureus, andP. aeruginosa, (c) recycling experiments of photocatalytic disinfection. [J. Colloid Interfaces Sci., 2019, 533, 358-368.]. (d)E. colisurvival curves, (e) photocatalytic anti-microbial rate histogram ofE. coli,S. aureusandP. aeruginosaunder visible light with 0.5InVO4/AgVO3 for 30 min, (f) schematic diagram of the proposed mechanism. [Appl. Catal. B: Environ., 2018, 220, 57-66.]. (g-i) the total bacterial counts (CFU) as a function of time using photocatalysts. The measure reflects the antibacterial effectiveness againstEscherichia coli(E. coli). [Sep. Purif. Technol., 2023, 327, 125011].

3小结

本论文总结了近年来InVO4基光催化剂在模拟可见光照射条件下用于清洁能源生产和环境污染物修复的强化策略和研究进展。随后，作者对未来本领域可能的研究方向进行了展望：

1）可结合大数据和机器学习等技术快速筛选高催化活性的InVO4基光催化材料；

2）形貌控制、掺杂工程、缺陷裁剪、助催化剂改性、晶面工程、构建异质结等策略可增强InVO4基材料的光催化活性，但过程机制目前仍不清晰，后续应结合先进表征技术，明确光催化过程增强机制；

3）拓展InVO4基材料的光催化应用领域，如光催化回收贵金属材料，建筑自清洁玻璃、自清洁织物等；

4）结合其它单元操作提升清洁能源生产和环境污染物修复效率，如光电催化、光热催化、光催化/压电催化、光催化/膜分离等。

文献：

第一作者：赵国庆

通讯作者：赵国庆，焦飞鹏，卢丽敏

通讯单位：江西农业大学化学与材料学院、中南大学化学化工学院

DOI：10.1016/j.seppur.2024.127462

通讯作者简介：

赵国庆，男，博士，江西农业大学青年教授，研究方向为能源环境光催化材料的设计合成与性能研究。目前主持江西农业大学博士科研启动基金项目1项。以第一作者/通讯作者在Coor. Chem. Rev., Small, Chem. Eng. J. Sep. Purif. Technol., 等国际权威期刊发表SCI论文20余篇，其中ESI（1%）高被引论文2篇。通讯邮箱：guoqingzhao@jxau.edu.cn; zhaogq8893@163.com

焦飞鹏，男，博士，中南大学三级教授，博士生导师，化工系副主任，中国工程教育认证专家，普通高校本科教育教学评估专家。主要从事光电催化反应工程、油水膜分离工程方面研究。主持或参与国家重点研发计划项目、国家自然科学基金项目、省部级科研项目等20余项。以第一作者/通讯作者在Chem. Eng. J., J. Membr. Sci., ACS Appl. Mater. Interf.等国际权威期刊发表SCI论文150余篇。通讯邮箱：jiaofp@csu.edu.cn; jiaofp@163.com

卢丽敏，博士，博士，江西农业大学教授，博士生导师，化学与材料学院副院长，南昌市植物资源化学利用重点实验室主任。研究方向为功能纳米材料制备及传感应用研究。主持国家自然科学基金项目5项、省部级科研课题9项；以第一作者/通讯作者在J. Am. Chem. Soc., Chem. Eng. J., J. Hazard. Mater., Chem. Commun., 等杂志发表SCI论文120余篇，其中ESI（1%）高被引论文5篇。入选江西省百千万人才工程、江西省青年井岗学者、江西省杰出青年科学基金资助计划、中国博士后基金资助者选介人物，江西省“百人远航”工程计划。获江西省自然科学三等奖1项。担任Journal of Analysis and Testing青年编委、Frontiers in Chemistry客座编委。通讯邮箱：lulimin816@hotmail.com

文章链接

https://www.sciencedirect.com/science/article/pii/S1383586624012012

　　来源：材料分析与应用