原位水热法可控合成Bi2MoO6/MoO3复合纤维及其高效光催化产氢性能

doi:10.11949/0438-1157.20251106

摘要/Abstract

摘要：

以静电纺丝制备的MoO₃纳米纤维为基质与钼源，采用原位水热法可控合成Bi₂MoO₆/MoO₃复合纤维。通过调控反应液pH值、反应温度及保温时间等参数，实现对复合纤维物相组成、微观形貌及界面结构的精准调控，并系统探究其光吸收性能、载流子分离效率与光催化产氢活性的构效关系。结果显示，当pH调节为3.0时，所制备的BMM-3.0复合纤维呈现出优异的微观结构，Bi₂MoO₆纳米片沿MoO₃纤维表面均匀且有序地生长，二者形成紧密清晰的异质结界面；其吸收边红移至498 nm，光致发光强度最低，瞬态光电流强度最大，表明光吸收能力与载流子分离效率显著提升。光催化性能测试表明：BMM-3.0的析氢速率达4.39 mmol·g^-1·h^-1，分别为纯相MoO₃的10倍与纯相Bi₂MoO₆的6倍，且循环使用后产氢率仍保持90% 以上；机理分析证实，材料通过形成S型异质结与界面内置电场，有效抑制光生载流子无效复合，促进光生电子-空穴对分离与定向传输。本研究为高性能铋基复合光催化材料设计提供新途径，为光催化产氢技术实用化奠定实验基础。

关键词: 水热, Bi₂MoO₆/MoO₃, S 型异质结, 复合材料, 制氢

Abstract:

Using MoO₃nanofibers prepared by electrospinning as the matrix and molybdenum source, Bi₂MoO₆/MoO₃ composite fibers were controllably synthesized via an in-situ hydrothermal method. By adjusting parameters such as the pH value of the reaction solution, reaction temperature, and holding time, precise regulation of the phase composition, micro-morphology, and interface structure of the composite fibers was achieved. Additionally, the structure-activity relationships among their light absorption performance, carrier separation efficiency, and photocatalytic hydrogen production activity were systematically investigated. The results show that when the pH value is adjusted to 3.0, the prepared BMM-3.0 composite fibers exhibit an excellent microstructure, where Bi₂MoO₆ nanosheets grow uniformly and orderly along the surface of MoO₃ fibers, forming a tight and clear heterojunction interface between the two. The absorption edge of BMM-3.0 redshifts to 498 nm, accompanied by the lowest photoluminescence intensity and the highest transient photocurrent intensity, indicating significant improvements in light absorption capacity and carrier separation efficiency. Photocatalytic performance tests demonstrate that the hydrogen evolution rate of BMM-3.0 reaches 4.39 mmol·g^-1·h^-1, which is 10 times that of pure-phase MoO₃ and 6 times that of pure-phase Bi₂MoO₆. Moreover, the hydrogen production rate remains above 90% after cyclic use. Mechanism analysis confirms that the material effectively suppresses the invalid recombination of photogenerated carriers and promotes the separation and directional transfer of photogenerated electron-hole pairs by forming an S-scheme heterojunction and an internal electric field at the interface. This study provides a new approach for the design of high-performance bismuth-based composite photocatalytic materials and lays an experimental foundation for the practical application of photocatalytic hydrogen production technology.

Key words: Hydrothermal, Bi₂MoO₆/MoO₃, S-scheme heterojunction, Composites, Hydrogen production

中图分类号:

O643

曹铁平, 李跃军, 孙大伟, 肖磊. 原位水热法可控合成Bi₂MoO₆/MoO₃复合纤维及其高效光催化产氢性能[J]. 化工学报, DOI: 10.11949/0438-1157.20251106.

Tieping CAO, Yuejun LI, Dawei SUN, Lei XIAO. Controlled Synthesis of Bi₂MoO₆/MoO₃ Composite Fibers via In-Situ Hydrothermal Method and Their High-Efficiency Photocatalytic Hydrogen Production Performance[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251106.

图/表 7

图1 不同样品的X射线衍射（XRD）图谱注:图1为不同样品的X射线衍射(XRD)谱图。如图所示,MoO3纳米纤维位于2θ=23.4°、25.7°、27.3°、38.9°处的主要衍射峰(对应JCPDS No.35-0609),与正交晶系α-MoO3特征峰完全吻合,表明其物相纯净;Bi2MoO6纳米粉体位于2θ=28.3°、32.6°、42.3°处的主要衍射峰(对应JCPDS No.72-1524),与正交晶系 γ-Bi2MoO6标准特征峰精准匹配,证明其为单一 γ 相;样品BMM-1.5的XRD谱中同时出现α-MoO3和γ-Bi2MoO6特征峰且峰位不变,说明 Bi2MoO6/MoO3复合物已合成; BMM-3.0的XRD谱与BMM-1.5相比,α-MoO3特征峰的峰位基本不变,但 γ-Bi2MoO6峰形变窄、峰强度升高,表明纤维表面Bi2MoO6的结晶度增强且负载量增大;BMM-6.0样品的XRD谱中,只检测α-MoO3特征峰,说明该条件下Bi2MoO6没有负载到MoO3纳米纤维上(或负载量低于XRD检测限);样品BMM-PM的XRD图谱中同时检测α-MoO3和γ-Bi2MoO6特征峰,表明物理混合样品由Bi2MoO6与MoO3两相复合而成。

Fig.1 XRD Patterns for Different Samples

图2 不同样品的扫描电子显微镜（SEM）图像与透射电子显微镜（TEM）图像

Fig. 2 SEM and TEM Images of Different Samples

图3 样品BMM-3.0 (a, b, c, d), Bi2MoO6(b)和MoO3(c, d)的XPS谱图

Fig.3 X-ray photoelectron spectroscopy spectra of samples BMM-3.0 (a, b, c, d), Bi2MoO6(b) and MoO3(c, d)

图4 不同样品的光电性能

Fig.4 Optoelectronic properties of the different samples

图5 样品的光催化产氢性能，表观量子效率和循环性能曲线

Fig.5 Curves of the sample's photocatalytic hydrogen production performance, apparent quantum efficiency, and cyclic performance

Fig.6 Work function calculation of Bi2MoO6 and MoO36 样品Bi2MoO6和MoO3 的功函数

图7 Bi2MoO6与MoO3复合纤维光催化产氢机制示意图注:(a) 接触前 (b) 接触后 (c) 光照射下

Fig.7 Schematic Diagram of Photocatalytic Hydrogen Production Mechanism of Bi2MoO6/MoO3 Composite Fibers

参考文献 30

[1]	Liu H M, Peng J Y, Zhang X, et al. Engineering atomic Pt-N₃sites on CdS nanorods for overcoming the rate-determining organic dehydrogenation in photocatalytic coproduction of H₂ and value-added chemicals[J]. Chemical Engineering Journal, 2025, 504: 158618.
[2]	宋粉红, 王文光, 郭亮, 等. C元素修饰g-C₃N₄对TiO₂的调控及复合材料光催化产氢性能研究[J]. 化工学报, 2025, 76(6): 2983-2994.
	Song F H, Wang W G, Guo L, et al. Modulation of TiO₂by C-element modified g-C₃N₄and photocatalytic hydrogen production performance of composites[J]. CIESC Journal, 2025, 76(6): 2983-2994.
[3]	Yuan C Y, Yin H F, Li J, et al. Light-induced CoO_x surface reconstruction in hollow heterostructure for durable photocatalytic seawater splitting[J]. Nature Communications, 2025, 16: 6607.
[4]	Li H J, Zhou Z D, Cao X H, et al. Fabrication and performance of 3C–SiC photocathode materials for water splitting[J]. Progress in Natural Science: Materials International, 2024, 34(1): 12-25.
[5]	Yao S M, Wang D H, Li J H, et al.Gas sensing activity and mechanism of Aurivillius-type Bi₂MoO₆ nanosheets with different crystal facets[J]. Sensors and Actuators B: Chemical, 2024, 418: 136290.
[6]	Wang G A, Huo T T, Deng Q H, et al. Surface-layer bromine doping enhanced generation of surface oxygen vacancies in bismuth molybdate for efficient photocatalytic nitrogen fixation[J]. Applied Catalysis B: Environmental, 2022, 310: 121319.
[7]	Phuruangrat A, Buapoon S, Bunluesak T, et al. Degradation of rhodamine B photocatalyzed by hydrothermally prepared Pd-doped Bi₂MoO₆ nanoplates[J]. Journal of the Australian Ceramic Society, 2022, 58(1): 71-82.
[8]	Pinchujit S, Phuruangrat A, Wannapop S, et al. Sonochemical-assisted synthesis of Pt/Bi₂MoO₆ nanocomposites for efficient photodegradation of rhodamine B[J]. Optical Materials, 2023, 135: 113265.
[9]	李晓萍, 李跃军, 曹铁平, 等. 简易合成Bi/Bi₂MoO₆/TiO₂复合纳米纤维及其增强的可见光催化性能[J]. 无机材料学报, 2019, 34(11): 1193-1199.
	Li X P, Li Y J, Cao T P, et al. Facile synthesis of Bi/Bi₂MoO₆/TiO₂ composite nanofibers with enhanced photocatalytic activity under visible light[J]. Journal of Inorganic Materials, 2019, 34(11): 1193-1199.
[10]	Li Y J, Cao T P, Mei Z M, et al. Separating type I heterojunction of NaBi(MoO₄)₂/Bi₂MoO₆ by TiO₂ nanofibers for enhanced visible-photocatalysis[J]. Chemical Physics, 2020, 533: 110696.
[11]	李跃军, 曹铁平, 梅泽民, 等. Pr掺杂Bi₂MoO₆/TiO₂复合纳米纤维的制备及可见光催化性能[J]. 高等学校化学学报, 2017, 38(12): 2313-2319.
	Li Y J, Cao T P, Mei Z M, et al. Preparation and photocatalytic properties of Pr-doped Bi₂MoO₆/TiO₂composite nanofibers under visible light irradiation[J]. Chinese Journal of Chemistry, 2017, 38(12): 2313-2319.
[12]	Adhikari S, Lee H H, Kim D H. Efficient visible-light induced electron-transfer in z-scheme MoO₃/Ag/C₃N₄ for excellent photocatalytic removal of antibiotics of both ofloxacin and tetracycline[J]. Chemical Engineering Journal, 2020, 391: 123504.
[13]	Wei Y C, Zhang Q Q, Zhou Y, et al. Noble-metal-free plasmonic MoO_3-x-based S-scheme heterojunction for photocatalytic dehydrogenation of benzyl alcohol to storable H₂ fuel and benzaldehyde[J]. Chinese Journal of Catalysis, 2022, 43(10): 2665-2677.
[14]	Zou X W, Sun B, Wang L, et al. Enhanced photocatalytic degradation of tetracycline by SnS₂/Bi₂MoO_6-x heterojunction: Multi-electric field modulation through oxygen vacancies and Z-scheme charge transfer[J]. Chemical Engineering Journal, 2024, 482: 148818.
[15]	Sun Z L, Yang X L, Yu X F, et al. Surface oxygen vacancies of Pd/Bi₂MoO_6-x acts as "Electron Bridge" to promote photocatalytic selective oxidation of alcohol[J]. Applied Catalysis B: Environmental, 2021, 285: 119790.
[16]	霍彦廷,舒庆. 双Z型异质结BiOI/MoO₃/g-C₃N₄的构建及其光催化性能研究[J]. 有色金属科学与工程, 2023, 14(1): 74-85.
	Huo Y T, Shu Q. Construction of double Z-scheme heterojunction BiOI/MoO₃/g-C₃N₄ and its photocatalytic performance[J]. Nonferrous Metals Science and Engineering, 2023, 14(1): 74-85.
[17]	Zhang J L, Zhang L S, Yu N, et al. Flower-like Bi₂S₃/Bi₂MoO₆heterojunction superstructures with enhanced visible-light-driven photocatalytic activity[J]. RSC Advances, 2015, 5(92): 75081-75088.
[18]	李红英, 龚海明, 靳治良. In₂O₃修饰三维纳米花 MoS_x构建S型异质结用于高效光催化产氢[J]. 物理化学学报, 2022, 38(12): 232-241.
	Li H Y, Gong H M, Jin Z L. In₂O₃-Modified Three-dimensional nanoflower MoS_x form S-scheme heterojunction for efficient hydrogen production[J], Acta Physico-Chimica Sinica, 2022, 38(12): 232-241.
[19]	Panda S R, Singh R K, Priyadarshini B, et al. Nanoceria: a rare-earth nanoparticle as a promising anti-cancer therapeutic agent in colon cancer[J]. Materials Science in Semiconductor Processing, 2019, 104: 104669.
[20]	Chen Y R, Liu L, Zhang L, et al. Construction of Z-type heterojunction BiVO₄/Sm/α-Fe₂O₃ photoanode for selective degradation: efficient removal of bisphenol A based on multifunctional Sm-doped modification[J]. Applied Catalysis B: Environment and Energy, 2023, 333: 122775.
[21]	Takahashi H, Okazaki R, Terasaki I, et al. Origin of the energy gap in the narrow-gap semiconductor FeSb₂ revealed by high-pressure magnetotransport measurements[J]. Physical Review B, 2013, 88(16): 165205.
[22]	Gao Z, Shi L L, Yan F, et al. Two-dimensional supramolecular polymers based on selectively recognized aromatic cation-π and donor-acceptor motifs for photocatalytic hydrogen evolution[J]. Angewandte Chemie International Edition, 2023, 62(21): e202302274.
[23]	Qi J Q, Suo W Q, Liu J, et al. Direct observation of all open-shell Intermediates in a photocatalytic cycle[J]. Journal of the American Chemical Society, 2024, 146(11): 7140-7145.
[24]	Pan R L, Ge X, Liu Q, et al. Synergic delocalized-conjugate and electron-deficient effect and mesoporous channel promote photocatalytic coupling H₂ evolution with benzyl-alcohol oxidation[J]. Advanced Functional Materials, 2024, 34(17): 2315212.
[25]	Qiao X Q, Li C, Chen W X, et al. Optimization of Schottky barrier height and LSPR effect by dual defect induced work function changes for efficient solar-driven hydrogen production[J]. Chemical Engineering Journal, 2024, 490: 151822.
[26]	Zhang L Y, Zhang J J, Yu J G, et al. Charge-transfer dynamics in S-scheme photocatalyst[J]. Nature Reviews Chemistry, 2025, 9(5): 328-342.
[27]	Wu Y H, Yan Y Q, Deng Y X, et al. Rational construction of S-scheme CdS quantum dots/In₂O₃ hollow nanotubes heterojunction for enhanced photocatalytic H₂ evolution[J]. Chinese Journal of Catalysis, 2025, 70: 333-340.
[28]	Xu J, Zhang X Q, Chen X D, et al. Carbon doping regulates charge transfer paths via a type-II to S-scheme transformation to improve photocatalytic performance[J]. Inorganic Chemistry, 2024, 63(38): 17937-17945.
[29]	万俊, 宋佳芮, 范春煌, 等. 高效空穴转移助力光催化碱性甲醇-水溶液制氢[J]. 化工学报, 2025, 76(3): 1064-1075.
	Wan J, Song J R, Fan C H, et al. Highly efficient hole transfer for promoting photocatalytic hydrogen production from alkaline methanol aqueous solution[J]. CIESC Journal, 2025, 76(3): 1064-1075.
[30]	周云龙, 叶校源, 林东尧. 在紫外光下以玉米秸秆为牺牲剂提升光催化分解水制氢[J]. 化工学报, 2019, 70(7): 2717-2726.
	Zhou Y L, Ye X Y, Lin D Y. Photocatalytic hydrogen evolution by using corn stover as sacrificial agent under UV light irradiation[J]. CIESC Journal, 2019, 70(7): 2717-2726.

原位水热法可控合成Bi₂MoO₆/MoO₃复合纤维及其高效光催化产氢性能

Controlled Synthesis of Bi₂MoO₆/MoO₃ Composite Fibers via In-Situ Hydrothermal Method and Their High-Efficiency Photocatalytic Hydrogen Production Performance

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