一维S型异质结W18O49-SiC海胆状复合催化剂增强光催化CO2还原

doi:10.1016/S1872-2067(23)64477-8

催化学报 ›› 2023, Vol. 50: 239-248.DOI: 10.1016/S1872-2067(23)64477-8

一维S型异质结W₁₈O₄₉-SiC海胆状复合催化剂增强光催化CO₂还原

林敏^a, 罗美兰^a, 柳勇志^a, 沈锦妮^a, 龙金林^a, 张子重^a^,^b^,^*()

^a福州大学化学学院能源与环境光催化国家重点实验室, 福建福州 350108
^b清源创新实验室, 福建泉州 362801

收稿日期:2023-04-28 接受日期:2023-06-16 出版日期:2023-07-18 发布日期:2023-07-25
通讯作者: *电子信箱: z.zhang@fzu.edu.cn (张子重).
基金资助:
国家自然科学基金(21972020);清远创新实验室重大项目(00121001);福建省自然科学基金(2021H0002)

1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction

Min Lin^a, Meilan Luo^a, Yongzhi Liu^a, Jinni Shen^a, Jinlin Long^a, Zizhong Zhang^a^,^b^,^*()

^aState Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, Fujiang, China
^bQingyuan Innovation Laboratory, Quanzhou 362801, Fujiang, China

Received:2023-04-28 Accepted:2023-06-16 Online:2023-07-18 Published:2023-07-25
Contact: *E-mail: z.zhang@fzu.edu.cn (Z. Zhang).
Supported by:
National Natural Science Foundation of China(21972020);Major Program of Qingyuan Innovation Laboratory(00121001);Natural Science Foundation of Fujian Province of China(2021H0002)

摘要/Abstract

摘要：

光催化转化CO₂与H₂O反应生成燃料或化学品是一种可持续太阳能存储和CO₂利用的理想策略. 由于CO₂还原和H₂O氧化的高电位和多重电子传递要求, CO₂ + H₂O反应过程在动力学上是一个缓慢的过程, 并且光催化剂仍存在可见光响应范围窄、载流子分离效率低的问题. 因此, 开发可见光光催化剂实现有效的CO₂还原转化仍然极具挑战性. 构建异质结是提高光催化剂CO₂还原性能的重要途径. 单一光催化剂之间以颗粒-颗粒、层-层和核-壳等多种纳米结构进行复合, 这样形成的异质结通常以三维(3D)或二维(2D)的结构模型存在于两组分催化剂界面. 目前, 复合光催化剂的一维(1D)异质结的研究较少. 理论上, 光催化剂的一维(1D)异质结具有突出的优势, 反应物分子能够充分接触到一维(1D)异质结界面的所有原子以提供更多的反应和吸附活性位点, 还可以增强异质结效应对光生电子和空穴的高效率分离, 从而有效提高光催化性能.

本文采用简单的溶剂热法将W₁₈O₄₉纳米片原位生长在SiC纳米空心球笼上, 构建了具有海胆状形貌的S型异质结光催化剂. 扫描电镜证明成功合成了海胆状形貌的异质结. N₂吸附-脱附和接触角测试结果表明, W₁₈O₄₉纳米片在SiC纳米球笼表面的生长不仅可以增强复合催化剂材料的CO₂吸附性能, 还可以改变SiC纳米球笼表面的润湿性能, 提高其对反应物H₂O分子的亲和力. X射线光电子能谱、开尔文探针力显微镜和紫外-可见光谱等表征结果表明, SiC和W₁₈O₄₉之间存在着紧密接触的S型异质结界面, 内建电场有助于光生载流子的分离和迁移, 从而增强光催化CO₂还原性能. 该结构催化剂不仅为光催化剂与反应物分子的接触提供了更大的表面积, 而且缩短了电子和空穴的扩散路径. 这些优势加速了CO₂和H₂O分子在SiC-W₁₈O₄₉复合光催化剂表面的反应动力学过程. 复合光催化剂上快速的H₂O分子氧化形成更多的质子, 有利于质子参与CO₂还原过程. 与单一SiC光催化剂主要将CO₂还原为CO相比, SiC-W₁₈O₄₉复合材料不仅光催化活性大大提高, 而且产物选择性发生了从CO向多质子产物CH₄和CH₃OH转变的显著变化. SiC-W₁₈O₄₉复合材料的光催化CO₂还原生成CO + CH₄ + CH₃OH产物, 总产物生成速率可达21.87 μmol g^‒1 h^‒1. 综上, 复合光催化剂的异质结电子结构和维度结构对光催化CO₂还原性能具有重要影响, 这对设计高效CO₂还原的异质结光催化剂具有重要参考意义.

关键词: 一维异质结, S型, 海胆状结构, CO₂还原, SiC-W₁₈O₄₉

Abstract:

Constructing heterojunction is an important method to improve the performance of photocatalyst for CO₂ reduction. In this work, W₁₈O₄₉ nanosheets (NSs) were grown on the surface of SiC nanocages (NCs) to form the sea urchin ball morphology by solvothermal method. The SiC-W₁₈O₄₉ composite photocatalyst processes 1D S-scheme heterojunction electron transport pathway. The special urchin morphology provides a large surface area for the contact between photocatalyst and CO₂ reactants. Meantime, the S-scheme internal electric field at the heterogeneous interface of SiC-W₁₈O₄₉ composite photocatalyst can effectively promote the separation and migration of photogenerated carrier pairs owing to 1D heterojunction structure. The photocatalytic CO₂ reduction products (CO + CH₄ + CH₃OH) can be produced up to 21.87 μmol g^-1 h^-1 by SiC-W₁₈O₄₉ composite photocatalyst, which was 3.38 and 3.71 times of the total reduction activity of the parent SiC and W₁₈O₄₉, respectively. This work will provide a new idea for the design of heterojunction morphology and structure for boosting photocatalytic CO₂ reduction.

Key words: 1D heterojunction, S-scheme, Sea-urchin-structure, CO₂ reduction, SiC-W₁₈O₄₉

林敏, 罗美兰, 柳勇志, 沈锦妮, 龙金林, 张子重. 一维S型异质结W₁₈O₄₉-SiC海胆状复合催化剂增强光催化CO₂还原[J]. 催化学报, 2023, 50: 239-248.

Min Lin, Meilan Luo, Yongzhi Liu, Jinni Shen, Jinlin Long, Zizhong Zhang. 1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2023, 50: 239-248.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64477-8

https://www.cjcatal.com/CN/Y2023/V50/I7/239

图/表 11

Fig. 1. XRD patterns of W18O49, SiC and SiC-W18O49 composite samples.

Fig. 2. SEM and TEM images of SiC NCs (a,c) and SW-2 (b,d) samples. (e) HRTEM image of the SiC-W18O49 heterojunction.

Fig. 3. Nitrogen adsorption and desorption isotherms (a) and CO2 adsorption isotherms (b) of SiC NCs, SiC-W18O49 composites, and W18O49 NSs.

Fig. 4. (a) The photocatalytic product generation rate of SiC, W18O49, SiC-W18O49 composites. (b) Photocatalytic stability of the SiC-W18O49. (c) The formation rates of CO, CH4, and CH3OH in SW-2 samples under different reaction conditions. (d) Isotope labeling experiment (C13 isotope) test experiment.

Table 1 The results compared with other systems.

Photocatalyst	Major products (μmol g^‒1 h^‒1)	Ref.
SiC-W₁₈O₄₉ (SW-2)	(CO=11.96, CH₄=6.62, CH₃OH=3.29)	this work
SiC-W₁₈O₄₉ (SW-5)	(CO=3.53, CH₄=9.08, CH₃OH=3.21)	this work
SiC nanosheets	CO=6.29	[41]
NH₂-UiO-66/SiC	CO=7.30	[42]
VG@SiC/C	CO=25.48	[43]
α-Fe₂O₃/g-C₃N₄	CH₃OH= 5.63	[44]
BiVO₄/Bi₄Ti₃O₁₂	CH₃OH=16.6, CO=13.29	[45]
W₁₈O₄₉/Cu₂O	CH₄=17.20	[46]
g-C₃N₄/ZnO	CH₃OH=0.6	[47]
Bi₂MoO₆	CH₄=1.50	[48]
Ni₂O₃/SrTiO₃	CO=3.86, CH₄=0.50	[49]
SrTiO₃@NiFe LDH	CO= 7.9	[50]
ZnGa₂O₄ nanocubes	CH₄=1.28	[51]

Fig. 5. UV-vis DRS spectra (a) and Mott Schottky curve (b) of SiC. UV-vis DRS spectra (c) and Mott Schottky curve (d) of W18O49.

Fig. 6. W 4f (a) and Si 2p (b) XPS spectra of W18O49, SiC and SiC-W18O49 photocatalysts.

Fig. 7. (a) The measured CPD of W18O49 and SiC. (b) The band structure arrangement of SiC and W18O49. EPR signals of DMPO-O2?- of SiC, SW-2 (c) and DMPO-?OH of W18O49, SW-2 (d), under illumination for 5 min. (e) S-scheme charge transfer mechanism in SiC-W18O49 composite under visible light.

Fig. 8. Transient photocurrent response (a) and electrochemical impedance (b) of the SiC and SiC-W18O49. Steady-state PL spectra (c) and TRPL decay spectra (d) of the SiC, W18O49 and W18O49-SiC.

Fig. 9. In situ FTIR spectra of CO2 reduction with H2O vapor over SiC (a) and SiC-W18O49 (b) under the dark condition and light irradiation.

Fig. 10. Mechanism diagram of CO2 reduction by SiC-W18O49.

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一维S型异质结W₁₈O₄₉-SiC海胆状复合催化剂增强光催化CO₂还原

1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction

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