双反应位点共修饰WO3光催化活化甲烷

doi:10.1016/S1872-2067(22)64169-X

催化学报 ›› 2023, Vol. 46: 103-112.DOI: 10.1016/S1872-2067(22)64169-X

双反应位点共修饰WO₃光催化活化甲烷

王珂然^a, 罗磊^a^,^*(), 王超^b, 唐军旺^b^,^*()

^a西北大学, 化学与材料科学学院, 能源与催化中心, 合成天然功能分子化学教育部重点实验室, 陕西西安 710127, 中国
^b伦敦大学学院, 化学工程系, 伦敦, 英国

收稿日期:2022-09-22 接受日期:2022-10-15 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子信箱: junwang.tang@ucl.ac.uk (唐军旺),luol@dicp.ac.cn (罗磊)
基金资助:
陕西省重点研发计划(2020GY-244);中国博士后科学基金(2019M663802)

Photocatalytic methane activation by dual reaction sites co-modified WO₃

Keran Wang^a, Lei Luo^a^,^*(), Chao Wang^b, Junwang Tang^b^,^*()

^aKey Lab of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, the Energy and Catalysis Hub, College of Chemistry and Materials Science, Northwest University, Xi’an 710127, Shaanxi, China
^bDepartment of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, UK

Received:2022-09-22 Accepted:2022-10-15 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: junwang.tang@ucl.ac.uk (J. Tang), luol@dicp.ac.cn (L. Luo)
Supported by:
Shaanxi Key Research(2020GY-244);The China Postdoctoral Science Foundation(2019M663802)

摘要/Abstract

摘要：

在温和条件下将CH₄转化为液态含氧化合物, 对解决能源和环境问题, 实现可持续发展具有重要意义. 光催化CH₄转化技术可利用光能驱动载流子分离, 实现温和条件下CH₄直接转化. 然而, 该过程面临着活性低和选择性差的瓶颈问题. WO₃作为常见的光催化剂之一, 具有热稳定好、可见光响应性能好和价带空穴氧化能力强等特性, 但存在光生电荷容易复合的问题. 助催化剂能够发挥促进光生电荷分离和加速表面催化反应的双重作用, 有助于局域电子密度的重新分布, 从而促进光生电荷的分离和转移. 然而, 单一助催化剂促进光生电荷分离具有一定局限性, 为了进一步加强光生电荷的分离和转移, 引入氧空位(OVs)是个很好的选择, OVs不仅可通过插入杂质能级增强光吸收和促进电荷分离, 而且可以促进小分子吸附和活化, 进而加速表面反应动力学.

本文采用双活性位点Pd纳米颗粒和OVs改性的WO₃为催化剂, 实现温和条件下CH₄转化为液体含氧化合物. 参照文献(J. Am. Chem. Soc., 2017, 139, 4486‒4492)报道, 采用水热法合成了Pd纳米颗粒和OVs共改性的Pd_x-def-WO₃光催化剂. 电子顺磁共振波谱(EPR)、X射线光电子能谱(XPS)和透射电镜(TEM)等表征结果表明, OVs和Pd成功修饰在WO₃基底上. 光催化CH₄转化反应结果表明, 与WO₃相比, 优化的Pd_0.5-def-WO₃光催化剂使C1含氧化合物产量提高近33倍, 产率为7018 μmol·g^-1·h^-1, 对初级产物(CH₃OH和CH₃OOH)的选择性高达81%. 稳态荧光光谱和电化学测试实验表明Pd_0.5-def-WO₃催化剂的光生电荷的分离能力最强. 原位光照XPS谱表明Pd 3d结合能在光照下向高结合能方向移动, 证明了Pd纳米粒子是光生空穴受体. 原位光照EPR结果表明, 光照下OVs信号的增强, 证明了OVs作为光生电子受体. 因此, Pd和OVs协同促进光生电荷分离, 实现CH₄高活性和高选择性转化. 同位素实验表明, O₂是液态含氧化合物的主要氧源, H₂O的作用主要是通过产生羟基自由基(·OH)促进CH₄的活化. 因此, 在H₂O的辅助下, Pd纳米颗粒和OVs双反应位点共修饰的WO₃光催化剂实现了CH₄在室温下被O₂选择性氧化为液态含氧化合物. 综上, 本工作为CH₄选择性氧化反应的活性和选择性调控提供了深入的理解.

关键词: 光催化甲烷转化, 助催化剂, 氧化钨, 氧空位

Abstract:

Methane (CH₄) upgrading into liquid oxygenates under mild conditions is of great significance to sustainable energy and clean environment, whilst holds great challenges of achieving superior activity and selectivity. Herein, tungsten oxide (WO₃) modified with palladium (Pd) nanoparticles and oxygen vacancies (OVs) was employed as dual reaction sites to drive CH₄ conversion with O₂ at room temperature. Optimized Pd_0.5-def-WO₃ photocatalyst enables almost 33 times improvement in oxygenates production compared with WO₃, with a yield of 7018 μmol·g^-1·h^-1, and a high selectivity of 81% towards primary products (CH₃OH and CH₃OOH), which is superior to most of the previous reported. In-situ XPS spectra proved Pd nanoparticles were the hole acceptors based on the shift of Pd₃_d to high binding energy under light irradiation. The in-situ solid-state EPR spectra demonstrate an enhancement of OVs signal which proves the role of OVs as the electron acceptors. Consequently, efficient charge separation has been achieved, contributing to the superior activity and selectivity for CH₄ conversion.

Key words: Photocatalytic methane conversion, ocatalyst, Tungsten oxide, Oxygen vacancies

王珂然, 罗磊, 王超, 唐军旺. 双反应位点共修饰WO₃光催化活化甲烷[J]. 催化学报, 2023, 46: 103-112.

Keran Wang, Lei Luo, Chao Wang, Junwang Tang. Photocatalytic methane activation by dual reaction sites co-modified WO₃[J]. Chinese Journal of Catalysis, 2023, 46: 103-112.

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图/表 7

Fig. 1. XRD patterns (a) and EPR spectra (b) of WO3, def-WO3, Pd0.5-def-WO3 and Pd0.5-WO3. High-resolution W 4f (c) and O 1s (d) XPS spectra of WO3 and Pd0.5-def-WO3.

Fig. 2. HRTEM images (a,b), and EDS-mapping images (c-e) of Pd0.5-def-WO3. Tungsten (c), palladium (d), and oxygen (e) elements were represented by red, green and blue colors, respectively. HAADF-STEM image (f) and O-K EELS at different positions (g) on amorphous layer of Pd0.5-def-WO3. Positions 1, 2 and 3 were three different positions on amorphous layer in (f).

Fig. 3. (a) Photocatalytic CH4 conversion over WO3, def-WO3, Pdx-def-WO3 and Pd0.5-WO3 photocatalysts. Reaction conditions: 20 mg catalyst, 100 mL H2O, 1.9 MPa CH4, 0.1 MPa O2, 2 h, 25 °C, 100 mW·cm-2. Investigation on effects of molar ratio of CH4 to O2 (b) and H2O amount (c).

Fig. 4. (a) UV-DRS spectra of different photocatalysts. (b) In-situ Pd 3d XPS spectra of Pd0.5-def-WO3 in dark and under light irradiation. (c) In-situ solid-state EPR spectra of def-WO3 in dark and under light irradiation; Steady-state PL spectra (d), transient photocurrent responses (e) and EIS plots (f) of different photocatalysts.

Fig. 5. (a) In-situ EPR spectra to monitor of DMPO-OOH over Pd0.5-def-WO3 in CH3OH solution. (b) First-order kinetic constant of NBT photodegradation reaction for detection of ·OOH radicals formation. (c) In-situ EPR spectra to monitor of DMPO-OH over Pd0.5-def-WO3 in water. (d) PL spectra of the as-generated 7-HC over different photocatalysts.

Fig. 6. GC-MS spectra of the generated CH3OH over Pd0.5-def-WO3 with 18O2 + H216O or 16O2 + H218O in photocatalytic CH4 oxidation.

Scheme 1. Proposed reaction process of photocatalytic CH4 oxidation over Pd0.5-def-WO3 with O2 as the oxidant.

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双反应位点共修饰WO₃光催化活化甲烷

Photocatalytic methane activation by dual reaction sites co-modified WO₃

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