氧空位修饰的暴露TiO2{001}的Ru/TiO2增强光热协同CO2甲烷化活性和稳定性

doi:10.1016/S1872-2067(21)63825-1

催化学报 ›› 2022, Vol. 43 ›› Issue (2): 391-402.DOI: 10.1016/S1872-2067(21)63825-1

氧空位修饰的暴露TiO₂{001}的Ru/TiO₂增强光热协同CO₂甲烷化活性和稳定性

王可^a, 何仕辉^a^,^b, 林云志^a, 陈旬^a, 戴文新^a^,^b^,^*(), 付贤智^a^,^#()

^a福州大学光催化研究所, 能源与环境光催化国家重点实验室, 福建福州 350108
^b福州大学生态环境材料先进技术重点实验室, 福建福州 350108

收稿日期:2021-02-22 接受日期:2021-02-22 出版日期:2022-02-18 发布日期:2021-05-19
通讯作者: 戴文新,付贤智
基金资助:
国家重点研发计划(2018YFE0208500);国家自然科学基金(21872030)

Photo-enhanced thermal catalytic CO₂ methanation activity and stability over oxygen-deficient Ru/TiO₂ with exposed TiO₂ {001} facets: Adjusting photogenerated electron behaviors by metal-support interactions

Ke Wang^a, Shihui He^a^,^b, Yunzhi Lin^a, Xun Chen^a, Wenxin Dai^a^,^b^,^*(), Xianzhi Fu^a^,^#()

^aResearch Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350108, Fujian, China
^bKey Laboratory of Eco-Materials Advanced Technology, Fuzhou University, Fuzhou 350108, Fujian, China

Received:2021-02-22 Accepted:2021-02-22 Online:2022-02-18 Published:2021-05-19
Contact: Wenxin Dai, Xianzhi Fu
Supported by:
This work was supported by the National Key R&D Program of China(2018YFE0208500);the National Natural Science Foundation of China(21872030)

摘要/Abstract

摘要：

利用太阳能在温和条件下实现CO₂还原反应, 不仅可以缓解过度消耗化石能源造成的能源危机, 还可以改善诸如温室效应和海洋酸化等环境问题. 光热协同催化可以有效降低催化反应温度, 具有较大的应用前景.
本文利用Ru与暴露TiO₂{001}晶面的TiO₂载体产生的金属-载体相互作用, 经过高温氢气煅烧后, 获得具有丰富表面氧空位的Ru/TiO₂催化剂. 活性测试结果表明, 具有丰富表面氧空位的Ru/TiO₂表现出优异的CO₂甲烷化活性, 反应过程中甲烷的TOF值在300 °C时可以达到22 h ^-1, 但该催化剂却表现出较差的稳定性, 在反应10小时后, 甲烷的TOF值逐渐降低到19 h ^-1. 将紫外光引入到Ru/TiO₂热催化甲烷化体系中, 甲烷的TOF值增加到30 h ^-1, 且兼具高稳定性. 热催化反应过程中逐渐消失的表面氧空位和部分氧化的Ru是活性降低的主要原因. 在光热协同反应中, 光生电子的产生稳定了Ru表面的电子密度, 同时也再生了催化剂上表面氧空位, 这有效地提高了反应的活性和稳定性.
程序升温原位红外和X射线光电子能谱实验结果表明, 当催化剂表面具有丰富的表面氧空位时, CO₂可以有效地在Ru纳米粒子上解离成CO中间体, 随后吸附在Ru上的CO中间体解离成表面碳物种, 并加氢产生甲烷. 在热催化反应过程中, Ru纳米粒子逐渐被氧化成RuO_x物种, 且表面氧空位被CO中间物种覆盖, 降低了催化反应的稳定性. 当紫外光引入到上述反应中, 催化剂的表面氧空位可有效提高光生载流子的分离能力. TiO₂载体产生的光电子转移至Ru表面, 稳定了金属Ru纳米粒子的价态. 另外, 载体产生的光生空穴加速了H₂质子化, 提高了催化剂对氢气的活化迁移能力, 促进了CO中间体的加氢甲烷化反应, 进而再生表面氧空位. 因此在紫外光照下, 兼顾提高了热催化CO₂甲烷化的活性和稳定性. 值得注意的是, 当Ru负载于暴露少量TiO₂{001}晶面的TiO₂载体上时, 产生了强金属-载体相互作用并抑制了H₂在催化剂上的吸附活化, 不利于产生表面氧空位. 因此暴露少量TiO₂{001}晶面的Ru/TiO₂催化剂也不利于光生载流的产生和分离, 这导致热催化或光热协同催化反应活性较低.

关键词: 光热协同催化CO₂还原, 氧空位, Ru/TiO₂, 金属-载体相互作用

Abstract:

In this study, two Ru/TiO₂ samples with different TiO₂ facets were prepared to investigate their photo-thermal catalytic CO₂ + H₂ reaction behavior. Without UV irradiation, the Ru/TiO₂ with 67% {001} facet (3RT) displayed improved thermal catalytic activity for CO₂ methanation than that of Ru/TiO₂ with 30% {001} facet (0RT). After H₂ pretreatment, both samples exhibited enhanced thermal catalytic activities, but the H₂-treated 3RT (3RT-H) exhibited superior activity to that of the H₂-treated 0RT (0RT-H). Under UV irradiation, 3RT-H exhibited apparent photo-promoted thermal catalytic activity and stability, but the enhanced catalytic activity was lower than that of 0RT-H. Based on the characterization results, it is proposed that both the surface oxygen vacancies (Vos) (activating CO₂) and the metallic Ru nanoparticles (activating H₂) were mainly responsible for CO₂ methanation. For 0RT, H₂ pretreatment and subsequent UV irradiation did not promote the formation of Vos, resulting in low catalytic activity. For 3RT, on the one hand, H₂ pretreatment promoted the formation of Vos, which were regenerated under UV irradiation; on the other hand, the photogenerated electrons from TiO₂ transferred to Ru to maintain the metallic Ru nanoparticles. Both behaviors promoted the activation of CO₂ and H₂ and enhanced CO₂ methanation. Moreover, the photogenerated holes favored the dissociated H at Ru migrating to TiO₂, also promoting CO₂ methanation. These behaviors occurring on 3RT-H may be attributed to the suitable metal-support interaction between the Ru nanoparticles and TiO₂ {001}, resulting in the easy activation of lattice oxygen in TiO₂to Vos. With reference to the analysis of intermediates, a photo-thermal reaction mechanism is proposed for the Ru/TiO₂ {001} facet sample.

Key words: Photo-thermal CO₂ reduction, Oxygen vacancy, Ru/TiO₂, Metal-support interaction

王可, 何仕辉, 林云志, 陈旬, 戴文新, 付贤智. 氧空位修饰的暴露TiO₂{001}的Ru/TiO₂增强光热协同CO₂甲烷化活性和稳定性[J]. 催化学报, 2022, 43(2): 391-402.

Ke Wang, Shihui He, Yunzhi Lin, Xun Chen, Wenxin Dai, Xianzhi Fu. Photo-enhanced thermal catalytic CO₂ methanation activity and stability over oxygen-deficient Ru/TiO₂ with exposed TiO₂ {001} facets: Adjusting photogenerated electron behaviors by metal-support interactions[J]. Chinese Journal of Catalysis, 2022, 43(2): 391-402.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63825-1

https://www.cjcatal.com/CN/Y2022/V43/I2/391

图/表 9

Fig. 1. XRD patterns (a) and UV-vis DRS spectra (b) of 0T, 3T, 0RT, and 3RT; SEM images of 0RT (c) and 3RT (d), and TEM images of 0RT (e) and 3RT (f).

Fig. 2. TPR profiles (a), XPS spectra (b) of the Ru species; EPR (c) and XPS (d) spectra of the O species within the various samples.

Fig. 3. CO2 methanation using 0RT (a), 3RT (b), 0RT-H (c), and 3RT-H (d); (e) Stability of 3RT-H at 300 °C under UV irradiation or in darkness; (f) Action spectrum of 3RT-H at 300 °C.

Fig. 4. XPS spectra, after various treatments, of Ru and C species on 0RT-H (a) and 3RT-H (b). (1) After H2 treatment; (2) After CO2 methanation without UV irradiation, (3) After CO2 methanation under UV irradiation. The quasi-situ electron paramagnetic resonance spectra, after various treatments, of 0RT-H (c) and 3RT-H (d).

Fig. 5. In situ DRIFS spectra of CO2 activation at various temperatures on 0RT-H (a) and 3RT-H (c) in darkness, and 0RT-H (b) and 3RT-H (d) under UV irradiation.

Fig. 6. In situ DRIFS spectra of CO2 + H2 methanation at various temperatures on 0RT-H (a) and 3RT-H (c) in darkness, and 0RT-H (b) and 3RT-H (d) under UV irradiation.

Fig. 7. H2-pulse studies of 0RT-H (a) and 3RT-H (c) in darkness, and 0RT-H (b) and 3RT-H (d) under UV irradiation.

Fig. 8. (a) Photocurrent (inset: electrochemical impedance spectra), (b) PL spectra, and (c) Fluorescence emission decay spectra of various samples; (d) Charge carrier transfer mechanism on 3RT-H.

Fig. 9. Possible mechanisms of CO2 methanation over 3RT-H with or without ultraviolet (UV) irradiation. Upper: the thermal CO2 methanation, bottom: the photo-thermal CO2 methanation.

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氧空位修饰的暴露TiO₂{001}的Ru/TiO₂增强光热协同CO₂甲烷化活性和稳定性

Photo-enhanced thermal catalytic CO₂ methanation activity and stability over oxygen-deficient Ru/TiO₂ with exposed TiO₂ {001} facets: Adjusting photogenerated electron behaviors by metal-support interactions

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