La2FeMO6双钙钛矿中的不对称氧空位用于促进氧活化和H2S选择性氧化

doi:10.1016/S1872-2067(24)60051-3

催化学报 ›› 2024, Vol. 62: 198-208.DOI: 10.1016/S1872-2067(24)60051-3

La₂FeMO₆双钙钛矿中的不对称氧空位用于促进氧活化和H₂S选择性氧化

魏征, 蒋国霞, 王怡雯, 黎刚刚, 张中申, 程杰, 张凤莲^*(), 郝郑平^*()

中国科学院大学挥发性有机物污染控制材料与技术国家工程实验室, 环境材料与污染控制技术研究中心, 北京 101408

收稿日期:2024-02-28 接受日期:2024-05-08 出版日期:2024-07-18 发布日期:2024-07-10
通讯作者: *电子邮箱: zphao@ucas.ac.cn (郝郑平), zhangfenglian@ucas.ac.cn (张凤莲).
基金资助:
国家自然科学基金(22006148);国家自然科学基金(21976176);国家自然科学基金(22376196);中央高校基本科研业务费专项资金

Asymmetric oxygen vacancies in La₂FeMO₆ double perovskite for boosting oxygen activation and H₂S selective oxidation

Zheng Wei, Guoxia Jiang, Yiwen Wang, Ganggang Li, Zhongshen Zhang, Jie Cheng, Fenglian Zhang^*(), Zhengping Hao^*()

National Engineering Laboratory for VOCs Pollution Control Material & Technology, Research Center for Environmental Material and Pollution Control Technology, University of Chinese Academy of Sciences, Beijing 101408, China

Received:2024-02-28 Accepted:2024-05-08 Online:2024-07-18 Published:2024-07-10
Contact: *E-mail: zphao@ucas.ac.cn (Z. Hao), zhangfenglian@ucas.ac.cn (F. Zhang).
Supported by:
National Natural Science Foundation of China(22006148);National Natural Science Foundation of China(21976176);National Natural Science Foundation of China(22376196);Fundamental Research Funds for Central Universities

摘要/Abstract

摘要：

金属氧化物催化剂表面O₂分子的活化对于多相催化中氧化还原反应具有重要意义. 硫化氢(H₂S)选择性氧化是一个典型的氧化反应, 通常用于去除克劳斯工艺尾气中有害的H₂S, 同时回收化工产品硫磺. 受克劳斯反应的热力学限制, 工艺尾气中仍有近1%的H₂S残留, 在焚烧炉中会转化为有害的SO_x, 造成不必要的硫损失以及严重的环境问题. 研究表明, 氧分子活化解离产生的活性氧物种是H₂S选择氧化的关键活性物种. 然而, 受限于氧分子的低效活化, 传统催化剂需提高反应温度以获得令人满意的H₂S转化率, 这也促进了副反应的进行并生成有害副产物SO₂. 因此, 迫切需要在较低温度下实现氧分子的高效活化以促进H₂S选择氧化反应的进行, 从而最大限度地提高克劳斯工艺硫回收效率并降低运营成本. 目前, 大多数研究通过引入更多的氧空位促进氧分子的活化及氧化反应的进行, 但很少有人考虑氧空位本身结构的影响. 近年来, 研究者更多地关注不对称氧/空位(M₁-O-M₂或M₁-V_O-M₂), 该特殊结构可以有效地优化氧分子的活化, 提高催化性能.

本文报道了一种简单的氧空位调控策略用于H₂S选择氧化, 通过过渡金属(M = Mn, Co和Mo)取代策略在LaFeO₃钙钛矿催化剂中引入不对称氧空位, 从而激发氧分子活化以促进H₂S选择氧化的进行. X射线粉末衍射、Raman光谱及透射电镜结果表明, Mn和Co的引入形成了均匀的La₂FeMnO₆以及La₂FeCoO₆双钙钛矿相, 而Mo的引入则形成了La₂Mo₂O₉和LaFeO₃钙钛矿的混相. X射线光电子能谱及Mössbauer谱结果表明, Mn取代形成的La₂FeMnO₆双钙钛矿催化剂由于其结构中Mn与Fe的完全交替取代形成了丰富的不对称Fe-V_O-Mn位点, 结合H₂程序升温还原及O₂程序升温解吸结果, 可以推断不对称空位促进了催化剂上氧分子的活化, 进而提高了催化剂的氧迁移率和还原性. 模拟计算了氧分子在LaFeO₃及La₂FeMnO₆催化剂上的吸附及解离过程, 结果表明, 氧分子在对称的Fe-V_O-Fe位点上具有较高的吸附能及解离能, 在不对称的Fe-V_O-Mn位点上不存在稳定的吸附态, 倾向于直接解离形成活性氧物种. 具有丰富不对称Fe-V_O-Mn位点的La₂FeMnO₆催化剂的H₂S选择氧化低温活性和稳定性显著提高, 在较宽的温度窗口内均可保持较好的H₂S转化率(>90%)与硫选择性(接近100%).

综上, 本文通过取代策略实现了对催化剂氧空位结构的调控, 揭示了不对称氧空位对氧分子活化行为的促进机制. 研究结果不仅为合理设计高效氧化催化剂探明了一条可行的途径, 还对氧分子活化过程中氧空位结构的促进机制提供了深入的见解, 有望激发更多关于开发氧化还原反应高效催化材料的研究.

关键词: 双钙钛矿, 不对称氧空位, 氧分子活化, 硫化氢选择性氧化, 硫磺回收

Abstract:

Tuning oxygen vacancy (V_O) in metal oxides catalysts that efficiently activates O₂ molecule to promote oxidation reactions remains challenging. Herein, transition metal (M = Mn, Co, and Mo) doping was used to moderate the coordination environment of V_O in La₂FeMO₆ and promote activity for selective oxidation of hydrogen sulfide (H₂S). Various techniques reveal that the introduction of Mn and Co forms the homogeneous double perovskite phase, which results in the formation of asymmetric V_O. Although these asymmetric V_O are more difficult to form than symmetric Fe-V_O-Fe due to the shorter bond distance and stronger bond strength of Fe-O, they are more conducive to the dissociation of O₂ molecules. Among them, the formed rich Fe-V_O-Mn sites from the alternate substitution of Mn to Fe boosted the activation of O₂ molecules of Mn-substituted LaFeO₃. Therefore, enhanced catalytic activity and outstanding sulfur selectivity were achieved as a result of promoted oxygen mobility and reducibility. This work provides an attractive strategy for rational design of advanced oxidation catalysts.

Key words: Double perovskite, Asymmetric oxygen vacancy, O₂ activation, H₂S selective oxidation, Sulfur recovery

魏征, 蒋国霞, 王怡雯, 黎刚刚, 张中申, 程杰, 张凤莲, 郝郑平. La₂FeMO₆双钙钛矿中的不对称氧空位用于促进氧活化和H₂S选择性氧化[J]. 催化学报, 2024, 62: 198-208.

Zheng Wei, Guoxia Jiang, Yiwen Wang, Ganggang Li, Zhongshen Zhang, Jie Cheng, Fenglian Zhang, Zhengping Hao. Asymmetric oxygen vacancies in La₂FeMO₆ double perovskite for boosting oxygen activation and H₂S selective oxidation[J]. Chinese Journal of Catalysis, 2024, 62: 198-208.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60051-3

https://www.cjcatal.com/CN/Y2024/V62/I7/198

图/表 10

Fig. 1. XRD patterns (a) and Raman spectra (b) of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 2. HR-TEM and the corresponding IFFT images of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 3. La 3d (a), Fe 2p (b) and O 1s (c) XPS spectra of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 4. Fe K edge XANES spectra (a) and Fourier transformed (FT) k3-weighted EXAFS spectra (b) of LaFe, LaFeMn and LaFeCo.

Fig. 5. 57Fe M?ssbauer spectra fitting results of LaFe (a), LaFeMn (b), LaFeCo (c) and LaFeMo (d). The solid lines show the curve fits to the raw data.

Table 1 57Fe M?ssbauer spectra results of LaFe, LaFeMn, LaFeCo and LaFeMo.

Catalyst	IS (mm s^‒1)^a	QS (mm s^‒1)^b	H_in (kOe) ^c	P (%) ^d	Fe state
LaFe	(a) 0.18	0.99	—	4.5	small particle
LaFe	(b) 0.37	‒0.03	514.5	95.5	Fe³⁺ (Oh, Fe-O-Fe)
LaFeMn	(a) 0.35	0.52	—	100	Fe³⁺ (Oh, Fe-O-Mn) and small particle
LaFeCo	(a) 0.33	0.44	—	49.4	Fe³⁺ (Oh, Fe-O-Co) and small particle
	(b) 0.36	‒0.03	490.8	19.4	Fe³⁺ (Oh, Fe-O-Fe)
	(c) 0.77	‒0.88	249.6	31.2	Fe³⁺ (Oh, Fe-Co random)
LaFeMo	(a) 0.29	1.01	—	11.0	small particle
LaFeMo	(b) 0.37	‒0.03	502.1	89.0	Fe³⁺ (Oh, Fe-O-Fe)

Fig. 6. (a) O2 desorption profiles in O2-TPD. H2 consumption (b) and O2 desorption profiles (c) in H2-TPR of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 7. Adsorption (a) and dissociation state (b) of O2 molecule on constructed LaFeO3 (110) slabs with VO. (c) Dissociation state of O2 molecule on constructed La2FeMnO6 (110) slabs with VO.

Fig. 8. H2S conversion (a), sulfur selectivity (b) and sulfur yield (c) for H2S oxidation of LaFe, LaFeMn, LaFeCo and LaFeMo.

Fig. 9. Effects of GHSV (a), H2S/O2 (b) molar ratio and H2O content (c) on the catalytic performance of LaFeMn.

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La₂FeMO₆双钙钛矿中的不对称氧空位用于促进氧活化和H₂S选择性氧化

Asymmetric oxygen vacancies in La₂FeMO₆ double perovskite for boosting oxygen activation and H₂S selective oxidation

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