乙酸调控MIL-53(Fe)的形貌演变及其高效选择性氧化H2S性能

doi:10.1016/S1872-2067(20)63625-7

催化学报 ›› 2021, Vol. 42 ›› Issue (2): 279-287.DOI: 10.1016/S1872-2067(20)63625-7

乙酸调控MIL-53(Fe)的形貌演变及其高效选择性氧化H₂S性能

郑笑笑, 齐思慧, 曹彦宁, 沈丽娟^*(), 区泽棠, 江莉龙^#()

福州大学化肥催化剂国家工程研究中心, 福建福州350002

收稿日期:2020-03-27 接受日期:2020-05-11 出版日期:2021-02-18 发布日期:2021-01-21
通讯作者: 沈丽娟,江莉龙
基金资助:
国家杰出青年科学基金(21825801);国家自然科学基金(21603034);福建省自然科学基金(2017J05022)

Morphology evolution of acetic acid-modulated MIL-53(Fe) for efficient selective oxidation of H₂S

Xiaoxiao Zheng, Sihui Qi, Yanning Cao, Lijuan Shen^*(), Chaktong Au, Lilong Jiang^#()

National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, Fujian, China

Received:2020-03-27 Accepted:2020-05-11 Online:2021-02-18 Published:2021-01-21
Contact: Lijuan Shen,Lilong Jiang
About author:^#Tel: +86-591-83731234; E-mail: jll@fzu.edu.cn
^*Tel: +86-591-83731234; E-mail: syhgslj@fzu.edu.cn;
Supported by:
National Science Fund for Distinguished Young Scholars of China(21825801);National Natural Science Foundation of China(21603034);Natural Science Foundation of Fujian Province(2017J05022)

摘要/Abstract

摘要：

硫化氢(H₂S)广泛存在于以煤、石油和天然气等为原料的化工生产过程中, 不仅腐蚀管道和设备, 而且还会对健康和环境造成危害. 因此, 高效脱除H₂S已成为工业废气减排的重点. 在各种方法中, H₂S选择性氧化技术(H₂S + (1/2)O₂ → (1/n)S_n + H₂O)由于具有设备需求低、反应不受热力学平衡限制、理论转化率可达100%等优点展现出了巨大的应用前景. 实现这一过程的关键在于发展高效稳定的催化剂. 作为一类新兴的多孔材料, 金属-有机骨架材料(MOFs)由于其独特的结构和性质吸引了广泛的研究兴趣. 与传统的脱硫材料相比, MOFs的优势主要体现在: 1) 高度分散的金属原子可作为催化活性中心; 2) 超高比表面积和规则的孔结构有利于反应物与活性位点之间的接触; 3) 结构可调变性高, 通过在合成过程中有目的地引入配体或调控剂可产生额外的活性位点, 满足特定催化的需求. 基于以上特点可知, MOFs是一类有潜力的催化剂, 但目前将其应用于H₂S选择性氧化领域的研究尚处于起步阶段.
本文以典型的铁基MOFs MIL-53(Fe)为研究对象, 在制备MIL-53(Fe)过程中添加乙酸(HAc)作为调控剂, 通过控制HAc的量, 得到一系列具有不同形貌的MIL-53(Fe)-xH样品, 并将其应用于H₂S选择性氧化反应. SEM结果表明, 在MIL-53(Fe)的合成过程中引入乙酸可以显著影响样品的形貌和尺寸. 活化前后样品的XRD结果表明, HAc具有与对苯二甲酸(H₂BDC)相似羧基基团, 二者均可与Fe-O团簇配位. 此外, TG-DSC结果证实, 随着HAc加入量的提高, 与Fe³⁺形成配位的HAc/H₂BDC比值随之增加. FT-IR和Raman结果进一步证明HAc成功地配位到MIL-53(Fe)的框架中, 并且参与配位的HAc可通过真空活化移除从而暴露出Fe³⁺不饱和位点. H₂S选择性氧化测试表明, MIL-53(Fe)-xH的脱硫活性随着HAc含量的提高先增加然后降低, 其中MIL-53(Fe)-5H活性最优. 此外, MIL-53(Fe)-5H催化剂在连续运行55 h后仍能保持100%H₂S转化率和86%硫选择性, 性能远优于传统的Fe₂O₃催化剂. 吡啶原位红外光谱结果表明, HAc的引入可以产生额外的Lewis酸性位点(LAS), LAS含量的不同是造成催化剂活性差异的主要原因.

关键词: 金属有机骨架材料, 硫化氢, 选择性氧化, 可控合成, 乙酸, 调控

Abstract:

MIL-53(Fe) was synthesized using a “modulator approach” that utilizes acetic acid (HAc) as an additive to control the size and morphology of the resulting crystals. We demonstrate that after activation under vaccum at 100 °C, the MIL-53(Fe) functions well for H₂S selective oxidation. The introduction of acetic acid in the presence of benzene-1,4-dicarboxylic acid (H₂BDC) would result in a series of MIL-53(Fe) nanocrystals (denoted as MIL-53(Fe)-xH, x stands for the volume of added HAc with morphology evoluting from irregular particles to short hexagonal columns. The vacuum treatment facilitates the removal of acetate groups, thus generating Fe ³⁺ Lewis acid sites. Consequently, the resulted MIL-53(Fe)-xH exhibits good catalytic activity (98% H₂S conversion and 92% sulfur selectivity ) at moderate reaction temperatures (100-190 °C). The MIL-53(Fe)-5H is superior to the traditional iron-based catalysts, showing stable performance in a test period of 55 h.

Key words: Fe-metal-organic frameworks, Hydrogen sulfide, Selective oxidation, Controllable synthesis, Acetic acid, Modulation

郑笑笑, 齐思慧, 曹彦宁, 沈丽娟, 区泽棠, 江莉龙. 乙酸调控MIL-53(Fe)的形貌演变及其高效选择性氧化H₂S性能[J]. 催化学报, 2021, 42(2): 279-287.

Xiaoxiao Zheng, Sihui Qi, Yanning Cao, Lijuan Shen, Chaktong Au, Lilong Jiang. Morphology evolution of acetic acid-modulated MIL-53(Fe) for efficient selective oxidation of H₂S[J]. Chinese Journal of Catalysis, 2021, 42(2): 279-287.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63625-7

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图/表 10

Fig. 1. (A) Schematic of MIL-53(Fe)-xH preparation (Gray, C; Blue, O; Aqua, Fe3+; Light Orange, Fe3+ Lewis acid sites; Purple dotted line, missing linker defects); SEM images of (B) MIL-53(Fe), (C) MIL-53(Fe)-3H, (D) MIL-53(Fe)-5H, and (E) MIL-53(Fe)-10H.

Fig. 2. XRD patterns of MIL-53(Fe) and MIL-53(Fe)-xH (before vacuum treatment at 100 °C).

Fig. 3. DSC (red) and TG (black) curves of prepared samples: (A) MIL-53(Fe), (B) MIL-53(Fe)-3H, (C) MIL-53(Fe)-5H, and (D) MIL-53(Fe)-10H.

Fig. 4. (A) FT-IR spectra and (B) Raman spectra of MIL-53(Fe)-xH.

Fig. 5. XPS spectra of MIL-53(Fe)-xH: (A) survey; (B) C 1s; (C) O 1s; and (D) Fe 2p.

Fig. 6. Effect of reaction temperature on (A) conversion of H2S, (B) sulfur selectivity, and (C) sulfur yield over MIL-53(Fe), MIL-53(Fe)-xH and commercial Fe2O3.

Fig. 7. Time-on-stream behavior of Fe2O3, MIL-53(Fe), and MIL-53(Fe)-5H for H2S selective oxidation at 190 °C.

Fig. 8. Py-FT-IR spectra of (A) MIL-53(Fe), (B) MIL-53(Fe)-3H, (C) MIL-53(Fe)-5H, and (D) MIL-53(Fe)-10H after degassing at 30, 100, and 150 °C.

Fig. 9. Pyridine sorption peak area (at 1070 cm-1) and H2S conversion over MIL-53(Fe)-xH.

Fig. 10. Diagram of the selective conversion of H2S to sulfur over MIL-53(Fe)-xH.

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乙酸调控MIL-53(Fe)的形貌演变及其高效选择性氧化H₂S性能

Morphology evolution of acetic acid-modulated MIL-53(Fe) for efficient selective oxidation of H₂S

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