催化甲醇选择性氧化制甲醛的铁钒催化剂活性位点的识别

doi:10.1016/S1872-2067(24)60279-2

催化学报 ›› 2025, Vol. 72: 334-343.DOI: 10.1016/S1872-2067(24)60279-2

催化甲醇选择性氧化制甲醛的铁钒催化剂活性位点的识别

詹钰捷^a^,^b, 钟承钦^c, 毕明莉^b, 梁亚飞^b, 祁玉基^b, 陈家琪^b^,^d, 刘家旭^c, 张新党^e, 张帅^e, 王业红^b^,^d^,^*(), 王峰^b^,^d

^a中国科学技术大学化学与材料科学学院, 安徽合肥 230026
^b中国科学院大连化学物理研究所, 辽宁大连 116023
^c大连理工大学化工学院, 智能材料化工前沿科学中心, 精细化工国家重点实验室, 辽宁大连 116024
^d中国科学院大学, 北京 100049
^e恒力石化(大连)新材料科技有限公司, 辽宁大连 116318

收稿日期:2024-12-12 接受日期:2025-02-10 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: wangyehong@dicp.ac.cn (王业红).
基金资助:
国家自然科学基金(U23A2088);国家自然科学基金(21991094);国家自然科学基金(22025206);国家自然科学基金(22472016);大连市高层次人才创新支持计划(2022RG13);大连化物所创新研究基金(DICP I202234);大连化物所创新研究基金(DICP I202453);中央高校基本科研业务费(20720220008);国家重点研发计划(2022YFA1504402)

Unveiling the catalytic active sites of iron-vanadium catalysts for the selective oxidation of methanol to formaldehyde

Yujie Zhan^a^,^b, Chengqin Zhong^c, Mingli Bi^b, Yafei Liang^b, Yuji Qi^b, Jiaqi Chen^b^,^d, Jiaxu Liu^c, Xindang Zhang^e, Shuai Zhang^e, Yehong Wang^b^,^d^,^*(), Feng Wang^b^,^d

^aSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, Anhui, China
^bDalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cState Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China
^eHengli Petrochemical (Dalian) New Materials Technology Co., Ltd., Dalian 116318, Liaoning, China

Received:2024-12-12 Accepted:2025-02-10 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: wangyehong@dicp.ac.cn (Y. Wang).
Supported by:
National Natural Science Foundation of China(U23A2088);National Natural Science Foundation of China(21991094);National Natural Science Foundation of China(22025206);National Natural Science Foundation of China(22472016);Dalian Innovation Support Plan for High Level Talents(2022RG13);DICP(DICP I202234);DICP(DICP I202453);Fundamental Research Funds for the Central Universities(20720220008);National Key Research and Development Program of China(2022YFA1504402)

摘要/Abstract

摘要：

甲醛是一种重要的化工中间体, 广泛应用于建筑材料、纺织工业、制药和农药等领域. 目前, 超90%的工业甲醛采用甲醇氧化路线获得. 铁钼法催化甲醇氧化体系因其生产的甲醛纯度高、反应条件温和等优势, 近年来成为工业甲醛生产的主要催化体系. 然而, 铁钼催化剂中活性钼物种容易在反应条件下与甲醇反应形成挥发性甲氧基钼物种而引起催化剂失活. 因此, 迫切需要开发兼具优异催化性能和稳定性的新型非铁钼催化剂. 钒基催化剂由于其独特的氧化还原性和抗流失性, 在氧化反应中表现出优异的催化活性和稳定性. 铁钒(FeV)作为钒基催化剂中的一类典型催化剂, 对甲醇选择性氧化制甲醛具有独特的催化活性. 但由于FeV结构的复杂性, 对于其催化活性位点的识别与催化作用机制目前仍存在争议. 活性本体FeVO₄相存在的同时往往伴随着多种表面钒物种的形成, 具体包括单位点VO_x、低聚态V_nO_x和结晶态V₂O₅等. 因此, 可控构筑表面钒物种并识别催化活性位点有利于指导设计具有优异催化活性的FeV催化剂.

本文采用共沉淀法制备了系列FeV催化剂, 通过控制制备条件(pH值和V/Fe摩尔比), 获得以下不同的FeV催化剂组成: (1) 纯相FeVO₄; (2) FeVO₄与Fe₂O₃的复合体系; (3) FeVO₄与单位点VO_x的复合体系; (4) FeVO₄与低聚态V_nO_x的复合体系; (5) FeVO₄与结晶态V₂O₅的复合体系, 并将其应用于甲醇氧化制甲醛反应. 结果表明, V过量的FeV催化剂(FeV_1.1)表现出优异的催化性能, 甲醇转化率为92.3%, 甲醛选择性为90.6%, 与铁钼催化剂相当. X射线衍射、Raman、X射线荧光和紫外-可见光光谱综合分析结果表明, 该高效FeV_1.1催化剂由低聚态V_nO_x与FeVO₄组成. CH₃OH-IR、O₂脉冲和控制实验结果表明, 低聚态V_nO_x与FeVO₄相之间存在协同作用, 增强其供氧能力, 同时具备对甲醛中间体适宜的吸附强度, 从而具有突出的催化活性和甲醛选择性. 与之相比较, 含单位点VO_x物种的FeV_1.05催化剂中, 由于其与甲醛中间体较强的绑定作用, 倾向于将醛基中间物种过氧化成CO_x. 而含结晶态V₂O₅的FeV_1.4催化剂, 其过量活性钒物种发生聚集, 暴露程度受限, 且有可能覆盖了表面部分FeVO₄物种, 降低了供氧能力, 进而降低了甲醇转化率.

综上, 本文通过精准控制系列FeV催化剂中活性钒物种的存在状态, 并关联其催化甲醇氧化制甲醛的反应性能, 揭示了FeVO₄与低聚态V_nO_x之间协同效应的催化本质. 本研究不仅为甲醇氧化制甲醛高性能催化剂的设计提供了思路, 还加深了对FeV催化剂复杂表面活性位点和催化机理的理解.

关键词: 铁钒催化剂, 选择性氧化, 甲醇, 甲醛, 协同效应

Abstract:

Iron-Vanadium (FeV) catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde; however, due to its complex compositions, the identification of catalytic active sites still remains challenging, inhibiting the rational design of excellent FeV-based catalysts. Here, in this work, a series of FeV catalysts with various compositions, including FeVO₄, isolated VO_x, low-polymerized V_nO_x, and crystalline V₂O₅ were prepared by controlling the preparation conditions, and were applied to methanol oxidation to formaldehyde reaction. A FeV_1.1 catalyst, which consisted of FeVO₄ and low-polymerized V_nO_x species showed an excellent catalytic performance with a methanol conversion of 92.3% and a formaldehyde selectivity of 90.6%, which was comparable to that of conventional iron-molybdate catalyst. The results of CH₃OH-IR, O₂ pulse and control experiments revealed a crucial synergistic effect between FeVO₄ and low-polymerized V_nO_x. It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates, contributing to the high catalytic activity and formaldehyde selectivity. This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.

Key words: Iron-vanadium, Selective oxidation, Methanol, Formaldehyde, Synergistic effect

詹钰捷, 钟承钦, 毕明莉, 梁亚飞, 祁玉基, 陈家琪, 刘家旭, 张新党, 张帅, 王业红, 王峰. 催化甲醇选择性氧化制甲醛的铁钒催化剂活性位点的识别[J]. 催化学报, 2025, 72: 334-343.

Yujie Zhan, Chengqin Zhong, Mingli Bi, Yafei Liang, Yuji Qi, Jiaqi Chen, Jiaxu Liu, Xindang Zhang, Shuai Zhang, Yehong Wang, Feng Wang. Unveiling the catalytic active sites of iron-vanadium catalysts for the selective oxidation of methanol to formaldehyde[J]. Chinese Journal of Catalysis, 2025, 72: 334-343.

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图/表 8

Fig. 1. V/Fe molar ratios and preparation yield (a), XRD patterns (b), Raman spectra (c), and UV-vis spectra (d) of FeV catalysts prepared at different pH values. a Obtained from XRF results.

Fig. 2. V/Fe molar ratios and preparation yield (a), XRD patterns (b), UV-vis spectra (c), Raman spectra (d), and enlarged Raman spectra (e) in the range of 980-1040 cm-1 of FeV catalysts prepared under different feed V/Fe molar ratios from 1.2 to 1.8. a Molar ratio of NH4VO3 to Fe(NO3)3·9H2O during catalyst preparation. b Obtained from XRF results.

Table 1 Typical catalysts composition and supposed structure.

Entry	Catalyst	Fe	V
1	FeV_0.5	Fe₂O₃	FeVO₄
2	FeV_1.0	—	FeVO₄
3	FeV_1.05	—	FeVO₄ + VO_x
4	FeV_1.1	—	FeVO₄ + V_nO_x
5	FeV_1.4	—	FeVO₄ + V₂O₅

Fig. 3. Catalytic performances of typical FeV catalysts: Methanol conversion and formaldehyde selectivity. Reaction conditions: catalyst (0.9 mL, 40-60 mesh), 230 °C, 0.1 MPa, CH3OH/O2/N2 as feedstock, GHSV = 9000 h-1.

Table 2 Catalytic performances of typical FeV catalysts in methanol oxidation at similar MeOH consumption rates.

Catalyst	T (°C)	Surface area ^a	MeOH rate ^b	Selectivity (%)
Catalyst	T (°C)	Surface area ^a	MeOH rate ^b	HCHO	HCOOH	CO_x	CH₂(OCH₃)₂	Others
FeV_1.05	220	17.10	1.06	90.52	3.38	1.19	1.28	3.63
FeV_1.1	210	11.11	1.05	93.31	1.39	0.39	2.76	2.15
FeV_1.4	230	12.86	1.04	94.61	1.04	0.49	1.21	2.24

Fig. 4. Catalytic performances of FeV1.1 catalyst at different reaction temperatures (a) and different GHSV (b). Reaction conditions: catalyst (0.9 mL, 40-60 mesh), 0.1 MPa, CH3OH/O2/N2 as feedstock.

Fig. 5. CH3OH-IR spectra of FeV1.1 (a), FeV1.4 (b), and FeV1.05 (c) catalysts, and normalized intensity of ν(C=O) (d). Normalization procedure: Subtract the peak value of ν(C=O) at each target temperature from the peak value at room temperature (where methanol does not dissociate to form an aldehyde group), and divide all differences by the maximum difference obtained.

Fig. 6. O2 pulse experiments on FeV1.1 (a), FeV1.4 (b), and FeV1.05 (c) catalysts at 230 °C. (d) H2-TPR profiles of three catalysts. All catalysts were pretreated with methanol before O2 pulse experiments.

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催化甲醇选择性氧化制甲醛的铁钒催化剂活性位点的识别

Unveiling the catalytic active sites of iron-vanadium catalysts for the selective oxidation of methanol to formaldehyde

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