Catalytic CO oxidation activity and sulfur resistance of Pt-based catalyst modified by WO3 with phosphotungstic acid assist

doi:10.16085/j.issn.1000-6613.2024-1676

Abstract

Abstract:

Impurities such as SO₂ and H₂O in industrial waste gas often lead to the performance decline of CO catalyst. Although traditional doping techniques improve the sulfur resistance, they tend to reduce the catalytic oxidation activity. In this study, the TiO₂ support was modified by phosphotungstic acid (PWA), and Pt-WO₃ was formed by the high-temperature decomposition of PWA and anchored to TiO₂ to prepare the Pt-P&W/TiO₂ series of catalysts. Performance tests showed that Pt-0.125P&W/TiO₂ exhibited the best CO catalytic oxidation activity and good sulfur resistance stability. However, Pt-0.5P&W/TiO₂ with a higher PWA content has the best sulfur resistance but decreased catalytic oxidation activity. Transmission electron microscopy showed that in Pt-0.125P&W/TiO₂, Pt and TiO₂/WO₃ formed a double-interface interaction, while excessive WO₃ in Pt-0.5P&W/TiO₂ hindered the interaction between Pt and TiO₂. This led to the content of reactive oxygen species (23.8%) significantly lower than that of Pt-0.5P&W/TiO₂ (28.35%), which was the main reason for the decline in the catalytic CO oxidation activity. The NH₃-TPD test revealed that the enhancement of catalyst acidity due to dopants as the key to the improvement of sulfur resistance. Theoretical calculations further verified that the dual interface sites reduced the adsorption energy of CO and SO₂ (from -2.56eV and -1.31eV to -1.96eV and -1.01eV, respectively), promoting the catalytic CO oxidation activity and sulfur resistance.

Key words: dopants, CO catalysis, sulfur resistance, theoretical calculation

摘要：

工业废气中SO₂、H₂O等杂质常导致CO催化剂性能下降，传统掺杂技术虽提升抗硫性能，但容易降低催化氧化活性。本研究通过磷钨酸（PWA）改性TiO₂载体，利用PWA高温分解形成Pt-WO₃锚定于TiO₂，制备Pt-P&W/TiO₂系列催化剂。性能测试表明，Pt-0.125P&W/TiO₂展现最佳CO催化氧化活性与较好抗硫稳定性，而PWA含量更多的Pt-0.5P&W/TiO₂抗硫性最强但催化氧化活性下降。透射电镜显示，Pt-0.125P&W/TiO₂中Pt与TiO₂/WO₃形成双界面相互作用，而Pt-0.5P&W/TiO₂中过多的WO₃阻碍了Pt和TiO₂的相互作用，导致了活性氧含量（23.8%）显著低于Pt-0.5P&W/TiO₂（28.35%），这是CO催化氧化活性下降的主要原因。NH₃-TPD测试揭示掺杂剂增强催化剂酸性是抗硫性提升的关键。理论计算进一步验证，双界面位点降低了CO和SO₂吸附能（分别从-2.56eV和-1.31eV降至-1.96eV和-1.01eV），促进CO催化氧化活性与抗硫性。

关键词: 掺杂剂, CO催化, 抗硫, 理论计算

CLC Number:

X511

CUI Bing, CHEN Qingrong, WANG Zhongquan, HE Junda, WANG Weineng. Catalytic CO oxidation activity and sulfur resistance of Pt-based catalyst modified by WO₃ with phosphotungstic acid assist[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6376-6386.

崔兵, 陈庆荣, 王忠泉, 何俊达, 王伟能. 磷钨酸辅助构建WO₃修饰的Pt基催化剂CO催化氧化活性和抗硫性能[J]. 化工进展, 2025, 44(11): 6376-6386.

Figures/Tables 15

References 35

[1]	NI Lijun, ZHOU Yuwei, TAN Wei, et al. Asymmetric coordinative modulation boosting the activity and thermal stability of Pt₁/CeO₂ for CO oxidation under harsh condition[J]. Chemical Engineering Journal, 2024, 501: 157250.
[2]	GAO Fengyu, TANG Xiaolong, YI Honglong, et al. Promotional mechanisms of activity and SO₂ tolerance of Co-or Ni-doped MnO _x -CeO₂ catalysts for SCR of NO _x with NH₃ at low temperature[J]. Chemical Engineering Journal, 2017, 317: 20-31.
[3]	YANG Weiwei, GONG Jian, WANG Xiang, et al. A review on the impact of SO₂ on the oxidation of NO, hydrocarbons, and CO in diesel emission control catalysis[J]. ACS Catalysis, 2021, 11(20): 12446-12468.
[4]	LEE Minwoo, LEE Eunjun, LEE Kwanyoung. Comparative analysis of NO _x reduction on Pt, Pd, and Rh catalysts by DFT calculation and microkinetic modeling[J]. Applied Surface Science: A Journal Devoted to the Properties of Interfaces in Relation to the Synthesis and Behaviour of Materials, 2023, 611: 155572.
[5]	LI Yuan, SHEN Meiqing, WANG Jianqiang, et al. Influence of sulfation and regeneration on Pt/Al₂O₃for NO oxidation[J]. Catalysis Science & Technology, 2015, 5: 1731-1740.
[6]	YAN Daiwei, LI Qinru, CHEN Hangrong. A highly dispersed mesoporous zeolite@TiO₂-supported Pt for enhanced sulfur-resistance catalytic CO oxidation[J]. Catalysis Communications, 2020, 142: 106042.
[7]	XU Tieyao, LIU Xiaolong, ZHU Tingyu, et al. New insights into the influence mechanism of H₂O and SO₂ on Pt-W/Ti catalysts for CO oxidation[J]. Catalysis Science & Technology, 2022, 12: 1574-1585.
[8]	ZHANG Tong, QIU Wenge, ZHU Hongtai, et al. Promotion effect of the Keggin structure on the sulfur and water resistance of Pt/CeTi catalysts for CO oxidation[J]. Catalysts, 2022, 12: 4.
[9]	PAN Chunjern, TASA Mengche, SU Weinien, et al. Tuning/exploiting strong metal-support interaction (SMSI) in heterogeneous Catalysis[J]. journal of the Taiwan Institute of Chemical Engineers, 2017, 74: 154-186.
[10]	ZHANG Bin, ASAKURA Hiroyuki, ZHANG Jia, et al. Stabilizing a platinum single-atom catalyst on supported phosphomolybdic acid without compromising hydrogenation activity[J]. Angewandte Chemie International Edition, 2016, 55(29): 8319-8323.
[11]	SIAKA Hermann, DUJARDIN Christophe, MOISSETTE Alain, et al. Revisiting the impact of tungsten on the catalytic properties of ammonia-SCR V₂O₅-WO₃/TiO₂ catalysts: Geometric vs. electronic effects[J]. Chemistry, 2023, 5: 294-313.
[12]	GRIMME S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction[J].Journal of Computational Chemistry, 2010, 27(15): 1787-1799. DOI:10.1002/jcc.20495 .
[13]	HE Junda, LI Jian, LIANG Wenjun, et al. Unveiling the promotional performance of CO oxidation over Na-doped Pt-0.5P&W/TiO₂ catalyst: “SMSI” effect of Na in catalysis[J]. Fuel, 2024, 372: 132199.
[14]	FENG Chenglin, LIU Xiaolong, ZHU Tianyu, et al. Catalytic oxidation of CO over Pt/TiO₂ with low Pt loading: The effect of H₂O and SO₂ [J]. Applied Catalysis A General, 2021, 622(3824): 118218.
[15]	LUCA Consentino, GIUSEPPE Pantaleo, VALERIA Laparola, et al. Role of vanadium in thermal and hydrothermal aging of a commercial V₂O₅-WO₃/TiO₂ monolith for selective catalytic reduction of NO _x : A case study[J]. 2024, 14: 241.
[16]	DONG Jinshi, HUANG Shijun, LI Shengtong, et al. The evolution of Pt with different initial sizes during propane oxidation over Pt-CeO₂ catalysts[J]. Catalysis Science & Technology, 2024, 14: 5211-5217.
[17]	SIVA Sankarreddyputluru, LEONHARD Schill, ANITA Godiksen, et al. Promoted V₂O₅/TiO₂ catalysts for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Applied Catalysis B Environmental, 2016, 183: 282-290.
[18]	TOMISHIGE Keiichi, YOSHINAO Nakagawa, MASAZUMI Tamura. Selective hydrogenolysis and hydrogenation using metal catalysts directly modified with metal oxide species[J]. Green Chemistry, 2017, 19: 2876-2924.
[19]	LIU Yong, ZHANG He, JU Aimin, et al. Supported bimetallic Pt-Pd/ZrVFeTi catalyst for H₂ oxidation and its enhanced catalytic hydrogen elimination performance[J]. Journal of Energy Storage, 2024, 104: 114731.
[20]	HE Junda, LI Jian, CAI Jianyu. Strong metal support interaction (SMSI) and MoO₃ synergistic effect of Pt-based catalysts on the promotion of CO activity and sulfur resistance[J]. Environmental Science and Pollution Research, 2024, 31(1): 1530-1542.
[21]	PENG Ruosi, WEN Shuxian, ZHANG Haozhi, et al. Catalytic oxidation of toluene over Pt/CeO₂ catalysts: A double-edged sword effect of strong metal-support interaction[J]. Langmuir: The ACS Journal of Surfaces and Colloids, 2024, 40: 13984-13994.
[22]	YE Jiawei, ZHU Bicheng, CHENG Bei, et al. Synergy between platinum and gold nanoparticles in oxygen activation for enhanced room-temperature formaldehyde oxidation[J]. Advanced functional materials, 2022, 32: 2110423.
[23]	ZHANG Changbin, HE Hong, TANAKA Kenichi. Catalytic performance and mechanism of a Pt/TiO₂ catalyst for the oxidation of formaldehyde at room temperature[J]. Applied Catalysis B, 2006, 65: 37-43.
[24]	GAO Qi, DONG Changqing, HU Xiaoying, et al. Effect of the Fe₂O₃@TiO₂ core-shell structure on CO catalytic oxidation and SO₂ poisoning resistance[J]. Molecular Catalysis, 2023, 547: 113308.
[25]	SAOWS Zafeiratos, GFDVG Papakonstantinou, MMFSHH Jacksic, et al. The effect of Mo oxides and TiO₂ support on the chemisorption features of linearly adsorbed CO on Pt crystallites: An infrared and photoelectron spectroscopy study[J]. Journal of Catalysis, 2005, 232(1): 127-136.
[26]	YANG Weiwei, LI Li, SHAN Yulong, et al. Interfacial structure-governed SO₂ resistance of Cu/TiO₂ catalysts in the catalytic oxidation of CO[J]. Catalysis Science & Technology, 2020, 10: 1661-1674.
[27]	ZHU Hongtai, QIU Wenge, WU Rui, et al. Alkali metal modified Pt/EG-TiO₂ catalysts for CO oxidation with efficient resistance to SO₂ and H₂O[J]. Catalysis Science & Technology, 2024, 11: 6050-3063.
[28]	WANG Zhiwei, LI Sha, XIE Shaohua, et al. Supported ultralow loading Pt catalysts with high H₂O-, CO₂-, and SO₂-resistance for acetone removal[J]. Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications, 2019, 579: 106-115.
[29]	LIAO Wenmin, FANG Xiuxiu, CEN Bingheng, et al. Deep oxidation of propane over WO₃ ^-promoted Pt/BN catalysts: The critical role of Pt-WO₃ interface[J]. Applied Catalysis B: Environmental, 2020, 272: 118858.
[30]	WU Xiaomin, SUN Shaodi, WANG Ruichen, et al. Pt single atoms and defect engineering of TiO₂-nanosheet-assembled hierarchical spheres for efficient room-temperature HCHO oxidation[J]. Journal of Hazardous Materials, 2023, 454: 131431-131434.
[31]	BSLOX Hammer, YYINT Morikawa, JKOOWS Osxiousa. CO Chemisorption at metal surfaces and overlayers[J]. Physical Review Letters, 1996, 76(12): 2141-2144.
[32]	LI Shuangyu, SONG Liyun, HE Hong. Promotional mechanisms of activity and SO₂ tolerance of NdVO _x /TiO₂ catalysts for selective catalytic reduction of NO _x with NH₃ [J]. ACS catalysis, 2023, 13: 2867-2884.
[33]	CHANG Huazhen, LI Junhua, CHEN Xiaoyin, et al. Effect of Sn on MnO _x -CeO₂ catalyst for SCR of NO _x by ammonia: Enhancement of activity and remarkable resistance to SO₂ [J]. Catalysis Communications, 2012, 27: 54-57.
[34]	YI Tingfeng, ZHANG Yibo, LI Jingwei, et al. Promotional effect of H₃PO₄ on ceria catalyst for selective catalytic reduction of NO by NH₃ [J]. Chinese Journal of Catalysis, 2016, 37(2): 300-307.
[35]	TONG Dapeng, LI Yushi, ZHANG Zhiping, et al. Boosting resistance to H₂O and SO₂ in low-temperature NH₃-SCR denitrification reaction by W addition in Cu_0.1- _m W _m TiO _x (m=0.04—0.09) due to modulating the synergistic effect of oxidation property and acidity[J]. Fuel, 2023, 347: 128443.

催化剂	H₂消耗量/μmol·g^-1
催化剂	<100℃	150～450℃	>500℃	总计
Pt-0.5P&W/TiO₂	0.95	37.75	7.24	45.81
Pt-0.125P&W/TiO₂	1.03	45.38	0.12	46.54
Pt/TiO₂	0.02	49.93	—	49.95

催化剂	H₂消耗量/μmol·g^-1
催化剂	<100℃	150～450℃	>500℃	总计
Pt-0.5P&W/TiO₂	0.95	37.75	7.24	45.81
Pt-0.125P&W/TiO₂	1.03	45.38	0.12	46.54
Pt/TiO₂	0.02	49.93	—	49.95

催化剂	Ti 2p_3/2 (BE)/eV	Ti 2p_1/2 (BE)/eV	[O_α/(O_latt+O_α)]/%
Pt/TiO₂	458.8	464.6	19.16
Pt-0.125P&W/TiO₂	458.9	464.7	28.35
Pt-0.5P&W/TiO₂	458.9	464.7	23.03

催化剂	Ti 2p_3/2 (BE)/eV	Ti 2p_1/2 (BE)/eV	[O_α/(O_latt+O_α)]/%
Pt/TiO₂	458.8	464.6	19.16
Pt-0.125P&W/TiO₂	458.9	464.7	28.35
Pt-0.5P&W/TiO₂	458.9	464.7	23.03

催化剂	B酸/μmol·g^-1	L酸/μmol·g^-1	总酸/μmol·g^-1
Pt/TiO₂	6.1	118.4	124.5
Pt-0.125P&W/TiO₂	8.8	121	129.8
Pt-0.5P&W/TiO₂	12.1	128.3	140.4

Catalytic CO oxidation activity and sulfur resistance of Pt-based catalyst modified by WO₃ with phosphotungstic acid assist

磷钨酸辅助构建WO₃修饰的Pt基催化剂CO催化氧化活性和抗硫性能

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References 35

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催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	CO 吸附量/μmol·g^-1	Pt分散度/%	TOF（100℃）/10^-3s^-1
Pt/TiO₂	60	0.29	8.7×10^-3	42	20
Pt-0.125P&W/TiO₂	59	0.28	3.2×10^-3	18	188
Pt-0.5P&W/TiO₂	62	0.28	4.1×10^-3	25	46

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