以结构规整的棒状SBA-15分子筛为载体,通过调控过渡金属Co的含量,制备不同Pd-Co摩尔比的Pd1Cox/SBA-15贵金属-过渡金属耦合催化剂,用于丙酮(C3H6O)的催化氧化研究.结果表明,Pd1Co1/SBA-15催化剂展现出最佳的丙酮低温氧化活性,其在220℃时即可实现90%的丙酮转化率,并表现出优异的CO2选择性与热稳定性.通过SEM,XRD,FT-IR和N2吸脱附表征分析可知,Pd1Co1/SBA-15具有最佳的Pd-Co配比和比表面积,有利于活性位点的锚定与暴露.H2-TPR,O2-TPD和XPS表征结果表明,Pd1Co0.5/SBA-15与Pd1Co3/SBA-15中的主要活性氧物种为化学吸附氧,而Pd1Co1/SBA-15中的主要活性氧物种为表面晶格氧,且Pd1Co1/SBA-15催化剂具有丰富的活性氧物种,在反应过程中保持了高效的晶格氧迁移与循环.通过原位红外光谱揭示了丙酮的反应机理,Pd1Co1/SBA-15催化剂上丙酮转化路径为:C3H6O→CH3CH2OH→CH3COO-→COO-→CO2,丰富的晶格氧是丙酮活化和裂解的关键.
Abstract
Taking the well-structured rod-like SBA-15 as support, Pd1Cox/SBA-15 bimetallic catalysts with different palladium(Pd) and cobalt(Co) molar ratios were prepared by adjusting the Co content for acetone (C3H6O) catalytic oxidation. Among these, the Pd1Co1/SBA-15 catalyst was found to exhibit superior performance for the low-temperature oxidation of C3H6O, achieving 90% conversion at 220°C, along with high CO2 selectivity and thermal stability. Characterization by SEM, XRD, FT-IR, and N₂ adsorption-desorption was conducted, and it was revealed that Pd1Co1/SBA-15 possessed the optimal Pd/Co ratio and a higher specific surface area, which were crucial for the stabilization and exposure of active sites. Further investigations using H2-TPR, O2-TPD, and XPS indicated that the primary active oxygen species in Pd1Co0.5/SBA-15 and Pd1Co3/SBA-15 were chemisorbed oxygen, while surface lattice oxygen was predominantly present in Pd1Co1/SBA-15. Moreover, the transformation of abundant active oxygen species in Pd1Co1/SBA-15 was significantly promoted. The reaction mechanism of acetone oxidation over Pd1Co1/SBA-15 was elucidated by in-situ infrared spectroscopy. The decomposition path of acetone molecules over Pd1Co1/SBA-15 catalyst was determined as C3H6O→CH3CH2OH→CH3COO-→COO-→CO2, which further indicated that enhanced surface lattice oxygen can significantly accelerate activation and cleavage during the acetone oxidation process.
关键词
棒状SBA-15 /
双金属催化剂 /
丙酮 /
催化氧化 /
活性氧物种
Key words
rod-like SBA-15 /
bimetallic catalyst /
acetone /
catalytic oxidation /
active oxygen species
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] Salar-Garcia M J, Ortiz-Martinez V M, Hernandez-Fernandez F J, et al. Ionic liquid technology to recover volatile organic compounds (VOCs) [J]. Journal of Hazardous Materials, 2017,321:484-499.
[2] Scire S, Liotta L F. Supported gold catalysts for the total oxidation of volatile organic compounds [J]. Applied Catalysis B: Environmental, 2012,125:222-246.
[3] Guo Y, Wen M, Li G, et al. Recent advances in VOC elimination by catalytic oxidation technology onto various nanoparticles catalysts: A critical review [J]. Applied Catalysis B: Environmental, 2021,281: 119447.
[4] Yang C, Miao G, Pi Y, et al. Abatement of various types of VOCs by adsorption/catalytic oxidation: A review [J]. Chemical Engineering Journal, 2019,370:1128-1153.
[5] 杨莉哲.分子筛限域Pt/PtMn催化剂的制备及其催化氧化VOCs的性能研究 [D].天津:天津大学, 2022. Yang L Z. Synthesis of zeolite confined Pt/PtMn catalysts and catalytic performance for oxidation of VOCs [D]. Tianjin: Tianjin University, 2022.
[6] Wang F, Dai H, Deng J, et al. Manganese oxides with rod-, wire-, tube-, and flower-like morphologies: Highly effective catalysts for the removal of toluene [J]. Environmental Science & Technology, 2012, 46(7):4034-4041.
[7] He C, Cheng J, Zhang X, et al. Recent advances in the catalytic oxidation of volatile organic compounds: A review based on pollutant sorts and sources [J]. Chemical Reviews, 2019,119(7):4471-4568.
[8] 郭娜,张金瑶,蒋鹭翔,等.负载型钌铈催化剂的甲苯催化氧化性能 [J].环境工程学报, 2022,16(6):1853-1861. Guo N, Zhang J Y, Jiang L X, et al. Catalytic oxidation of toluene by supported ruthenium-cerium catalyst [J]. Chinese Journal of Environmental Engineering, 2022,16(6):1853-1861.
[9] Zhao D, Huo Q, Feng J, et al. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, Mesoporous Silica Structures [J]. Journal of the American Chemical Society, 1998,120(24):6024-6036.
[10] Ma M, Huang H, Chen C, et al. Highly active SBA-15-confined Pd catalyst with short rod-like micro-mesoporous hybrid nanostructure for n-butylamine low-temperature destruction [J]. Molecular Catalysis, 2018,455:192-203.
[11] Yu C, Fan J, Tian B, et al. Morphology development of mesoporous materials: a colloidal phase separation mechanism [J]. Chemistry of Materials, 2004,16(5):889-898.
[12] Colilla M, Balas F, Manzano M, et al. Novel method to enlarge the surface area of SBA-15 [J]. Chemistry of Materials, 2007,19(13): 3099-3101.
[13] 孔文晶,林佳佳,钟雪芸,等.Pd/CeO2上乙酸丁酯高效深度氧化性能与机理研究 [J].能源环境保护, 2024,38(4):198-208. Kong W J, Lin J J, Zhong X Y, et al. Study on the performance and mechanism of high-efficiency deep oxidation of butyl acetate over Pd/CeO2 [J]. Energy Environmental Protection, 2024,38(4):198-208.
[14] Wang L, Wang L, Meng X, et al. New strategies for the preparation of sinter-resistant metal-nanoparticle-cased catalysts [J]. Advanced Materials, 2019,31(50):1901905.
[15] Ararwa N, Freakle S J, Mcvicke R U, et al. Aqueous Au-Pd colloids catalyze selective CH4oxidation to CH3OH with O2 under mild conditions [J]. Science, 2017,358(6360):223-227.
[16] Sankar M, Dimitratos N, Miedzlak P J, et al. Designing bimetallic catalysts for a green and sustainable future [J]. Chemical Society Reviews, 2012,41:8099-8139.
[17] Enache D I, Edwards J K, Landon P, et al. Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO2 catalysts [J]. Science, 2006,311(5759):362-365.
[18] Zhao Q, Ge Y, Fu K, et al. Catalytic performance of the Pd/TiO2 modified with MnOx catalyst for acetone total oxidation [J]. Applied Surface Science, 2019,496:143579.
[19] Wu Y, Wang Y, Liu J, et al. Promoting intermediates transformation by boosting H2O dissociation over core-shell Pd@CoO Janus for acetone efficacious oxidation [J]. Applied Catalysis B: Environment and Energy, 2024,354:124113.
[20] Chen C, Yu Y, He C, et al. Efficient capture of CO2 over ordered micro-mesoporous hybrid carbon nanosphere [J]. Applied Surface Science, 2018,439:113-121.
[21] Ma M, Jian Y, Chen C, et al. Spherical-like Pd/SiO2 catalysts for n-butylamine efficient combustion: Effect of support property and preparation method [J]. Catalysis Today, 2020,339:181-191.
[22] Mu X, Ding H, Pan W, et al. Research progress in catalytic oxidation of volatile organic compound acetone [J]. Journal of Environmental Chemical Engineering, 2021,9(4):105650.
[23] Bendahou K, Cherif L, Siffert S, et al. The effect of the use of lanthanum-doped mesoporous SBA-15on the performance of Pt/SBA-15 and Pd/SBA-15catalysts for total oxidation of toluene [J]. Applied Catalysis A: General, 2008,351(1):82-87.
[24] Bai P, Zhao Z, Zhang Y, et al. Rational design of highly efficient PdIn-In2O3 interfaces by a capture-alloying strategy for benzyl alcohol partial oxidation [J]. ACS Applied Materials & Interfaces, 2023,15(15):19653-19664.
[25] Wang J, Jiang Z, Xu H, et al. Elucidating confinement and microenvironment of Ru clusters stably confined in MFI zeolite for efficient propane oxidation [J]. Angewandte Chemie International Edition, 2024,64(5),e202417618.
[26] Shan C, Zhang Y, Zhao Q, et al. Acid etching-induced in situ growth of λ-MnO2over CoMn spinel for low-temperature volatile organic compound oxidation [J]. Environmental Science & Technology, 2022, 56(14):10381-10390.
[27] Wang J, Yoshida A, Wang P, et al. Catalytic oxidation of volatile organic compound over cerium modified cobalt-based mixed oxide catalysts synthesized by electrodeposition method [J]. Applied Catalysis B: Environmental, 2020,271:118941.
[28] 陈曦,贾子良,王梦雪,等.RuOx分散性导致的活性氧异化与氯苯氧化相关性研究 [J].中国环境科学, 2025,45(4):1820-1832. Chen X, Jia Z L, Wang M X, et al. Correlation between chlorobenzene oxidation and active oxygen species induced by the dispersity of RuOx [J]. China Environmental Science, 2025,45(4):1820-1832.
[29] Zhu D, Huang Y, Li R, et al. Constructing active Cu2+-O-Fe3+ sites at the CuO-Fe3O4 interface to promote activation of surface lattice oxygen [J]. Environmental Science & Technology, 2023,57(45): 17598-17609.
[30] Bi F, Zhao Z, Yang Y, et al. Chlorine-coordinated Pd single atom enhanced the chlorine resistance for volatile organic compound degradation: mechanism study [J]. Environmental Science & Technology, 2022,56(23):17321-17330.
[31] Zhang W, Li J, Li Y, et al. Acetone efficient degradation under simulated humid conditions by Mn-O-Pt interaction taming-triggered water dissociation intensification [J]. Environmental Science & Technology, 2023,57(49):20962-20973.
[32] 杨旸,郑雯,程党国,等.原位FT-IR技术在研究甲烷氧化反应中的应用 [J].化学进展, 2009,21(10):2205-2211. Yang Y, Zheng W, Chen D G, et al. The application of in situ FT-IR in the research of methane oxidation [J]. Progress in Chemistry, 2009, 21(10):2205-2211.
[33] Jiang Z, Dong R, Tian M, et al. Achieving acetone efficient deep decomposition by strengthening reactants adsorption and activation over difunctional Au(OH)Kx/hierarchical MFI catalyst [J]. Journal of Colloid and Interface Science, 2022,612:504-515.
[34] Dong A, Gao S, Wan X, et al. Labile oxygen promotion of the catalytic oxidation of acetone over a robust ternary Mn-based mullite GdMn2O5 [J]. Applied Catalysis B: Environmental, 2020,271:118932.
[35] Zhang W, Wu K, Zhao J, et al. Promotional effects of calcination temperature and H2O on the catalytic activity of Al-substituted MnAlO catalysts for low-temperature acetone oxidation [J]. Chemosphere, 2022,301:134722.
基金
国家自然科学基金资助项目(22406146);中国博士后科学基金资助项目(2023M732783);国家重点研发计划(2022YFB4101500)
PDF(1300 KB)
京公网安备 11010802030352号 
