液相还原温度对草酸酯加氢制乙醇酸甲酯银硅催化剂性能的影响

doi:10.11949/0438-1157.20211097

摘要/Abstract

摘要：

以表面氨基功能化修饰的介孔二氧化硅纳米微球(AS)为载体，乙醇为还原剂，通过调变前体AgNO₃的还原温度，制得了四种不同银催化剂(Ag/AS)，结合催化剂表征技术和催化性能研究，探讨了液相还原温度对银硅催化剂上草酸二甲酯(DMO)加氢制乙醇酸甲酯(MG)反应性能的影响规律。X射线衍射、氮气物理吸附、透射电镜、X射线光电子能谱等研究结果表明，Ag/AS催化剂随着还原温度的升高Ag颗粒的平均粒径呈指数型增大，对应的表面Ag原子配位数也随之增大。DMO吸附的原位红外光谱和DMO程序升温脱附实验表明，还原温度升高引起的表面原子配位数的增大，减弱了DMO在催化剂上的吸附进而降低了DMO加氢制MG的活性。

关键词: 草酸二甲酯, 加氢, 乙醇酸甲酯, 催化剂, 还原温度, 活性

Abstract:

Four amino-functionalized SiO₂nanospheres supported silver catalysts (Ag/AS) were synthesized in this work by adjusting the temperature of the reduction process for the AgNO₃ precursor with using ethanol as the reductant. The catalyst characterization and the catalytic performance tests clearly show the effect of liquid-phase reduction temperature on the performance of Ag/AS catalysts for hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG). X-Ray diffraction, N₂ physical adsorption, transmission electron microscopy and X-ray photoelectron spectroscopy measurements indicate that the particle size of Ag particles increases significantly with the increasing reduction temperature, which results in increase of surface Ag coordination number. In-situ infrared spectroscopy of DMO adsorption and DMO temperature-programmed desorption experiments show that the increase in the coordination number of surface atoms caused by the increase of reduction temperature weakens the adsorption of DMO on the catalyst and thus reduces the activity of DMO hydrogenation to MG.

Key words: dimethyl oxalate, hydrogenation, methyl glycolate, catalyst, reduction temperature, reactivity

中图分类号:

TQ 032.4

董桂霖, 罗祖伟, 曹约强, 周静红, 李伟, 周兴贵. 液相还原温度对草酸酯加氢制乙醇酸甲酯银硅催化剂性能的影响[J]. 化工学报, 2022, 73(1): 232-240.

Guilin DONG, Zuwei LUO, Yueqiang CAO, Jinghong ZHOU, Wei LI, Xinggui ZHOU. Effect of liquid-phase reduction temperature on performance of silver-silica catalysts for hydrogenation of dimethyl oxalate to methyl glycolate[J]. CIESC Journal, 2022, 73(1): 232-240.

图/表 9

图1 不同还原温度制得的Ag/AS催化剂的TEM图及其对应的Ag粒径分布

Fig.1 Typical TEM images of the Ag/AS catalysts reduced at different temperature and the corresponding histograms of the particle size distributions

图2 Ag纳米颗粒粒径与还原温度的关系

Fig.2 Ag particle size as a function of reduction temperature

表1 Ag/AS催化剂的物理化学性质

Table 1 Physicochemical properties of the Ag/AS catalysts

Sample	Ag content^①/%	S_BET^②/(m²·g^-1)	V_pore^③/(cm³·g^-1)	D_pore^③/nm	d_Ag·TEM^④/nm	d_Ag·XRD^⑤/nm	D^⑥/%	S_Ag^⑥/(m²·g^-1)	TOF/h^-1
Ag/AS_70	2.9	242	0.33	6.12	5.5±0.9	nd	31.7	4.46	230^⑦
Ag/AS_75	2.6	210	0.26	5.43	7.3±1.7	6.7	19.0	2.40	179^⑧
Ag/AS_80	2.3	162	0.21	5.27	11.4±2.1	11.0	13.3	1.48	123^⑨
Ag/AS_85	2.1	117	0.17	5.15	20.6±2.8	20.4	5.7	0.58	72^⑩

图3 不同还原温度制得的Ag/AS催化剂XRD谱图

Fig.3 XRD patterns of Ag/AS catalysts synthesized at different reduction temperature

图4 不同还原温度制得的Ag/AS催化剂Ag 3d XPS谱图

Fig.4 Ag 3d XPS spectra of Ag/AS catalysts synthesized at different reduction temperature

图5 不同还原温度下制得的Ag/AS催化剂高倍透射电镜图

Fig.5 Typical HRTEM images of Ag/AS catalysts synthesized at different reduction temperature

图6 2.0 MPa、220℃、H2/DMO为80时Ag/AS催化剂在DMO加氢制MG反应中的性能考评

Fig.6 Performance evaluation of Ag/AS catalysts in DMO hydrogenation to MG under 2.0 MPa，220℃，H2/DMO 80

图7 气相DMO分子的FTIR谱图和DMO吸附于Ag/AS催化剂上的FTIR谱图

Fig.7 FTIR spectra of the gas-phase DMO molecule and the adsorbed ones on the Ag/AS catalysts

图8 Ag/AS催化剂上的DMO-TPD曲线

Fig.8 DMO-TPD profiles for the Ag/AS catalysts

参考文献 37

1	王登豪, 张传彩, 朱明远, 等. 高效稳定的铜镍催化剂在草酸二甲酯加氢中的应用[J]. 化工学报, 2017, 68(7): 2739-2745.
	Wang D H, Zhang C C, Zhu M Y, et al. Efficient and stable hydrogenation of dimethyl oxalate via copper-nickel catalysts[J]. CIESC Journal, 2017, 68(7): 2739-2745.
2	Sun Y, Wang H, Shen J H, et al. Highly effective synthesis of methyl glycolate with heteropolyacids as catalysts[J]. Catalysis Communications, 2009, 10(5): 678-681.
3	Lee K Y, Bouhadir K H, Mooney D J. Degradation behavior of covalently cross-linked poly(aldehyde guluronate) hydrogels[J]. Macromolecules, 2000, 33(1): 97-101.
4	Yue H R, Zhao Y J, Ma X B, et al. Ethylene glycol: properties, synthesis, and applications[J]. Chemical Society Reviews, 2012, 41(11): 4218-4244.
5	Xu Q. Metal carbonyl cations: generation, characterization and catalytic application[J]. Coordination Chemistry Reviews, 2002, 231(1/2): 83-108.
6	王克冰, 姚洁, 雷永诚, 等. 硫酸氢钠催化甲醛与甲酸甲酯的偶联反应[J]. 化工学报, 2007, 58(4): 897-902.
	Wang K B, Yao J, Lei Y C, et al. Coupling reaction of formaldehyde and methyl formate over sodium bisulfate catalyst[J]. Journal of Chemical Industry and Engineering (China), 2007, 58(4): 897-902.
7	龚海燕. Cu/SiO₂催化草酸二甲酯加氢制乙醇酸甲酯的反应性能[J]. 化学反应工程与工艺, 2014, 30(2): 169-174.
	Gong H Y. Hydrogenation of dimethyl oxalate to methyl glycolate on Cu/SiO₂ catalyst[J]. Chemical Reaction Engineering and Technology, 2014, 30(2): 169-174.
8	穆仕芳, 尚如静, 魏灵朝, 等. 草酸二甲酯选择性加氢非硅基催化体系分析[J]. 现代化工, 2016, 36(10): 34-37.
	Mu S F, Shang R J, Wei L C, et al. Analysis of non-silica catalytic system for selective hydrogenation of dimethyl oxalate[J]. Modern Chemical Industry, 2016, 36(10): 34-37.
9	Huang W G, He D H, Liu J Y, et al. Catalytic condensation of formaldehyde and methyl formate over 12-tungstosilicic compounds[J]. Applied Catalysis A: General, 2000, 199(1): 93-98.
10	Celik F E, Lawrence H, Bell A T. Synthesis of precursors to ethylene glycol from formaldehyde and methyl formate catalyzed by heteropoly acids[J]. Journal of Molecular Catalysis A: Chemical, 2008, 288(1/2): 87-96.
11	Zhang L, Han L P, Zhao G F, et al. Structured Pd-Au/Cu-fiber catalyst for gas-phase hydrogenolysis of dimethyl oxalate to ethylene glycol[J]. Chemical Communications, 2015, 51(52): 10547-10550.
12	Zheng J W, Zhou J F, Lin H Q, et al. CO-mediated deactivation mechanism of SiO₂-supported copper catalysts during dimethyl oxalate hydrogenation to ethylene glycol[J]. The Journal of Physical Chemistry C, 2015, 119(24): 13758-13766.
13	俞金山, 冯翀, 刘甜甜, 等. 可抑制1, 2-丁二醇生成的高性能草酸二甲酯加氢B-Cu/MS催化剂的研究[J]. 天然气化工(C1化学与化工), 2021, 46(4): 33-40.
	Yu J S, Feng C, Liu T T, et al. Study on high performance B-Cu/MS catalyst for suppressing by-product 1, 2-butanediol in hydrogenation of dimethyl oxalate[J]. Natural Gas Chemical Industry, 2021, 46(4): 33-40.
14	Zhou J F, Duan X P, Ye L M, et al. Enhanced chemoselective hydrogenation of dimethyl oxalate to methyl glycolate over bimetallic Ag-Ni/SBA-15 catalysts[J]. Applied Catalysis A: General, 2015, 505: 344-353.
15	Li M M J, Ye L M, Zheng J W, et al. Surfactant-free nickel-silver core@shell nanoparticles in mesoporous SBA-15 for chemoselective hydrogenation of dimethyl oxalate[J]. Chemical Communications, 2016, 52(12): 2569-2572.
16	李祥祥, 朱贻安, 周静红, 等. 银和铜催化草酸二甲酯加氢制乙醇酸甲酯反应机理的理论研究[J]. 天然气化工(C1化学与化工), 2018, 43(6): 17-23.
	Li X X, Zhu Y A, Zhou J H, et al. Insights into the reaction mechanism of dimethyl oxalate hydrogenation to methyl glycolate over Ag and Cu catalysts[J]. Natural Gas Chemical Industry, 2018, 43(6): 17-23.
17	Dong G L, Cao Y Q, Zheng S N, et al. Catalyst consisting of Ag nanoparticles anchored on amine-derivatized mesoporous silica nanospheres for the selective hydrogenation of dimethyl oxalate to methyl glycolate[J]. Journal of Catalysis, 2020, 391: 155-162.
18	Hu Y W, Wang N, Zhou Z M. Synergetic effect of Cu active sites and oxygen vacancies in Cu/CeO₂-ZrO₂ for the water-gas shift reaction[J]. Catalysis Science & Technology, 2021, 11(7): 2518-2528.
19	何璐铭, 辛忠, 高文莉, 等. 静电纺丝法制备高活性多孔Ni/SiO₂甲烷化催化剂[J]. 化工学报, 2020, 71(11): 5007-5015.
	He L M, Xin Z, Gao W L, et al. Highly efficient porous Ni/SiO₂ catalysts prepared by electrospinning method for CO methanation[J]. CIESC Journal, 2020, 71(11): 5007-5015.
20	Zheng J W, Lin H Q, Wang Y N, et al. Efficient low-temperature selective hydrogenation of esters on bimetallic Au-Ag/SBA-15 catalyst[J]. Journal of Catalysis, 2013, 297: 110-118.
21	吴岳峰, 曲永芳, 李大欢, 等. 聚离子液体载MoO₂/Ag催化分子氧氧化苯乙烯的研究[J]. 化工学报, 2020, 71(11): 4990-4998.
	Wu Y F, Qu Y F, Li D H, et al. Study on oxidation of styrene with molecular oxygen catalyzed by MoO₂/Ag on polyionic liquid[J]. CIESC Journal, 2020, 71(11): 4990-4998.
22	Zheng J W, Lin H Q, Zheng X L, et al. Highly efficient mesostructured Ag/SBA-15 catalysts for the chemoselective synthesis of methyl glycolate by dimethyl oxalate hydrogenation[J]. Catalysis Communications, 2013, 40: 129-133.
23	邓湘玲, 叶松寿, 曹志凯, 等. Ag/Ce_0.75Zr_0.25O₂催化剂中Ag的负载量对碳烟燃烧活性的影响[J]. 化工学报, 2017, 68(8): 3064-3070.
	Deng X L, Ye S S, Cao Z K, et al. Effect of Ag loading on soot oxidation for Ag/Ce_0.75Zr_0.25O₂ catalysts[J]. CIESC Journal, 2017, 68(8): 3064-3070.
24	Chen H M, Tan J J, Cui J L, et al. Promoting effect of boron oxide on Ag/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to methyl glycolate[J]. Molecular Catalysis, 2017, 433: 346-353.
25	曹昊苏, 张荣成, 朱长俊, 等. Ag-H₂Ti₄O₉复合材料的制备以及可见光下对甲苯降解的研究[J]. 硅酸盐通报, 2018, 37(11): 3623-3629, 3636.
	Cao H S, Zhang R C, Zhu C J, et al. Preparation of Ag doped H₂Ti₄O₉ and the study on its photocatalytic degradation of toluene under visible light[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(11): 3623-3629, 3636.
26	Bergman S L, Ganguly A S, Bernasek S L. XPS characterization of a plasmonic sensor for catalysis studies by controlled differential charging[J]. Journal of Electron Spectroscopy and Related Phenomena, 2018, 222: 88-94.
27	Bukhtiyarov V I, Prosvirin I P, Kvon R I, et al. XPS study of the size effect in ethene epoxidation on supported silver catalysts[J]. Journal of the Chemical Society, Faraday Transactions, 1997, 93(13): 2323-2329.
28	Chen J Y, Cui P X, Zhao G Q, et al. Low-coordinate iridium oxide confined on graphitic carbon nitride for highly efficient oxygen evolution[J]. Angewandte Chemie International Edition, 2019, 58(36): 12540-12544.
29	Hu J, Wu L, Kuttiyiel K A, et al. Increasing stability and activity of core-shell catalysts by preferential segregation of oxide on edges and vertexes: oxygen reduction on Ti-Au@Pt/C[J]. Journal of the American Chemical Society, 2016, 138(29): 9294-9300.
30	Zhang J Y, Qian J M, Ran J Q, et al. Engineering lower coordination atoms onto NiO/Co₃O₄ heterointerfaces for boosting oxygen evolution reactions[J]. ACS Catalysis, 2020, 10(21): 12376-12384.
31	Zheng J W, Duan X P, Lin H Q, et al. Silver nanoparticles confined in carbon nanotubes: on the understanding of the confinement effect and promotional catalysis for the selective hydrogenation of dimethyl oxalate[J]. Nanoscale, 2016, 8(11): 5959-5967.
32	Ma X B, Chi H W, Yue H R, et al. Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu-MCM-41 catalysts[J]. AIChE Journal, 2013, 59(7): 2530-2539.
33	Cui G Q, Meng X Y, Zhang X, et al. Low-temperature hydrogenation of dimethyl oxalate to ethylene glycol via ternary synergistic catalysis of Cu and acid-base sites[J]. Applied Catalysis B: Environmental, 2019, 248: 394-404.
34	Fleming I. Molecular Orbitals and Organic Chemical Reactions[M]. Chichester, UK: John Wiley & Sons, Ltd., 2010.
35	Dong G L, Luo Z W, Cao Y Q, et al. Understanding size-dependent hydrogenation of dimethyl oxalate to methyl glycolate over Ag catalysts[J]. Journal of Catalysis, 2021, 401: 252-261.
36	Hartfelder U, Kartusch C, Makosch M, et al. Particle size and support effects in hydrogenation over supported gold catalysts[J]. Catal. Sci. Technol., 2013, 3(2): 454-461.
37	Kasinathan P, Hwang D W, Lee U H, et al. Effect of Cu particle size on hydrogenation of dimethyl succinate over Cu-SiO₂ nanocomposite[J]. Catalysis Communications, 2013, 41: 17-20.

[1]	杨欣, 王文, 徐凯, 马凡华. 高压氢气加注过程中温度特征仿真分析[J]. 化工学报, 2023, 74(S1): 280-286.
[2]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[3]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[4]	曹跃, 余冲, 李智, 杨明磊. 工业数据驱动的加氢裂化装置多工况切换过渡状态检测[J]. 化工学报, 2023, 74(9): 3841-3854.
[5]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[6]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[7]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[8]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[9]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[10]	吕龙义, 及文博, 韩沐达, 李伟光, 高文芳, 刘晓阳, 孙丽, 王鹏飞, 任芝军, 张光明. 铁基导电材料强化厌氧去除卤代有机污染物：研究进展及未来展望[J]. 化工学报, 2023, 74(8): 3193-3202.
[11]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.
[12]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[13]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[14]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[15]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.