基于生物模板制备二氧化碳加氢反应的Cu/ZnO催化剂

doi:10.11949/0438-1157.20201893

摘要/Abstract

摘要：

采用油菜花粉作为生物模板制备了具有多层次孔结构的ZnO，再通过浸渍还原法将Cu负载于ZnO上制备了具有不同结构的Cu/ZnO负载型催化剂（bio-CZ-500），研究发现在500℃条件下焙烧制备的bio-CZ-500催化剂在CO₂加氢反应中经过100 h测试活性几乎不变，同时甲醇选择性高达81%。相比之下，无生物模板制备的Cu/ZnO催化剂显示出较低甲醇选择性（50%），且催化剂在12 h内快速失活。通过透射电镜、扫描电镜、氮气吸脱附、红外光谱、X射线衍射、X射线光电子能谱、接触角测试、程序升温等表征技术揭示了bio-CZ-500催化剂具有多级孔碳结构、丰富的Cu-ZnO活性界面和较高的水接触角。催化剂的弱亲水性加快了副产物水的扩散，促进了中间体分解制甲醇，同时抑制了铜颗粒的烧结失活，从而提高甲醇的选择性与催化剂的稳定性。该工作为制备高效稳定的Cu基工业催化剂提供了新方法。

关键词: 生物模板, CO₂加氢, Cu/ZnO催化剂, Cu-ZnO界面, 稳定性

Abstract:

Rape pollen was used as a biological template to prepare ZnO with a multi-layered pore structure, and Cu/ZnO supported catalysts (bio-CZ-500) with different structures were prepared by dipping and reducing Cu on ZnO. The obtained Cu/ZnO catalyst (namely, bio-CZ-500 upon calcination under 500℃) exhibited a high methanol selectivity of 81% in CO₂ hydrogenation and the activity could remain almost unchanged over 100 h on stream. However, the Cu/ZnO catalyst prepared by a conventional deposition-precipitation method exhibited much lower methanol selectivity (50%) and a rapid deactivation within 12 h under the same operation conditions. Based on series of characterization results, including TEM, SEM, N₂ physisorption, FTIR, XRD, XPS, contact angle analysis, and temperature-programmed techniques, etc., it was revealed that the bio-CZ-500 catalyst had a hierarchically porous carbon structure, abundant Cu-ZnO active interfaces, and a relatively larger water contact angle. The relative hydrophobicity of the bio-CZ-500 catalyst surface could accelerate the desorption of the by-product H₂O, promote the transformation of reaction intermediates to methanol, and also inhibit the sintering of copper, which led to the enhancement of both methanol selectivity and catalyst stability. It is believed that this work will provide a novel synthetic strategy to fabricate highly efficient and stable Cu-based catalysts for industrial application.

Key words: bio-template, CO₂ hydrogenation, Cu/ZnO catalyst, Cu-ZnO interface, stability

中图分类号:

TQ 018

蔡中杰, 田盼, 黄忠亮, 黄猛, 黄加乐, 詹国武, 李清彪. 基于生物模板制备二氧化碳加氢反应的Cu/ZnO催化剂[J]. 化工学报, 2021, 72(7): 3668-3679.

CAI Zhongjie, TIAN Pan, HUANG Zhongliang, HUANG Meng, HUANG Jiale, ZHAN Guowu, LI Qingbiao. Preparation of Cu/ZnO nanocatalysts based on bio-templates for CO₂ hydrogenation[J]. CIESC Journal, 2021, 72(7): 3668-3679.

图/表 11

图1 bio-CZ-500催化剂与chem-CZ催化剂的制备流程示意图

Fig.1 Diagram of the preparation process of bio-CZ catalyst and chem-CZ catalyst

图2 原始花粉的扫描电镜图[(a)~(c)]；不同焙烧温度下制备的bio-ZnO的扫描电镜图: 500℃[(d)~(f)]，600℃[(g)~(i)]，700℃[(j)~(l)][其中图(d)、(g)、(j)中插图分别为该焙烧后样品的照片]

Fig.2 Representative SEM images of the original pollen [(a)—(c)] and bio-ZnO obtained at the calcination temperature of 500℃[(d)—(f)], 600℃[(g)—(i)], and 700℃[(j)—(l)] [Insets in (d), (g), and (j) are photos of the calcined samples]

图3 沉积沉淀法制备的chem-ZnO的扫描电镜图

Fig.3 Representative SEM images of chem-ZnO support prepared by deposition precipitation method

图4 不同样品的氮气吸脱附曲线（内插图为孔径分布）(a);红外谱图(methanol表示甲醇洗涤样品) (b); ZnO载体的XRD谱图(c);负载Cu后催化剂的XRD谱图(d)

Fig.4 N2 physisorption isotherms of different samples(inset shows corresponding pore size distribution curves) (a); FTIR spectra (b); XRD patterns of ZnO support samples (c); XRD patterns of catalyst samples (d)

图5 未焙烧Pollen-ZnO样品的热重图

Fig.5 TGA profile of the uncalcined Pollen-ZnO sample

图6 反应温度对两种催化剂活性的影响（内插图为催化剂相应的模型）(a)；Cu/Zn摩尔比对bio-CZ-500催化性能的影响(b)；四种催化剂的活性评价结果(c)；bio-CZ-500与chem-CZ催化剂的稳定性评价结果（图中实心图例代表bio-CZ-500，空心图例代表chem-CZ）(d)

Fig.6 Effect of reaction temperature on the catalytic performance of bio-CZ-500 and chem-CZ (insets are the structure model) (a); The effect of different molar ratios on the catalytic performance of bio-CZ-500 (b); Comparisons of catalytic performance of four catalysts (c); Long-term stability test of bio-CZ-500 and chem-CZ catalysts during 100 h on stream (the soild symbols represent bio-CZ-500 and hollow symbols represent chem-CZ) (d)

图7 反应前的bio-CZ-500催化剂的透射电镜图[(a)~(c)]；反应前的chem-CZ催化剂的透射电镜图[(d)~(f)];[其中图(b)、(e)中内插图为Cu颗粒的粒径分布]

Fig.7 Representative TEM images of fresh bio-CZ-500 catalyst[(a)—(c)] and fresh chem-CZ catalyst[(d)—(f)][Insets in (b), (e) show the particle size distributions of Cu nanoparticles]

图8 反应后的bio-CZ-500催化剂的TEM图[(a)~(c)]；反应后的chem-CZ催化剂的TEM图[(d)~(f)][其中图(b)、(e)中的内插图为Cu颗粒的粒径分布]

Fig.8 TEM images of spent bio-CZ-500 catalyst[(a)—(c)] and spent chem-CZ catalyst[(d)—(f)] [Insets in (b), (e) show the particle size distributions of Cu nanoparticles]

图9 反应前后bio-CZ-500与chem-CZ催化剂的XPS谱图

Fig.9 XPS spectra of bio-CZ-500 and chem-CZ catalysts before and after the catalytic reaction

图10 bio-CZ-500与chem-CZ催化剂的H2程序升温还原谱图

Fig.10 H2 TPR profiles of bio-CZ-500 and chem-CZ catalysts

图11 Cu/ZnO催化剂的结构与催化活性之间的构效关系

Fig.11 The structure-performance relationship of Cu/ZnO catalysts

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