化工学报 ›› 2021, Vol. 72 ›› Issue (7): 3668-3679.DOI: 10.11949/0438-1157.20201893
蔡中杰1(),田盼1,黄忠亮2,黄猛1,黄加乐1(),詹国武2(),李清彪1,3
收稿日期:
2020-12-22
修回日期:
2021-03-02
出版日期:
2021-07-05
发布日期:
2021-07-05
通讯作者:
黄加乐,詹国武
作者简介:
蔡中杰(1995—),男,硕士研究生,基金资助:
CAI Zhongjie1(),TIAN Pan1,HUANG Zhongliang2,HUANG Meng1,HUANG Jiale1(),ZHAN Guowu2(),LI Qingbiao1,3
Received:
2020-12-22
Revised:
2021-03-02
Online:
2021-07-05
Published:
2021-07-05
Contact:
HUANG Jiale,ZHAN Guowu
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。
中图分类号:
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]
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