无定形硅铝负载镍催化剂上乙烯齐聚反应的活性位点结构鉴定

doi:10.1016/S1872-2067(21)63827-5

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2181-2188.DOI: 10.1016/S1872-2067(21)63827-5

无定形硅铝负载镍催化剂上乙烯齐聚反应的活性位点结构鉴定

续晶华^a, 王瑞锋^a^,^b, 张亚茹^a^,^b, 李林^a, 严文君^c, 王俊英^c, 刘国东^a, 苏雄^a^,^#(), 黄延强^a^,^*(), 张涛^a

^a中国科学院大连化学物理研究所应用催化科学与技术中国科学院重点实验室, 辽宁大连116023
^b中国科学院大学, 北京100049
^c中国科学院山西煤炭化学所, 分析仪器中心, 山西太原030001

收稿日期:2021-02-01 接受日期:2021-02-01 出版日期:2021-12-18 发布日期:2021-05-20
通讯作者: 苏雄,黄延强
基金资助:
科技部重点研发计划(2016YFA0202804);中科院B类先导专项(XDB36030200);国家自然科学基金(21978286);国家自然科学基金(21925803);中科院青年创新促进会;中国博士后科学基金(2018M631835)

Identification of the structure of Ni active sites for ethylene oligomerization on an amorphous silica-alumina supported nickel catalyst

Jinghua Xu^a, Ruifeng Wang^a^,^b, Yaru Zhang^a^,^b, Lin Li^a, Wenjun Yan^c, Junying Wang^c, Guodong Liu^a, Xiong Su^a^,^#(), Yanqiang Huang^a^,^*(), Tao Zhang^a

^aCAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cAnalytical Instrumentation Center, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China

Received:2021-02-01 Accepted:2021-02-01 Online:2021-12-18 Published:2021-05-20
Contact: Xiong Su,Yanqiang Huang
About author:# E-mail: suxiong@dicp.ac.cn
* Tel: +86-411-84379416; Fax: +86-411-84685940; E-mail: yqhuang@dicp.ac.cn;
Supported by:
National Key R&D Program of China(2016YFA0202804);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB36030200);National Natural Science Foundation of China(21978286);National Natural Science Foundation of China(21925803);Youth Innovation Promotion Association(CAS);China Postdoctoral Science Foundation(2018M631835)

摘要/Abstract

摘要：

镍(Ni)基催化剂在低碳烯烃聚合领域具有重要的地位, 也是该领域研究的热点. 自Johnson等报道(J. Am. Chem. Soc., 1995, 117, 6414-6415)二亚胺配体络合的Ni(II)催化剂可有效降低烯烃聚合度, 降低产物中非线性烯烃的选择性, 甚至可以生成α-烯烃以来, 掀起了Ni基催化剂在烯烃聚合领域的研究热潮. 从均相到负载型多相Ni基催化剂, 从载体类型到配体性质, 从Ni纳米粒子的粒径调控到金属表面价态, 关于Ni活性中心的研究工作一直存在争论. 本课题组之前研究结果表明, 曾明确了无定形硅铝(ASA)载体负载的Ni催化剂, 经惰性气氛(N₂)预处理得到的一价Ni是烯烃齐聚反应的主要活性中心(J. Chem. Soc. Chem. Commun., 1991, 126-127).

本文进一步深入研究了不同Al₂O₃含量的ASA载体上Ni活性位点的结构及其在乙烯齐聚反应中的活性.²⁷Al NMR 结果表明, 催化剂中的铝存在三种配位方式, 分别为Al^Ⅳ、Al^Ⅴ和Al^Ⅵ, 其中Al^Ⅳ含量随Al₂O₃含量的增加而增加. 载体中铝配位方式的不同, 导致其表面金属负载的金属Ni活性位点所处的结构亦不同. 原位FTIR-CO和H₂-TPR实验结果表明, 催化剂表面存在两种不同结构分布的Ni位点, 分别是接枝在弱酸性硅醇上的Ni²⁺阳离子和Si-(OH)-Al桥式羟基离子交换位置的Ni²⁺阳离子. 多数研究者认为, 位于离子交换位置处孤立的Ni阳离子是反应的活性中心. 然而, 近期有研究者提出负载在酸性硅烷醇表面孤立的Ni²⁺阳离子为反应的活性中心物质. 本文研究发现, 随着Al₂O₃负载量的降低, 处于离子交换位置处的Ni²⁺离子含量逐渐减少, 而处于硅醇缺陷位点处的Ni²⁺离子含量则逐渐增多. 原位FTIR-CO分析结果表明, 处于硅醇缺陷位点处的Ni²⁺离子物种在惰性气氛中更易于转化为活性中心Ni⁺. 相应的催化反应结果表明, 相比于离子交换位置的Ni²⁺物种, 具有与硅醇缺陷位点相连的Ni²⁺离子结构更有利于表现出更高的乙烯齐聚化活性. 由此可知, 处于硅醇缺陷位点的Ni²⁺物种是乙烯齐聚反应的活性中心的前驱体.

本文进一步研究了硅醇缺陷位点处的Ni²⁺离子物种更易于转化为活性中心Ni⁺的原因. H₂-TPR结果表明, 相比于离子交换位置的Ni²⁺物种, 处于硅醇缺陷位点的Ni²⁺物种与载体之间的相互作用力更弱. C₂H₄-TPD结果进一步表明, 具有这种相对较弱的金属载体间作用力结构的催化剂对反应物C₂H₄分子的吸附作用力相对更强, 吸附量也相对增多, 因此其乙烯齐聚的催化性能更优. 本研究结果对理解活性中心结构和合理设计催化剂提供参考.

关键词: 负载镍催化剂, 无定型硅铝, 傅里叶变换红外, 活性中心, 乙烯齐聚

Abstract:

Abstract: The structure of Ni active sites supported on amorphous silica-alumina supports with different contents of Al₂O₃ loadings in relation to their activities in ethylene oligomerization were investigated. Two kinds of Ni sites were detected by in situ FTIR-CO and H₂-TPR experiments, that are Ni²⁺ cations as grafted on weak acidic silanols and Ni²⁺ cations at ion-exchange positions. The ethylene oligomerization activities of these Ni/ASA catalysts were found an ascending tendency as the Al₂O₃ loading decreased, which could be attributed to the enriched concentration of Ni²⁺ species on acidic silanols with a weaker interaction with the amorphous silica-alumina support. These Ni²⁺ species were more easily to be evolved into Ni⁺ species, which has been identified to be the active sites of ethylene oligomerization. Thus, it seems reasonable to conclude that Ni²⁺ species grafted on acidic silanols were the precursors of active sites.

Key words: Supported nickle catalyst, Amorphous silica-alumina, FT-IR, Active sites, Ethylene oligomerization

续晶华, 王瑞锋, 张亚茹, 李林, 严文君, 王俊英, 刘国东, 苏雄, 黄延强, 张涛. 无定形硅铝负载镍催化剂上乙烯齐聚反应的活性位点结构鉴定[J]. 催化学报, 2021, 42(12): 2181-2188.

Jinghua Xu, Ruifeng Wang, Yaru Zhang, Lin Li, Wenjun Yan, Junying Wang, Guodong Liu, Xiong Su, Yanqiang Huang, Tao Zhang. Identification of the structure of Ni active sites for ethylene oligomerization on an amorphous silica-alumina supported nickel catalyst[J]. Chinese Journal of Catalysis, 2021, 42(12): 2181-2188.

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图/表 7

Fig. 1. (a) 27Al NMR spectra of ASA supports with different contents of Al2O3 loadings; (b) The concentration of AlIV species as a function of Al2O3 loadings.

Scheme 1. Structural schematic representation of H atoms with (a) an ion-exchange position and (b) an acidic silanol position.

Fig. 2. Pyridine FT-IR spectra of Ni/ASA catalysts with different amount of Al2O3 loadings. The solid and dotted line indicate the pyridine-adsorption FT-IR spectra on the catalysts which were degassed at 150 and 350 °C after a saturated adsorption of pyridine, respectively.

Fig. 3. (a) DRIFT spectra of Ni/ASA catalysts with different amounts of Al2O3 loadings; (b) The fitted DRIFT spectra in an amplified wave number range of 2180-2200 cm-1. The FTIR spectra were recorded following an evacuation process until the physically adsorbed CO was desorbed.

Fig. 4. H2-TPR profiles of the Ni/ASA samples with different contents of Al2O3 loadings.

Fig. 5. C2H4-TPD spectra of Ni/ASA samples with different contents of Al2O3 loadings.

Fig. 6. Ethylene oligomerization activities of Ni/ASA catalysts with different contents of Al2O3 loadings. Reaction conditions: 0.5 g catalyst, 50% C2H4 balanced with N2 (15 mL min-1).

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无定形硅铝负载镍催化剂上乙烯齐聚反应的活性位点结构鉴定

Identification of the structure of Ni active sites for ethylene oligomerization on an amorphous silica-alumina supported nickel catalyst

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