Zn/ZSM-5催化剂中Zn物种与CO2和正丁烷耦合反应间相关性研究

doi:10.1016/S1872-2067(24)60036-7

催化学报 ›› 2024, Vol. 61: 154-163.DOI: 10.1016/S1872-2067(24)60036-7

Zn/ZSM-5催化剂中Zn物种与CO₂和正丁烷耦合反应间相关性研究

孙旭科^a^,^b, 刘荣升^a, 范改丽^a^,^c, 刘昱含^a^,^d, 叶芳秀^a^,^b, 于政锡^a^,^*(), 刘中民^a^,^b^,^*()

^a中国科学院大连化学物理研究所, 洁净能源国家实验室, 低碳催化技术国家工程研究中心, 辽宁大连 116023
^b中国科学院大学, 北京 100049
^c大连理工大学化学学院, 辽宁大连 116024
^d中国石油大学(华东)化学化工学院, 山东青岛 266580

收稿日期:2024-03-05 接受日期:2024-04-10 出版日期:2024-06-18 发布日期:2024-06-20
通讯作者: * 电子信箱: zhengxiyu@dicp.ac.cn (于政锡), liuzm@dicp.ac.cn (刘中民).
基金资助:
国家自然科学基金(21991093);国家自然科学基金(21991092);国家自然科学基金(21991090);科技部国家重点研发计划(2022YFE0116000);中国科学院战略性先导科技专项(XDA29000000)

Understanding the correlation between zinc speciation and coupling conversion of CO₂ and n-butane on zinc/ZSM-5 catalysts

Xuke Sun^a^,^b, Rongsheng Liu^a, Gaili Fan^a^,^c, Yuhan Liu^a^,^d, Fangxiu Ye^a^,^b, Zhengxi Yu^a^,^*(), Zhongmin Liu^a^,^b^,^*()

^aNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cSchool of Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China
^dCollege of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong, China

Received:2024-03-05 Accepted:2024-04-10 Online:2024-06-18 Published:2024-06-20
Contact: * E-mail: zhengxiyu@dicp.ac.cn (Z. Yu), liuzm@dicp.ac.cn (Z. Liu).
Supported by:
National Natural Science Foundation of China(21991093);National Natural Science Foundation of China(21991092);National Natural Science Foundation of China(21991090);National Key Research and Development Program of China(2022YFE0116000);Strategic Priority Research Program of the Chinese Academy of Sciences(XDA29000000)

摘要/Abstract

摘要：

随着全球温室气体排放的持续增长, 二氧化碳(CO₂)的高效转化与利用已成为应对气候变化、推动可持续发展的重要途径之一. 在本课题组的前期研究中, 以正丁烷为模型化合物, 成功实现了H-ZSM-5分子筛催化CO₂与正丁烷发生耦合反应. 实验还发现, 通过对H-ZSM-5进行Zn改性, 可以显著提高其催化性能, 这为CO₂的高效转化和利用提供了新的研究方向. 然而, 目前关于Zn-ZSM-5催化剂中Zn物种的具体存在状态及其与耦合反应性能之间的关系尚不明确, 这限制了高效催化剂的进一步设计. 因此, 深入探究Zn物种在Zn-ZSM-5催化剂中的存在状态及其与催化性能之间的关联机制, 从而设计和开发更高效的CO₂转化催化剂已成为当务之急.
本文通过紫外-可见光漫反射光谱、X-射线光电子能谱和¹H魔角旋转-核磁共振等多种技术系统地表征了Zn-ZSM-5分子筛中酸性中心和Zn物种存在状态的演变过程, 讨论了Zn物种活性中心与耦合反应之间的构-效关系, 阐明了耦合反应的机理. 研究表明, Zn-ZSM-5分子筛中Zn物种主要以ZnO团簇、Zn-OH⁺和(Zn-O-Zn)²⁺的形式存在, 且其含量随Zn负载量的变化而改变. 其中, ZnO团簇及(Zn-O-Zn)²⁺物种的含量随Zn负载量的增加而上升, 而Zn-OH⁺物种含量则先上升后下降, 这是由于部分Zn-OH⁺物种转化为(Zn-O-Zn)²⁺物种. 在CO₂与正丁烷的耦合反应中, 正丁烷的转化受到Brønsted酸位点的减少、Zn活性位点的形成以及粗晶ZnO物种的堆积等多种因素的影响. Zn-OH⁺物种是主要的CO₂催化转化活性中心, 而芳烃的生成则主要受Zn-OH⁺和(Zn-O-Zn)²⁺物种的影响. Zn-OH⁺和(Zn-O-Zn)²⁺物种均具有较强的脱氢性能, 可通过脱氢路径促进芳烃的生成. Zn5%-ZSM-5 (Zn负载量为5 wt%)样品表现出最优的催化性能: 正丁烷转化率为94.71%, CO₂转化率为30.43%, 芳烃选择性为53.71%. 原位实验进一步证实了内酯、羧酸和不饱和醛酮等含氧化合物作为中间体的存在. 基于上述研究, 我们提出了Zn-ZSM-5上CO₂和正丁烷耦合的反应机理, 主要包括以下三条反应路径: (1) 在Zn-OH⁺物种的催化作用下, 正丁烷和CO₂首先被耦合活化形成内酯, 随后经过一系列反应形成羧酸、酸酐和其他含氧化合物, 最终通过复杂的反应生成芳烃. (2) 部分CO₂在Zn-OH⁺物种的催化下, 通过逆水煤气变换(RWGS)反应以及与烃类化合物的干重整反应生成CO. 这些CO随后在Zn-OH⁺物种的催化下与烯烃发生耦合反应, 最终生成芳烃产物. (3) 正丁烷在Zn-OH⁺和(Zn-O-Zn)²⁺物种的催化下, 发生脱氢和异构化反应产生烯烃. 部分烯烃可通过与CO耦合或烯烃发生聚合、环化、脱氢等过程生成芳烃产物.
综上所述, 本文深入探讨了CO₂与正丁烷在Zn-ZSM-5催化剂上的耦合反应机制. 通过系统研究, 建立了催化剂中Zn物种与催化性能之间的构-效关系, 并提出了耦合反应的具体路径. 本文不仅有助于深入理解Zn-ZSM-5的催化作用机制, 而且对于未来设计和开发更高效的催化体系具有重要的参考价值.

关键词: 耦合反应, CO₂利用, 锌的引入, Zn-OH⁺, (Zn-O-Zn)²⁺, ZSM-5

Abstract:

The coupling reaction of alkanes and CO₂ into high value-added bulk chemical products is a promising way for CO₂ utilization. The Zn-introduced ZSM-5 catalyst plays an essential role in this process; however, the correlation between the catalytic performance and Zn species of the catalyst has yet to be established. Herein, the structural properties, the acid sites, and the existence status of the Zn species in the Zn-introduced catalysts were systematically characterized by several techniques. And the influence of the state of Zn species in the coupling reaction was discussed. The results indicate that the Zn species exist in the form of ZnO cluster, Zn-OH⁺, and (Zn-O-Zn)²⁺ species, thereinto (Zn-O-Zn)²⁺ species are produced by the Zn-OH⁺ group with the increasing Zn loading. The decrease of Brønsted acid sites, the formation of newly active sites caused by Zn species, and the accumulation of coarse ZnO species, are responsible for the change of n-butane conversion. The Zn-OH⁺ group serves as the primary catalytic center for the conversion of CO₂. Both the Zn-OH⁺ group and the (Zn-O-Zn)²⁺ species enhance the dehydrogenation performance of the Zn-introduced catalysts, thereby promoting the generation of aromatics. The Zn5%-ZSM-5 sample showed the most excellent catalytic performance; the n-butane conversion was 94.71%, the CO₂conversion was 30.43%, and the aromatics selectivity was 53.71%. Simultaneously, we propose a more specific mechanism for the coupling reaction.

Key words: Coupling reaction, CO₂ utilization, Zn-introduced, Zn-OH⁺, (Zn-O-Zn)²⁺, ZSM-5

孙旭科, 刘荣升, 范改丽, 刘昱含, 叶芳秀, 于政锡, 刘中民. Zn/ZSM-5催化剂中Zn物种与CO₂和正丁烷耦合反应间相关性研究[J]. 催化学报, 2024, 61: 154-163.

Xuke Sun, Rongsheng Liu, Gaili Fan, Yuhan Liu, Fangxiu Ye, Zhengxi Yu, Zhongmin Liu. Understanding the correlation between zinc speciation and coupling conversion of CO₂ and n-butane on zinc/ZSM-5 catalysts[J]. Chinese Journal of Catalysis, 2024, 61: 154-163.

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图/表 7

Fig. 1. Characterization results of all samples. (a) N2 sorption isotherms; (b) XRD patterns; (c) 27Al MAS NMR spectra; (d) 29Si MAS NMR spectra.

Fig. 2. (a) UV-vis spectra of all samples. (b) XPS spectra of Zn 2p3/2 for the Zn-introduced samples. (c) The distributions and content of Zn species in the Zn-introduced samples with increasing Zn loading and provided data are determined from the combination of XPS and XRF. (d) 1H MAS NMR spectra with corresponding deconvolution results of all samples. FTIR (e) and Py-FTIR (f) spectra of all samples.

Table 1 Zn species distribution of the Zn-introduced samples.

Sample	Zn by type
Sample	Total ^a (wt%)	Zn_fr ^b (wt%)	ZnO ^b (wt%)	Zn_fr/ZnO ^b
Zn3%-ZSM-5	3.12	1.93	1.19	1.62
Zn5%-ZSM-5	5.10	2.75	2.35	1.17
Zn7%-ZSM-5	6.92	2.91	4.01	0.73

Table 2 OH species concentration of all samples.

Sample	OH concentration/mmol g^‒1
Sample	Si-OH-Al_(H-bond)	Si-OH-Al	Al-OH	Si-OH	Zn-OH
H-ZSM-5	1.21	0.71	0.62	0.41	0
Zn3%-ZSM-5	0.52	0.52	0.15	0.29	0.17
Zn5%-ZSM-5	0.25	0.36	0.14	0.25	0.19
Zn7%-ZSM-5	0.16	0.14	0.09	0.17	0.07

Table 3 Acidic properties of all samples.

Sample	Acidity by strength ^a (mmol g^‒1)			Acidity by type ^b (mmol g^‒1)
Sample	Strong	Weak	Total	Brønsted	Lewis	B/L
H-ZSM-5	0.509	0.763	1.272	0.775	0.497	1.56
Zn3%-ZSM-5	0.404	0.863	1.267	0.140	1.127	0.12
Zn5%-ZSM-5	0.349	0.906	1.255	0.113	1.142	0.10
Zn7%-ZSM-5	0.331	0.917	1.248	0.067	1.181	0.06

Fig. 3. Catalytic performances of coupling reaction on all samples with the time on stream (TOS). (a) H-ZSM-5; (b) Zn3%-ZSM-5; (c) Zn5%-ZSM-5; (d) Zn7%-ZSM-5. Reaction conditions: 1 g sample, P = 1 bar, T = 550 °C, total WHSV = 5 h?1 (WHSVn-butane = 4.20 h?1, WHSVCO2 = 0.80 h?1), CO2/n-butane = 0.25 (molar ratio), TOS = 145 min. Notes: The product distribution of aromatics and others were shown in Figs. S5 and S6, respectively. The detailed product distribution, reactant conversion, and important product selectivity were shown in Tables S2 and S3.

Fig. 4. Proposed mechanism for the coupling reaction on the Zn-introduced catalysts.

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Zn/ZSM-5催化剂中Zn物种与CO₂和正丁烷耦合反应间相关性研究

Understanding the correlation between zinc speciation and coupling conversion of CO₂ and n-butane on zinc/ZSM-5 catalysts

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