合金纳米颗粒原子级分散制备的双位点催化剂中单点Ag1对Pd1在炔烃双烷氧羰基化反应中的促进作用

doi:10.1016/S1872-2067(23)64631-5

催化学报 ›› 2024, Vol. 59: 282-292.DOI: 10.1016/S1872-2067(23)64631-5

合金纳米颗粒原子级分散制备的双位点催化剂中单点Ag₁对Pd₁在炔烃双烷氧羰基化反应中的促进作用

李星局^a^,^c^,¹, 李峥^b^,¹, 冯四全^a^,¹, 宋宪根^a^,^*(), 严丽^a, 母佳利^a, 袁乔^a, 宁丽丽^a, 陈维苗^a, 韩仲康^b^,^*(), 丁云杰^a^,^c^,^d^,^*()

^a中国科学院大连化学物理研究所, 洁净能源国家实验室(筹), 辽宁大连 116023
^b浙江大学材料科学与工程学院, 浙江杭州 310027
^c中国科学技术大学化学物理系, 安徽合肥 230026
^d中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023

收稿日期:2023-12-08 接受日期:2024-02-18 出版日期:2024-04-18 发布日期:2024-04-15
通讯作者: *电子邮箱: dyj@dicp.ac.cn (丁云杰), xiangensong@dicp.ac.cn (宋宪根), hanzk@zju.edu.cn (韩仲康).
作者简介:
¹共同第一作者.
基金资助:
中国科学院稳定支持基础研究领域青年团队计划(YSBR-022);国家自然科学基金(22372161);国家自然科学基金(22108275);国家自然科学基金(22108276);国家自然科学基金(22102147);中国科学院战略性先导科技专项(XDA29040400);中国科学院青年创新促进会(2022179);中国科学院青年创新促进会(2021181);浙江省自然科学基金(LQ21B030009)

Promotional role of Ag₁ on Pd₁ in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation

Xingju Li^a^,^c^,¹, Zheng Li^b^,¹, Siquan Feng^a^,¹, Xiangen Song^a^,^*(), Li Yan^a, Jiali Mu^a, Qiao Yuan^a, Lili Ning^a, Weimiao Chen^a, Zhongkang Han^b^,^*(), Yunjie Ding^a^,^c^,^d^,^*()

^aDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bSchool of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
^cDepartment of Chemical Physics, University of Science and Technology of China, Hefei 230026, Anhui, China
^dState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2023-12-08 Accepted:2024-02-18 Online:2024-04-18 Published:2024-04-15
Contact: *E-mail: xiangensong@dicp.ac.cn (X. Song), hanzk@zju.edu.cn (Z. Han), dyj@dicp.ac.cn (Y. Ding).
About author:
¹Contributed equally to this work.
Supported by:
The CAS Project for Young Scientists in Basic Research(YSBR-022);The National Natural Science Foundation of China(22372161);The National Natural Science Foundation of China(22108275);The National Natural Science Foundation of China(22108276);The National Natural Science Foundation of China(22102147);The Strategic Priority Research Program of the Chinese Academy of Sciences(XDA29040400);The Youth Innovation Promotion Association of the Chinese Academy of Sciences(2022179);The Youth Innovation Promotion Association of the Chinese Academy of Sciences(2021181);Zhejiang Provincial Natural Science Foundation of China(LQ21B030009)

摘要/Abstract

摘要：

炔烃烷氧羰基化反应是一种原子经济反应, 可以生成α,β-不饱和羧酸、二羧羧酸酯及其衍生物. 其中, 乙炔的双烷氧羰基化产物(丁烯二酸二酯)可通过两段加氢制备1,4-丁二醇, 该反应路径对于生产生物可降解材料聚丁二酸丁二醇酯(PBS)具有重要意义. 然而, 目前广泛应用的均相Pd基催化体系存在催化剂分离困难、金属流失以及需要添加有机膦配体或各种磺酸助剂等问题, 这不仅增加了制备成本, 还可能引入不必要的杂质. 此外, 尽管纳米催化剂在催化领域有着广泛的应用, 但大多数纳米催化剂在炔烃双烷氧基羰基化反应中仍表现出反应活性低和稳定性差的问题, 这限制了其在工业生产中的应用. 相比之下, 多相单金属点催化剂因其100%的原子利用率和较好的催化活性而备受关注. 然而, 由于多相单金属点催化剂具有相对简单的结构和配位环境, 其应用仍受到一定的限制. 为了克服这一难题, 合成具有不同金属的双位点催化剂成为了一个研究热点. 双位点催化剂有望进一步释放单金属位点催化剂的潜力, 提高反应活性和稳定性. 然而, 尽管双位点催化剂具有巨大的应用前景, 但目前仍面临着制备方法的挑战. 如何设计并实用可行地制备出具有高效催化性能的双位点催化剂, 是当前科研领域亟待解决的问题.

本文提出一种由CO/CH₃I混合物诱导分散Pd-Ag合金纳米颗粒的处理方法, 用于制备Pd₁-Ag₁/AC双位点催化剂. 利用X射线衍射、X射线光电子能谱和高角环形暗场扫描透射电子显微镜等方法对分散过程进行表征. 结果表明, 在分散过程中, CO和CH₃I与金属发生协同作用, 通过配位生成一种独特的双核络合物(PdI₂(CO)-I₂-AgI)结构. 这种络合物结构逐一从合金纳米颗粒上剥落, 直至完成原子级的分散. 乙炔双烷氧羰基化反应结果表明, 与单金属Pd₁/AC相比, 在相同反应条件下, 双位点Pd₁-Ag₁/AC催化剂上的乙炔转化率提高了2倍. 同时, 在保持丁烯二酸二酯选择性为98%的情况下, 该催化剂循环使用10次后催化剂性能未见明显变化. 炔烃底物拓展结果表明, Pd₁-Ag₁/AC的协同作用不仅可以提高催化活性, 而且在高位阻存在的情况下可以提高产物的立体选择性, 这表明双位点协同促进作用对炔烃双羰基化反应具有良好的普适性. 微分吸附量热表征结果证明了通过碘配体桥连的Pd₁和Ag₁单金属点之间的协同效应可以增强催化剂对乙炔的吸附能力. 此外, 结合拓展边X射线精细结构等实验结果, 对催化剂的结构变化和反应机理进行了进一步的探究. 第一性原理计算得到的反应能垒和过渡态结果表明, 乙炔吸附是反应的速率决定步骤. 与Pd₁/AC相比, Pd₁-Ag₁/AC催化剂在反应决速步上表现出了更低的活化能, 这从热力学和动力学两个层面解释了其具有更好催化性能的原因. Bader电荷分析和投影态密度计算的结果表明, 由于Ag₁位点的引入, 使Pd₁-Ag₁/AC催化剂的电荷转移能力和吸附能力均得到增强. 相较于Pd₁/AC, Pd₁-Ag₁/AC具有更低的形成能, 表明Ag₁位点不仅可以提升催化活性, 也可以增强双位点结构的稳定性. 因此, 在催化反应中, Ag₁位点的存在起到了重要的促进作用, 使得Pd₁-Ag₁/AC催化剂表现出更优异的性能.

综上, 本文制备的双位点Pd₁-Ag₁/AC催化剂在乙炔双烷氧羰基化反应中表现出较好的催化活性和稳定性, 证明了双位点协同效应的重要性, 为高效催化剂的设计和应用提供了新的思路.

关键词: 协同促进作用, 双位点催化剂, 原子级分散, 合金纳米颗粒, 炔烃双烷氧羰基化, 稳定性

Abstract:

Heterogeneous single-metal-site catalysts frequently encounter issues related to the poor stability of their coordination structures, hindering their industrial applications. Synthesizing bimetallic single-metal-site catalysts with two closely connected single sites may realize the full potential of single-site catalysts. Herein, we present a “top-down” dispersion process to prepare bimetallic single-metal-site catalysts from Pd-Ag alloy nanoparticles induced by CO and CH₃I mixture, with the unique binuclear complex structure of Pd₁-Ag₁ established as PdI₂(CO)-I₂-AgI by combined characterization. The Pd₁-Ag₁/activated carbon (AC) catalyst showed a three times increase in conversion for acetylene dialkoxycarbonylation compared to Pd₁/AC, owing to the promotive effect of the single-Ag-site via the binuclear complex configuration. Moreover, Pd₁-Ag₁/AC showed 98% selectivity for 1,4-unsaturated dicarboxylic acid esters over ten cycles without apparent decay, with the activated adsorption amount of acetylene doubled and the reduction of active Pd₁^δ⁺ species partially inhibited. According to density functional theory calculations, the Pd₁-Ag₁/AC catalyst exhibited a substantially lower reaction energy barrier of 0.45 eV for the rate-determining step compared with that of the Pd₁/AC catalyst (1.06 eV). This study provides insight into the preparation and synergetic catalysis of bimetallic single-metal-site catalysts.

Key words: Promotive effect, Bimetallic single-metal-sites catalysts, Atomic dispersion, Alloy nanoparticles, Alkyne dialkoxycarbonylation, Durability

李星局, 李峥, 冯四全, 宋宪根, 严丽, 母佳利, 袁乔, 宁丽丽, 陈维苗, 韩仲康, 丁云杰. 合金纳米颗粒原子级分散制备的双位点催化剂中单点Ag₁对Pd₁在炔烃双烷氧羰基化反应中的促进作用[J]. 催化学报, 2024, 59: 282-292.

Xingju Li, Zheng Li, Siquan Feng, Xiangen Song, Li Yan, Jiali Mu, Qiao Yuan, Lili Ning, Weimiao Chen, Zhongkang Han, Yunjie Ding. Promotional role of Ag₁ on Pd₁ in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation[J]. Chinese Journal of Catalysis, 2024, 59: 282-292.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64631-5

https://www.cjcatal.com/CN/Y2024/V59/I4/282

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Fig. 1. (a) Schematic illustration for the synthesis of Pd1-Ag1/AC. (b) XRD patterns of Pd-Ag/AC treated with CO/CH3I at 513 K after reaction times of 0, 2, 5, 15, and 60 min. (c) HRTEM image of fresh Pd-Ag/AC. (d,e) HAADF-STEM images of samples treated with CO/CH3I for 2 min. (f) Corresponding EDS mapping to (e), the yellow dots represent I atoms, the pink dots represent Pd atoms and the red dots represent Ag atoms, 5 min (g), and 15 min (h). (i,j) Pd and Ag 3d XPS of Pd-Ag/AC treated with CO/CH3I at 513 K for 0, 2, 5, and 60 min.

Fig. 2. HRTEM (a) and HAADF-STEM (b) images of Pd1-Ag1/AC. (c,d) The R space EXAFS fitting curves of Pd-Ag/AC and Pd1-Ag1/AC. (e,f) Wavelet transform contour of Pd-Ag/AC and Pd1-Ag1/AC.

Table 1 The EXAFS fitting result of standard samples of Pd foil, Ag foil, Pd-Ag/AC and Pd1-Ag1/AC samples.

Sample	Shell	N	R (Å)	σ² (10^-3 Å²)	R-factor
Pd foil	Pd-Pd	12.0	2.74	5.3	0.004
Ag foil	Ag-Ag	12.0	2.87	9.4	0.008
Pd Pd-Ag/AC	Pd-O	0.7	2.00	3.0	0.011
Pd Pd-Ag/AC	Pd-Ag	7.8	2.78	9.0	0.011
Ag Pd-Ag/AC	Ag-O	1.2	2.04	9.5	0.015
Ag Pd-Ag/AC	Ag-Pd	8.0	2.80	7.3	0.015
Pd Pd₁-Ag₁/AC	Pd-CO	1.0	1.83	2.8	0.014
	Pd-(O=AC)	1.0	2.06	3.0
	Pd-I	3.8	2.60	3.3
Ag Pd₁-Ag₁/AC	Ag-(O=AC)	1.0	2.52	3.0	0.012
Ag Pd₁-Ag₁/AC	Ag-I	3.1	2.88	3.5	0.012

Fig. 3. (a) Activity comparison of different catalysts for acetylene dialkoxycarbonylation. Reaction conditions: catalyst (0.3 g Pd1/AC, 0.3 g Ag1/AC, 0.3 g Pd1-Ag1/AC, 0.3 g Pd-Ag/AC, 0.3 g Pd1/AC+0.3 g Ag1/AC; 0.8 wt% Pd, 1.7 wt% Ag), acetylene (8.0 mmol), CH3OH (12 mL), PCO = 2.6 MPa, Pair = 2.5 MPa, 333 K, 3.0 h. The Conv.% is the acetylene conversion and the Sel.% is the selectivity of alkyne dialkoxycarbonylation, including DMSu, DMM and DMF. (b) The reaction stability test of Pd1-Ag1/AC catalyst for acetylene dialkoxycarbonylation. Reaction conditions: catalyst (0.6 g Pd1-Ag1/AC, 0.8 wt% Pd, 1.7 wt% Ag), acetylene (8.0 mmol), CH3OH (12 mL), Pair = 2.5 MPa, PCO = 2.6 MPa, 333 K, 1.0 h. The Conv.% is the acetylene conversion and the Sel.% is the selectivity of alkyne dialkoxycarbonylation, including DMSu, DMM and DMF. (c) Pd 3d XPS of spent Pd1-Ag1/AC and spent Pd1/AC. (d) Arrhenius plots of the Pd1/AC and Pd1-Ag1/AC catalysts for C2H2 dialkoxycarbonylation.

Fig. 4. Differential heat of C2H2 adsorption over Pd1-Ag1/AC, Pd1/AC, and Ag1/AC (a), Pd-Ag/AC, Pd/AC, and Ag/AC (b).

Fig. 5. Proposed reaction mechanism comparison of acetylene dialkoxycarbonylation on Pd1-Ag1/AC (a) and Pd1/AC (b). (c) Energy diagram of the proposed catalytic cycle on Pd1-Ag1/AC and Pd1/AC and the side view of the corresponding structures. Yellow, gray, purple, red, green, and brown spheres indicate the Pd, Ag, I, O, H and C atoms, respectively.

Fig. 6. The PDOS (projected density of states) of Pd1/AC (a) and Pd1-Ag1/AC (b). Red, yellow, blue, and purple represent the d orbits of Pd, the d orbits of Ag, the p orbits of I and the s orbits of I, respectively. The black dotted line represents the center of the d-band of Pd.

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合金纳米颗粒原子级分散制备的双位点催化剂中单点Ag₁对Pd₁在炔烃双烷氧羰基化反应中的促进作用

Promotional role of Ag₁ on Pd₁ in dual-site configurations from atomic dispersion of alloy nanoparticles for alkyne dialkoxycarbonylation

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