钯核数与乙炔半氢化催化活性及选择性之间的关系

doi:10.1016/S1872-2067(26)64982-0

催化学报 ›› 2026, Vol. 85: 384-393.DOI: 10.1016/S1872-2067(26)64982-0

钯核数与乙炔半氢化催化活性及选择性之间的关系

Polina Lavrik^a, Jurjen Cazemier^a, Mohamed N. Hedhili^b, Sudheesh K. Veeranmaril^a, Abdallah Nassereddine^c, Antonio Aguilar-Tapia^d, Marina Chernova^a, Jean-Louis Hazemann^c, Alla Dikhtiarenko^b, Javier Ruiz-Martínez^a()

^a 阿卜杜拉国王科技大学物理科学与工程学院, 催化、纳米材料与光谱学小组, 图瓦尔, 沙特阿拉伯
^b 阿卜杜拉国王科技大学中心实验室, 图瓦尔, 沙特阿拉伯
^c 格勒诺布尔阿尔卑斯大学内尔研究所, 格勒诺布尔, 法国
^d 格勒诺布尔阿尔卑斯大学格勒诺布尔分子化学研究所, 格勒诺布尔, 法国

收稿日期:2025-09-25 接受日期:2025-11-14 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: javier.ruizmartinez@kaust.edu.sa (J. Ruiz-Martínez).

Relationship between palladium nuclearity and catalytic activity and selectivity in acetylene semi-hydrogenation

^a Catalysis, Nanomaterials, and Spectroscopy group (CNS), Physical Science and Engineering (PSE) Division, King Abdullah University of Science and Technology, Thuwal 23955, Saudi Arabia
^b King Abdullah University of Science and Technology, KAUST Core Labs, Thuwal 23955, Saudi Arabia
^c Institut Néel, UPR 2940 CNRS - Université Grenoble Alpes, Grenoble F-38000, France
^d Institut de Chimie Moléculaire de Grenoble, UAR 2607 CNRS, Université Grenoble Alpes, Grenoble F-38000, France

Received:2025-09-25 Accepted:2025-11-14 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: javier.ruizmartinez@kaust.edu.sa (J. Ruiz-Martínez).
About author:Author contributions
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.
P.L.: XRD, STEM characterization, data analysis, interpretation, manuscript drafting and editing; J.C.: catalytic experiments, data analysis, XAS data acquisition; M.N.H.: XPS characterization, data analysis; S.K.V.: XAS characterization, data analysis; A.N.: XAS characterization, data analysis: A.A.-T.: XAS characterization; M.C.: catalytic experiments, data analysis; J.-L.H.: XAS characterization; A.D.: PDF characterization, data analysis; J.R.-M.: conceptualization, supervision, manuscript drafting and editing, funding acquisition.

摘要/Abstract

摘要：

优化乙炔半加氢反应催化剂中贵金属的利用率和稳定性, 同时保持高活性和乙烯选择性, 对于催化剂的工业应用至关重要. 本文通过控制负载在氮掺杂碳上的单原子Pd催化剂的还原温度, 以调节Pd物种的分布与比例, 并量化它们对乙炔半氢化的贡献. X射线吸收近边结构线性组合拟合和扩展X射线吸收精细结构(EXAFS)小波变换分析, 辅以反应条件下的原位EXAFS, 解析了从孤立的Pd原子(Pd₁)到2-3个原子簇(Pd_2/3)、再到团簇和纳米粒子的演化过程. 200 °C还原可在钯单原子体系中形成约9%的Pd_2/3聚集体. 低转化率下的动力学测试表明, Pd_2/3的活性是Pd₁的10倍, 同时保持了高乙烯选择性和低乙烷生成; 原位EXAFS证实了这些Pd原子簇的稳定性. 将还原温度提高到400 °C可消除Pd_2/3, Pd团簇的单点转化频率约是Pd₁的25-30倍, 但乙烯选择性略有降低. 在600 °C还原后, 催化剂含有34±6%的Pd纳米粒子和17±6%的团簇, 可实现高转化率, 但乙烯选择性降至55%, 显著加剧乙烷的生成, 这与较大尺寸的Pd颗粒上乙炔过度氢化一致. 这些结果在Pd核活性和每位点动力学之间建立了定量联系.

关键词: 多相催化, 乙炔半加氢, Pd单原子催化剂, Pd聚集体, Pd簇, 构效关系

Abstract:

Optimizing the noble metal utilization and stability in catalysts for acetylene semi-hydrogenation reaction while maintaining high activity and ethylene selectivity is crucial for catalyst implementation on the industrial scale. Here we tune the reduction temperature of a single-atom Pd catalyst supported on N-doped carbon to regulate the populations of Pd species and quantify their contributions to acetylene semi-hydrogenation. X-ray absorption near-edge structure linear-combination fitting and extended X-ray absorption fine structure (EXAFS) wavelet transform analysis, complemented by in-situ EXAFS under reaction conditions, resolves the evolution from isolated Pd atoms (Pd₁) to 2-3 atom ensembles (Pd_2/3), clusters, and nanoparticles. Reduction at 200 °C generates around 9% Pd_2/3 within a Pd₁ population. Kinetic deconvolution at low conversion shows that Pd_2/3 are 10 times more active than Pd₁ while maintaining high ethylene selectivity and low ethane formation; in-situ EXAFS confirms the stability of these ensembles. Increasing the reduction temperature to 400 °C eliminates Pd_2/3 in favor of Pd clusters whose per-site turnover frequency is around 25-30 times higher than that of Pd₁ but with a slight decrease in ethylene selectivity. After reduction at 600 °C, the catalyst contains 34 ± 6% Pd nanoparticles and 17 ± 6% clusters, delivering high conversion yet reducing ethylene selectivity to ’55% and increasing ethane production, consistent with over-hydrogenation on larger Pd entities. These results establish a quantitative link between Pd nuclearity and per-site kinetics.

Key words: Heterogeneous catalysis, Acetylene semi-hydrogenation, Pd single atom catalyst, Pd ensembles, Pd cluster, Structure-activity relationship

Polina Lavrik, Jurjen Cazemier, Mohamed N. Hedhili, Sudheesh K. Veeranmaril, Abdallah Nassereddine, Antonio Aguilar-Tapia, Marina Chernova, Jean-Louis Hazemann, Alla Dikhtiarenko, Javier Ruiz-Martínez. 钯核数与乙炔半氢化催化活性及选择性之间的关系[J]. 催化学报, 2026, 85: 384-393.

Polina Lavrik, Jurjen Cazemier, Mohamed N. Hedhili, Sudheesh K. Veeranmaril, Abdallah Nassereddine, Antonio Aguilar-Tapia, Marina Chernova, Jean-Louis Hazemann, Alla Dikhtiarenko, Javier Ruiz-Martínez. Relationship between palladium nuclearity and catalytic activity and selectivity in acetylene semi-hydrogenation[J]. Chinese Journal of Catalysis, 2026, 85: 384-393.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)64982-0

https://www.cjcatal.com/CN/Y2026/V85/I6/384

图/表 7

Fig. 1. Characterization of Pd/CN. XRD pattern (a) and PDF spectra (b) of Pd/CN and simulated Pd-Pd and N-doped carbon. HAADF-STEM micro-graphs in low magnification (c) and atomically resolved (d). XPS signal of Pd 3d peaks and their deconvolution (e). Pd K-edge XANES (f) and FT EXAFS (g) spectra of Pd foil, PdN4, PdO references and Pd/CN. First derivative of XANES spectra (h).

Table 1 Element distribution in Pd/CN, Pd/CN-200, Pd/CN-400, and Pd/CN-600 calculated from XPS data.

Catalyst	C, at%	N, at%	Pd, at%	O, at%	C/N ratio
Pd/CN	52.7	45.5	0.2	1.6	1.16
Pd/CN-200	52.5	45.8	0.2	1.5	1.15
Pd/CN-400	52.3	46.3	0.2	1.2	1.13
Pd/CN-600	68.9	28.2	0.8	2.1	2.42

Fig. 2. Catalytic performance in acetylene hydrogenation reaction of Pd/CN, Pd/CN-200, Pd/CN-400, and Pd/CN-600 (a) and their selectivity to ethylene (b). HAADF-STEM images of Pd/CN-200 (c), Pd/CN-400 (d), and Pd/CN-600 (e) in low magnification and atomically resolved (in the upper right corner). The yellow circles are highlighting Pd particles.

Table 2 Detected species distribution for C, N and Pd in Pd/CN, Pd/CN-200, Pd/CN-400, and Pd/CN-600 calculated from XPS data.

Catalyst		Pd/CN	Pd/CN-200	Pd/CN-400	Pd/CN-600
C species, %	C=C/C-C	22	28	23	68
	C-N/C-O	19	19	18	19
	NC=N/C=O	57	51	57	6
	O-C=O	—	—	—	3
	Shake-up satellites	2	2	2	4
N species, %	C-N=C	64	64	63	55
	N-(C)₃	19	19	20	20
	C-N-H	11	11	11	18
	N*	—	—	—	3
	Shake-up satellites	6	6	6	4
Pd species, %	Pd²⁺	100	100	100	94
Pd species, %	Pd⁰	—	—	—	6

Fig. 3. XANES spectra of Pd/CN, Pd/CN-200, Pd/CN-400, Pd/CN-600, and Pd foil reference (a). In order to prevent the oxidation on air, spectra of Pd/CN-200, Pd/CN-400 and Pd/CN-600 were measured in-situ at room temperature after reduction of Pd/CN. Composition of Pd/CN, Pd/CN-200, Pd/CN-400 and Pd/CN-600 (b) summarized from the LCF (Fig. S8) of mentioned samples with measured Pd/CN as a Pd single atom reference, simulated Pd2/3/CN, simulated Pdclusters/CN, and Pd foil as metallic Pd reference. Wavelet transform graphs for Pd/CN (c), Pd/CN-200 (d), Pd/CN-400 (e), and Pd/CN-600 (f) catalysts.

Fig. 4. In-situ FT EXAFS measured under reaction conditions for Pd/CN-200 (a), Pd/CN-400 (b), and Pd/CN-600 (c). Pd/CN represents the initial state for all the catalysts; subsequent spectra were acquired after catalyst reduction. The reaction gases were introduced into the reactor and the catalysts were heated up to 85 and 135 °C with the ramp of 10 °C/min at which temperatures the spectra under the reaction conditions were obtained.

Table 3 TOF results for Pd/CN, Pd/CN-200, and Pd/CN-400 catalysts at 75 and 100 °C; calculated TOF of individual Pd1/CN, Pd2/3/CN, and Pdclusters/CN at the same temperatures if they would be the only types of species present in the catalyst in the same amount of moles.

Temperature, °C	TOF, h^-1			Estimated TOF of individual species, h^-1
Temperature, °C	Pd/CN	Pd/CN-200	Pd/CN-400	Pd₁/CN	Pd_2/3/CN	Pd_clusters/CN
75	3.2	4.9	11.4	3.2	21.9	77.4
100	6.9	12.6	29.3	6.9	70.5	210.7

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钯核数与乙炔半氢化催化活性及选择性之间的关系

Relationship between palladium nuclearity and catalytic activity and selectivity in acetylene semi-hydrogenation

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