调控炔烃半氢化反应的催化选择性: 实验和理论的最新进展

doi:10.1016/S1872-2067(21)64036-6

摘要/Abstract

摘要：

由于短链烯烃的广泛应用, 炔烃选择性加氢制备烯烃是一个非常重要的石油化学催化过程. 其中最简单的乙炔半氢化, 吸引了众多研究者的广泛研究, 是催化选择性调控的一个非常重要反应. 工业上, 由石油蒸汽裂解得到的乙烯往往混有微量(∼1%)的乙炔, 它会毒化乙烯聚合反应时所使用的Ziegler-Natta催化剂, 因此需要降低乙炔含量至5 × 10^-6以下. 这要求加氢催化剂具有很高的乙炔转化率(> 99%)和乙烯选择性(> 80%). Pd基催化剂因低温下的具有高活性, 是最常用的炔烃半氢化催化剂, 其中Pd-Ag合金催化剂已在工业界应用了数十年. 近十几年来, 新型的乙炔半氢化催化剂不断被提出, 其催化选择性的研究也取得了很大的进展.

本文对炔烃半氢化反应的最新研究进展进行了总结. 以乙炔加氢为例, 介绍了其工业反应的条件、反应的网络以及潜在的副反应. 归纳了提高加氢选择性的常见方法, 并总结了近十几年报道的性能较好的乙炔半氢化催化剂. 重点阐述了近年研究对加氢选择性的深入理解: Pd基催化剂的表面结构会随着反应条件和反应过程动态变化, 从而影响加氢选择性. 利用程序升温脱附和X射线光电子能谱研究催化剂的表面性质和相应的催化性能, 确认了次表层H和表层C的出现, 并发现了它们对催化选择性的重要影响. 理论模拟(DFT, SSW-NN)建立了催化活性中心的原子结构, 发现了Ag在PdAg合金表面的富集, 以及在反应条件下Pd原子偏析到(111)面, 阐明了晶面结构与催化选择性之间的定量关联. 综上, 实验和理论的结合不仅深化了研究者对加氢选择性的理解, 也为设计更好的催化剂提供了有效的指导.

关键词: 炔烃半氢化, 催化选择性, 表面科学, 机器学习, 神经网络势

Abstract:

Researchers have been attempting to characterize heterogeneous catalysts in situ in addition to correlating their structures with their activity and selectivity in spite of many challenges. Here, we review recent experimental and theoretical advances regarding alkyne selective hydrogenation by Pd-based catalysts, which are an important petrochemical reaction. The catalytic selectivity for the reaction of alkynes to alkenes is influenced by the composition and structure of the catalysts. Recent progress achieved through experimental studies and atomic simulations has provided useful insights into the origins of the selectivity. The important role of the subsurface species (H and C) was revealed by monitoring the catalyst surface and the related catalytic performance. The atomic structures of the Pd catalytic centers and their relationship with selectivity were established through atomic simulations. The combined knowledge gained from experimental and theoretical studies provides a fundamental understanding of catalytic mechanisms and reveals a path toward improved catalyst design.

Key words: Alkyne semihydrogenation, Catalytic selectivity, Surface science, Machine learning, Neural network potential

李晓天, 陈林, 商城, 刘智攀. 调控炔烃半氢化反应的催化选择性: 实验和理论的最新进展[J]. 催化学报, 2022, 43(8): 1991-2000.

Xiao-Tian Li, Lin Chen, Cheng Shang, Zhi-Pan Liu. Selectivity control in alkyne semihydrogenation: Recent experimental and theoretical progress[J]. Chinese Journal of Catalysis, 2022, 43(8): 1991-2000.

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https://www.cjcatal.com/CN/Y2022/V43/I8/1991

图/表 9

Fig. 1. Reaction network for acetylene hydrogenation. Blue arrows indicate the direct hydrogenation of acetylene and ethene, red arrows indicate isomerization to the asymmetric C2 species, while the green arrows indicate oligomerization to the C4 species. Arrows and lines of different sizes represent the different activation energies for the reactions (Ea < 1.5 eV for bold arrow, 1.5 eV < Ea < 2 eV for medium arrow, and Ea > 2 eV for thin arrow). Reproduced with permission [45]. Copyright 2018, American Chemical Society.

Fig. 2. Conversion (X) of acetylene and selectivity (S) for ethene, ethane, and oligomers over a Pd/γ-Al2O3 catalyst as a function of the CO:H2 ratio. Acetylene hydrogenation conditions: p(C2H2) = 0.025 bar, p(H2) = 0.125 bar, p(total) = 1 bar, T = 75 °C, SV = 16800 mL g-1 h-1. Reproduced with permission [54]. Copyright 2010, Elsevier.

Table 1 State-of-the-art catalysts for the selective hydrogenation of acetylene and their reaction parameters: conversion of acetylene (X), selectivity to ethene (S), feed gas (C2H2:H2:C2H4), space velocity (SV), and reaction temperature (T).

Type	Catalyst	X (%)	S (%)	C₂H₂:H₂:C₂H₄	SV (mL g^-1 h^-1)	T (°C)	Ref.
Pure metal	Tetra-Pd/MgAl-LDHs	93	53	0.3:0.6:32.9	10056	100	[65]
	Ga₂O₃-Pd/Al₂O₃	77	54	0.3:0.6:33.1	17060	100	[66]
	Cu/Al₂O₃	100	84	1:10:50	8 × 10⁵	179	[61]
	Au/SiO₂	82	78	0.8:16:83.2	92000	225	[62]
Alloy & intermetallics	PdAg₄	85	49	0.5:5:50	9000	200	[67]
	PdAg₃/MgAl₂O₄	95	55	0.5:10:50	40000	200	[68]
	PdAg₃/r-TiO₂	96	85	0.5:5:50	9.6 × 10⁶	80	[27]
	PdGa/Al₂O₃	83.9	82	0.5:5:50	24000	200	[31]
	Pd₂Ga/CNT	90	58.1	0.5:5:50	7.5 × 10⁶	200	[67]
	PdIn/MgAl₂O₄	96	92	0.5:5:50	2.88 × 10⁵	90	[33]
	PdIn/Al₂O₃	100	77	0.87:3.1:73	—	120	[34]
	Pd-Zn/ZnO	94	90	2:20:40	1.8 × 10⁵	80	[35]
	PdZn@ZIF-8C	70	80	0.65:5:50	48000	115	[36]
	PdBi₃/Calcite	100	99	1:20:20	1.2 × 10⁵	150	[69]
	Pd@C/CNF	100	93	0.6:1.2:5.4	2.4 × 10⁵	250	[70]
	Pd₄S/CNF	100	95	0.6:1.08:5.4	60000	250	[71]
	Ni₃Ga/MgAl₂O₄	90	77	0.5:10:50	40000	200	[68]
	Ni₃Ga-MIHMs	83	80	0.65:5:50	48000	125	[72]
	NiGa/MgAl-LDHs	73	75	1:10:20	1.44 × 10⁵	185	[73]
	Ni₃Sn₂/MgAl₂O₄	80	80	0.5:10:50	40000	200	[68]
	Ni₃ZnC_0.7/oCNT	99	94	0.5:4.5:20	—	200	[74]
	NiCu/CeO₂	100	52.1	0.6:2.4:5.4	98500	—	[75]
	Al₁₃Fe₄	80	84	0.5:5:50	90000	200	[4]
	Co₂Mn_0.5Fe_0.5Ge	100	90	0.1:40:10	4500	250	[76]
Coreshell	Pd@H-Zn/Co-ZIF	80	80	0.5:5:50	—	50	[77]
	Pd/CTS	100	74	1:2:20	90000	100	[78]
	Pd/PPS	100	74	0.6:0.9:49.3	28800	100	[79]
Single atom	Pd₁/ND@G	100	90	1:10:20	60000	180	[80]
	Pd₁/MPNC	83	82	0.5:5:50	2.42 × 10⁵	110	[81]
	AgPd_0.01/SiO₂	67	87	1:20:20	60000	160	[82]
	CuPd_0.006/SiO₂	100	85	1:20:20	60000	160	[39]
	Na-Ni@CHA	100	90	0.5:8:50	15000	170	[83]
	Cu₁/ND@G	95	98	1:10:20	3000	200	[60]
	Cu₁/Al₂O₃	100	91	1:10:50	8 × 10⁵	188	[61]
Metallic oxide	CeO₂	86	81	1:30:0	—	250	[84]
Metallic oxide	In₂O₃	100	85	1:30:0	—	350	[85]

Type	Catalyst	X (%)	S (%)	C₂H₂:H₂:C₂H₄	SV (mL g^-1 h^-1)	T (°C)	Ref.
Pure metal	Tetra-Pd/MgAl-LDHs	93	53	0.3:0.6:32.9	10056	100	[65]
	Ga₂O₃-Pd/Al₂O₃	77	54	0.3:0.6:33.1	17060	100	[66]
	Cu/Al₂O₃	100	84	1:10:50	8 × 10⁵	179	[61]
	Au/SiO₂	82	78	0.8:16:83.2	92000	225	[62]
Alloy & intermetallics	PdAg₄	85	49	0.5:5:50	9000	200	[67]
	PdAg₃/MgAl₂O₄	95	55	0.5:10:50	40000	200	[68]
	PdAg₃/r-TiO₂	96	85	0.5:5:50	9.6 × 10⁶	80	[27]
	PdGa/Al₂O₃	83.9	82	0.5:5:50	24000	200	[31]
	Pd₂Ga/CNT	90	58.1	0.5:5:50	7.5 × 10⁶	200	[67]
	PdIn/MgAl₂O₄	96	92	0.5:5:50	2.88 × 10⁵	90	[33]
	PdIn/Al₂O₃	100	77	0.87:3.1:73	—	120	[34]
	Pd-Zn/ZnO	94	90	2:20:40	1.8 × 10⁵	80	[35]
	PdZn@ZIF-8C	70	80	0.65:5:50	48000	115	[36]
	PdBi₃/Calcite	100	99	1:20:20	1.2 × 10⁵	150	[69]
	Pd@C/CNF	100	93	0.6:1.2:5.4	2.4 × 10⁵	250	[70]
	Pd₄S/CNF	100	95	0.6:1.08:5.4	60000	250	[71]
	Ni₃Ga/MgAl₂O₄	90	77	0.5:10:50	40000	200	[68]
	Ni₃Ga-MIHMs	83	80	0.65:5:50	48000	125	[72]
	NiGa/MgAl-LDHs	73	75	1:10:20	1.44 × 10⁵	185	[73]
	Ni₃Sn₂/MgAl₂O₄	80	80	0.5:10:50	40000	200	[68]
	Ni₃ZnC_0.7/oCNT	99	94	0.5:4.5:20	—	200	[74]
	NiCu/CeO₂	100	52.1	0.6:2.4:5.4	98500	—	[75]
	Al₁₃Fe₄	80	84	0.5:5:50	90000	200	[4]
	Co₂Mn_0.5Fe_0.5Ge	100	90	0.1:40:10	4500	250	[76]
Coreshell	Pd@H-Zn/Co-ZIF	80	80	0.5:5:50	—	50	[77]
	Pd/CTS	100	74	1:2:20	90000	100	[78]
	Pd/PPS	100	74	0.6:0.9:49.3	28800	100	[79]
Single atom	Pd₁/ND@G	100	90	1:10:20	60000	180	[80]
	Pd₁/MPNC	83	82	0.5:5:50	2.42 × 10⁵	110	[81]
	AgPd_0.01/SiO₂	67	87	1:20:20	60000	160	[82]
	CuPd_0.006/SiO₂	100	85	1:20:20	60000	160	[39]
	Na-Ni@CHA	100	90	0.5:8:50	15000	170	[83]
	Cu₁/ND@G	95	98	1:10:20	3000	200	[60]
	Cu₁/Al₂O₃	100	91	1:10:50	8 × 10⁵	188	[61]
Metallic oxide	CeO₂	86	81	1:30:0	—	250	[84]
Metallic oxide	In₂O₃	100	85	1:30:0	—	350	[85]

Fig. 3. TPD results for Pd/Al2O3 nano-catalyst and Pd(111) single crystal. Desorption peaks for C5H10 and D2 after their individual adsorption, and desorption peak for C5H10D2 after co-adsorption of C5H10 and D2 on Pd(111) (a) and on Pd/Al2O3 (b). Reprinted with permission from Ref. [88]. Copyright 2004, Elsevier.

Fig. 4. Sharp decrease in catalytic selectivity along with the α-PdH to β-PdH transition during the acetylene hydrogenation on a Pd/C catalyst. Reprinted with permission from Ref. [92]. Copyright 2020, American Chemical Society.

Fig. 5. (a) Catalytic selectivity as a function of H2 pressure in 1-pentyne hydrogenation on Pd black catalyst. (b,c) Corresponding Pd 3d5/2 XPS recorded at distinct H2 pressures (as marked by solid and open stars in (a)), over the Pd foil and the Pd black catalysts. The XPS peaks at 335 eV (solid line) correspond to metallic Pd, while the higher binding-energy peaks (dashed line) are attributed to the sum of adsorbate-induced surface components, especially the Pd-C phase. Reprinted with permission from Ref. [2]. Copyright 2008, the American Association for the Advancement of Science.

Fig. 6. (a,b) Pd-Ag-H surface contour maps for the formation free energies of Pd-Ag-H/Pd1Ag3(111) and Pd-Ag-H/Pd1Ag3(100), respectively, at 25 °C and p(H2) = 0.05 atm. (c,d) Stable surface configurations of Pd1Ag3(111) and Pd1Ag3(100), respectively, under typical reaction conditions, as identified from the Pd-Ag-H surface contour maps. Reprinted with permission from Ref. [27]. Copyright 2021, American Chemical Society.

Fig. 7. Adsorption energies of acetylene (circles) and ethene (triangles) plotted against the adsorption energy of methyl. Reprinted with permission from Ref. [1]. Copyright 2008, the American Association for the Advancement of Science.

Fig. 8. Gibbs free energy profiles for acetylene hydrogenation on (a) Pd(111), Pd4H3(111), (b) Pd(100), and Pd4H3(100). Pd and Pd4H3 are the detailed structures for α-PdH and β-PdH as determined by SSW-NN global optimization. The insets show the intermediates during the hydrogenation reactions. Color code: H atoms of adsorbates, yellow balls; H atoms bonded to adsorbates, pink balls; other H atoms, white balls; Pd atoms, indigo balls; and C atoms, gray balls). Reprinted with permission from Ref. [92]. Copyright 2020, American Chemical Society.

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