Employing PdCo/SiO2 catalyst in high activity dehydrogenation reaction of heterocyclic H2 storage carrier

doi:10.11949/0438-1157.20220857

Abstract

Abstract:

N-Ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) system was regarded as a promising hydrogen storage solution in the liquid organic hydrogen carriers (LOHC) filed. However, the design and development of high activity and selectivity dehydrogenation catalysts still chocked off the industrial application of NECZ/12H-NECZ system. Aiming to improve H₂ release efficiency of 12H-NECZ, bimetal catalyst Pd₁Co₃/SiO₂(Pd content:1.25%(mass)) with high dehydrogenation activity and high dehydrogenation selectivity was synthesized in this work. The structure properties were characterized by XPS, XRD and HRTEM. And its catalytic performance was evaluated in the dehydrogenation reaction of 12H-NECZ. Compared with commercial 5.0%(mass) Pd/SiO₂, it was indicated that the formation of PdCo alloy by the introducing of metal Co facilitated the dehydrogenation efficiency of 12H-NECZ and selectivity of NECZ. Both the reaction kinetics results and DFT calculation analyses showed the obvious decreasing of energy barriers of three elementary reactions by employing bimetal catalyst. Especially in the 2nd^{elementary reaction (8H-NECZ to 4H-NECZ), its efficiency was boosted a lot. The research content in this paper provides new ideas for revealing the mechanism of 12H-NECZ dehydrogenation reaction and designing and developing efficient catalysts for dehydrogenation reaction.}

Key words: organic hydrogen storage, catalytic dehydrogenation reaction, hydrogen, catalysis, bimetal catalyst, density functional theory, reaction kinetics, N-ethylcarbazole

摘要：

乙基咔唑/十二氢乙基咔唑（N-ethylcarbazole/dodecahydro-N-ethylcarbazole，NECZ/12H-NECZ）体系被认为在有机液体储氢领域具有较大的开发应用前景，但高活性、选择性的脱氢催化剂的设计开发制约着其工业应用。基于此，设计开发出一种具有高脱氢活性和高选择性的双金属催化剂Pd₁Co₃/ SiO₂（Pd质量分数为1.25%），对其结构进行了XPS、XRD、HRTEM等表征分析，并评价了其催化十二氢乙基咔唑的脱氢性能。与5.0%（质量分数）Pd/SiO₂相比，表明引入一定量的Co金属形成的PdCo合金可提高12H-NECZ脱氢反应效率和NECZ选择性，动力学与DFT计算发现双金属催化剂可以有效降低三步基元反应的能垒，大幅提升第二步基元反应（8H-NECZ到4H-NECZ）的脱氢反应速率。研究结果为揭示12H-NECZ脱氢反应机理和高效脱氢反应催化剂的设计与开发提供了新的思路。

关键词: 有机储氢, 催化脱氢, 氢, 催化, 双金属催化剂, 密度泛函理论, 反应动力学, 乙基咔唑

CLC Number:

TK 91

Xiang GONG, Linsen LI, Zhao JIANG. Employing PdCo/SiO₂ catalyst in high activity dehydrogenation reaction of heterocyclic H₂ storage carrier[J]. CIESC Journal, 2022, 73(10): 4448-4460.

龚翔, 李林森, 姜召. PdCo/SiO₂双金属催化剂用于杂环储氢载体的高效脱氢[J]. 化工学报, 2022, 73(10): 4448-4460.

Figures/Tables 15

Fig.1 The hydrogenation and dehydrogenation cycle process of LOHC

Fig.2 The hydrogenation and dehydrogenation reaction conditions of NECZ/12H-NECZ system

Fig.3 The three elementary reactions of H2 release process of 12H-NECZ

Fig.4 X-Ray diffraction patterns

Fig.5 XPS spectra of bimetal catalysts PdCo/SiO2 and monometal catalysts Pd/SiO2 & Co/SiO2

Table 1 XPS results of bimetal catalysts

催化剂	Pd⁰/eV		Pd ^δ⁺/eV		Co⁰/eV		Co ^δ⁺/eV		Pd⁰/Pd ^δ⁺	Co⁰/Co ^δ⁺
催化剂	3d_5/2	3d_3/2	3d_5/2	3d_3/2	3d_3/2	3d_1/2	3d_3/2	3d_1/2	Pd⁰/Pd ^δ⁺	Co⁰/Co ^δ⁺
Pd/SiO₂	335.1	340.4	336.6	341.9	—	—	—	—	84%/16%	—
Co/SiO₂	—	—	—	—	778.3	793.3	792.1	798.4	81%/19%	—
Pd₃Co₁/SiO₂	335.3	340.6	336.6	341.9	777.5	792.7	783.2	798.4	82%/18%	77%/23%
Pd₁Co₁/SiO₂	335.5	340.7	336.8	342.1	777.8	793.0	783.6	798.8	85%/15%	76%/24%
Pd₁Co₃/SiO₂	335.8	341.1	337.2	342.5	778.0	793.1	783.9	799.1	81%/19%	76%/24%

Fig.6 HRTEM images [(a), (b)] and particle size distributions (c) of Pd/SiO2; HRTEM images [(d), (e)], particle size distributions (f), mapping images [(g)—(i)] and line scanning images [(j)—(l)] of Pd1Co3/SiO2 catalyst

Fig.7 Hydrogen release amount (a) and product distributions [(b)—(f)] of 12H-NECZ dehydrogenation process on bimetal catalysts over 8 h

Table 2 H2 release amount and selectivity data of mentioned catalysts for 12H-NECZ dehydrogenation at 453 K

样品	脱氢量/%（质量）			12H-NECZ转化率/%	4H-NECZ选择性/%	NECZ选择性/%
样品	1 h	4 h	8 h	12H-NECZ转化率/%	4H-NECZ选择性/%	NECZ选择性/%
Pd/SiO₂	2.18	4.33	5.20	100	30.82	69.18
Pd₃Co₁/SiO₂	0.92	2.81	3.78	100	66.70	14.60
Pd₁Co₁/SiO₂	0.89	2.51	3.17	100	43.70	10.21
Pd₁Co₃/SiO₂	2.93	4.67	5.25	100	28.34	71.66
Pd₁Co₄/SiO₂	1.10	2.70	3.70	100	36.20	9.72
Pd₁Co₅/SiO₂	0.73	1.87	2.47	38.68	23.27	10.09
Co/SiO₂	0	0.07	0.12	4.10	1.05	0.0055

Fig.8 Summary data of 12H-NECZ release amounts by mono-metal and bimetal catalysts supported on SiO2

Table 3 Kinetic fitting results of 12H-NECZ sequential dehydrogenation process

样品

k₁/min^-1

k₂/min^-1

k₃/min^-1

R²

Pd/SiO₂

Pd₃Co₁/SiO₂

Pd₁Co₁/SiO₂

Pd₁Co₃/SiO₂

0.0276

0.0104

0.0096

0.0523

0.0192

0.0045

0.0026

0.0486

0.0031

0.0028

0.0013

0.0034

0.979

0.994

0.975

0.991

Fig.9 Optimized stable adsorption geometries of 12H-NECZ, 8H-NECZ, 4H-NECZ, and NECZ on the Pd (111) and Pd1Co3 (111) surfaces

Table 4 DFT calculated binding energies of 12H-NECZ， 8H-NECZ， 4H-NECZ， and NECZ on Pd （111） and Pd1Co3 （111） surfaces

表面	结合能/eV
表面	0H-NECZ	4H-NECZ	8H-NECZ	12H-NECZ
Pd (111)	-2.89	-2.66	-2.37	-2.16
Pd₁Co₃(111)	-5.44	-4.99	-3.98	-3.68

Table 5 Change of Gibbs free energies of three elementary reactions from 12H-NECZ dehydrogenation process to NECZ on the Pd （111） and Pd1Co3 （111） surfaces

反应路径	ΔG/eV
反应路径	Pd（111）	Pd₁Co₃（111）
12H8H+2H₂	0.96	0.85
8H4H+2H₂	1.25	0.54
4H0H+2H₂	1.36	1.14

Fig.10 DFT-calculated energy profile of 12H-NECZ dehydrogenation process to NECZ on the Pd (111) and Pd1Co3 (111) surfaces

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Employing PdCo/SiO₂ catalyst in high activity dehydrogenation reaction of heterocyclic H₂ storage carrier

PdCo/SiO₂双金属催化剂用于杂环储氢载体的高效脱氢

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