PdCo/SiO2双金属催化剂用于杂环储氢载体的高效脱氢

doi:10.11949/0438-1157.20220857

化工学报 ›› 2022, Vol. 73 ›› Issue (10): 4448-4460.DOI: 10.11949/0438-1157.20220857

• 催化、动力学与反应器 • 上一篇下一篇

PdCo/SiO₂双金属催化剂用于杂环储氢载体的高效脱氢

龚翔(), 李林森, 姜召()

西安交通大学化学工程系，陕西省能源化工过程强化重点实验室，陕西西安 710049

收稿日期:2022-06-21 修回日期:2022-09-07 出版日期:2022-10-05 发布日期:2022-11-02
通讯作者: 姜召
作者简介:龚翔（1994—），男，博士研究生，gx2017@stu.xjtu.edu.cn
基金资助:
国家自然科学基金项目(22075225);世界一流大学（学科）建设与中央高校特色发展专项引导资金项目(PY3A076);中国博士后科学基金项目(2020T130508);陕西省自然科学基础研究计划项目(2020JQ-023);中央高校基本科研业务费专项资金项目(cxtd2017004);太原理工大学煤炭清洁高效利用国家重点实验室项目(SKL202105);陕西省创新人才推进计划-科技创新团队项目(2019TD-039);碑林区科研经费项目(GX2017)

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

Xiang GONG(), Linsen LI, Zhao JIANG()

Department of Chemical Engineering, Xi’an Jiaotong University, Shaanxi Key Laboratory of Energy Chemical Process Intensification, Xi’an 710049, Shaanxi, China

Received:2022-06-21 Revised:2022-09-07 Online:2022-10-05 Published:2022-11-02
Contact: Zhao JIANG

摘要/Abstract

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

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

中图分类号:

TK 91

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.

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.

图/表 15

图1 有机液体氢载体的加脱氢循环示意图

Fig.1 The hydrogenation and dehydrogenation cycle process of LOHC

图2 乙基咔唑/十二氢乙基咔唑体系加脱氢反应条件

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

图3 十二氢乙基咔唑脱氢过程的3步基元反应

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

图4 X射线衍射图

Fig.4 X-Ray diffraction patterns

图5 双金属催化剂PdCo/SiO2和单金属催化剂Pd/SiO2及Co/SiO2的XPS图

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

表1 双金属催化剂XPS表征结果

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%

图6 Pd/SiO2的HRTEM图[（a）,（b）]和粒径分布（c）；Pd1Co3/SiO2的HRTEM图[（d）,（e）]、粒径分布（f）、mapping图[（g）~（i）]和线扫图[（j）~（l）]

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

图7 8 h反应脱氢量（a）和双金属催化剂8h脱氢反应产物分布[（b）~（f）]

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

表2 不同催化剂在453 K温度下反应脱氢量和选择性

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

图8 以SiO2为载体的单、双金属催化剂脱氢量

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

表3 脱氢反应动力学分析结果

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

图9 12H-NECZ、8H-NECZ、4H-NECZ和NECZ在Pd（111）和Pd1Co3（111）表面稳定吸附结构

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

表4 12H-NECZ、8H-NECZ、4H-NECZ和NECZ在Pd（111）和Pd1Co3（111）表面的结合能

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

表5 12H-NECZ脱氢三步基元反应在Pd（111）和Pd1Co3（111）表面的Gibbs自由能变化

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

图10 12H-NECZ在Pd（111）和Pd1Co3（111）表面脱氢至NECZ的反应势能

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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PdCo/SiO₂双金属催化剂用于杂环储氢载体的高效脱氢

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

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