压缩CO2中Co-N-C催化3-硝基苯乙烯选择性加氢反应动力学及相行为

doi:10.1016/S1872-2067(20)63785-8

催化学报 ›› 2021, Vol. 42 ›› Issue (9): 1617-1624.DOI: 10.1016/S1872-2067(20)63785-8

• 论文 • 上一篇

压缩CO₂中Co-N-C催化3-硝基苯乙烯选择性加氢反应动力学及相行为

周丹^a^,^b, 张磊磊^b^,^$(), 刘文刚^b, 徐刚^b, 杨级^b, 蒋齐可^c, 王爱琴^b^,^*(), 银建中^a^,^#()

^a大连理工大学化工学院, 精细化工国家重点实验室, 辽宁大连116024
^b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
^c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

收稿日期:2021-01-14 接受日期:2021-02-08 出版日期:2021-09-18 发布日期:2021-05-16
通讯作者: 张磊磊,王爱琴,银建中
基金资助:
国家重点研发计划(2020YFA0710202);国家自然科学基金(21690080);国家自然科学基金(21690084);国家自然科学基金(21673228);国家自然科学基金(21721004);中国科学院战略性先导科技专项(XDB17020100)

Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3-nitrostyrene over Co-N-C single-atom catalyst in compressed CO₂

Dan Zhou^a^,^b, Leilei Zhang^b^,^$(), Wengang Liu^b, Gang Xu^b, Ji Yang^b, Qike Jiang^c, Aiqin Wang^b^,^*(), Jianzhong Yin^a^,^#()

^aSchool of Chemical Engineering, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China
^bState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2021-01-14 Accepted:2021-02-08 Online:2021-09-18 Published:2021-05-16
Contact: Leilei Zhang,Aiqin Wang,Jianzhong Yin
About author:^$ E-mail: zhangleilei@dicp.ac.cn
^# E-mail: jzyin@dlut.edu.cn;
^* Tel/Fax: +86-411-84379348; E-mail: aqwang@dicp.ac.cn;
Supported by:
National Key R&D Program of China(2020YFA0710202);National Science Foundation of China(21690080);National Science Foundation of China(21690084);National Science Foundation of China(21673228);National Science Foundation of China(21721004);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020100)

摘要/Abstract

摘要：

对于苯环上含有各种可还原基团(如‒C=C, ‒CN, ‒C≡C)的硝基芳烃, 通过选择性加氢来制备芳香胺类化合物依然充满挑战. 负载型纳米催化剂通常存在过度加氢的缺陷, 虽然通过覆盖部分金属位点等方法可改善其选择性, 但多是以牺牲催化活性为代价. 得益于较高的原子利用率以及孤立的活性位结构, 单原子催化剂在硝基芳烃选择性加氢反应中崭露头角. 例如Pt₁/FeO_x单原子催化剂在3-硝基苯乙烯加氢反应中对目标产物的选择性高于99%, 且转化频率(TOF)是Pt纳米催化剂的20倍以上. 然而, 已报道的单原子催化体系中, 活性组分多为Pt族贵金属, 且以有机溶剂为反应介质, 不符合绿色化学理念.
本文以环境友好型溶剂——压缩CO₂为反应介质, 以氮掺杂碳负载非贵金属Co单原子(Co-N-C)为催化剂, 实现了3-硝基苯乙烯的选择性加氢, 且反应体系中无任何有机溶剂和助剂. 在温和(60°C, 3 MPa H₂(RT), 总压8.1 MPa)的反应条件下, 3-硝基苯乙烯可完全转化, 目标产物3-乙烯基苯胺的选择性达到> 99％, 且产物可通过简单卸压直接分离. Co-N-C单原子催化剂表现出较高的稳定性, 循环使用4次以后活性并无明显降低. HAADF-STEM表征发现反应后的催化剂中, Co仍然呈单原子分散.
研究发现, 通过改变CO₂压力(即CO₂相行为)可调变H₂在其中的溶解度以及在加氢反应中的反应级数, 进而调变反应速率. 通常认为, 催化活性会随CO₂压力增大呈线性增加, 而本文中转化率却随CO₂压力增加呈现“倒V型”曲线关系, 即当体系总压为8.1 MPa(P_CO2 = 5.0 MPa)时, 转化率达到最大值(100%), 而升高或降低CO₂压力均会显著降低催化活性.
为解释“倒V型”曲线的成因, 通过含可视窗的高压釜研究了3-硝基苯乙烯/CO₂/H₂三元体系的相行为. 发现当总压为13.4 MPa时, 体系为均匀的一相(即3-硝基苯乙烯完全溶解在CO₂中); 而当总压为8.1 MPa时, 却形成了气-液两相. 用激光笔照射高压釜上部的气相时, 出现了明显的丁达尔现象, 说明其中溶解有少量的3-硝基苯乙烯, 呈胶体分散; 底部为CO₂膨胀的3-硝基苯乙烯液相, 且该膨胀行为通过硝基苯-CO₂二元相行为研究得到证实(即在一定CO₂压力下, 6 mL硝基苯可被CO₂膨胀至充满整个高压釜(容积为29.3 mL)). 动力学研究发现, 在不含CO₂以及总压为11.2 MPa时, H₂的反应级数为~0.5; 而当总压为8.1 MPa(CO₂压力为5.0 MPa)时, H₂的级数降为0, 说明该压力下H₂的溶解度显著增加. 通过Peng-Robinson方程计算了不同CO₂压力下H₂的溶解度, 发现H₂溶解度与CO₂压力也呈“倒V型”曲线关系, 且最高点对应的CO₂压力与上述转化率-P_CO2曲线一致. 因此, 当总压为8.1 MPa, CO₂分压为5.0 MPa时形成了CO₂膨胀的3-硝基苯乙烯液体, 溶解入该膨胀液体的CO₂促进了H₂的溶解, 进而使H₂的反应级数降为0, 从而促进了加氢反应的进行.
综上, 本文以压缩CO₂为溶剂, 以非贵金属基Co-N-C为催化剂, 发展了一种3-硝基苯乙烯绿色选择性加氢途径. 同时发现, 改变CO₂压力可调变反应体系的相行为及反应动力学行为, 进而调变催化性能. 该研究结果可为调变压缩CO₂介质中进行的其它催化转化反应性能提供借鉴.

关键词: 单原子催化剂, Co-N-C, CO₂, 相行为, 化学选择性加氢, 3-硝基苯乙烯

Abstract:

Single-atom catalysts (SACs) have demonstrated excellent performances in chemoselective hydrogenation reactions. However, the employment of precious metals and/or organic solvents compromises their sustainability. Herein, we for the first time report the chemoselective hydrogenation of 3-nitrostyrene over noble-metal-free Co-N-C SAC in green solvent — compressed CO₂. An interesting inverted V-curve relation is observed between the catalytic activity and CO₂ pressure, where the conversion of 3-nitrostyrene reaches the maximum of 100% at 5.0 MPa CO₂ (total pressure of 8.1 MPa). Meanwhile, the selectivities to 3-vinylaniline at all pressures remain high (> 99%). Phase behavior studies reveal that, in sharp contrast with the single phase which is formed at total pressure above 10.8 MPa, bi-phase composed of CO₂/H₂ gas-rich phase and CO₂-expanded substrate liquid phase forms at total pressure of 8.1 MPa, which dramatically changes the reaction kinetics of the catalytic system. The reaction order with respect to H₂ pressure decreases from ~0.5 to zero at total pressure of 8.1 MPa, suggesting the dissolved CO₂ in 3-nitrostyrene greatly promotes the dissolution of H₂ in the substrate, which is responsible for the high catalytic activity at the peak of the inverted V-curve.

Key words: Single-atom catalyst, Co-N-C, CO₂, Phase behavior, Chemoselective hydrogenation, 3-Nitrostyrene

周丹, 张磊磊, 刘文刚, 徐刚, 杨级, 蒋齐可, 王爱琴, 银建中. 压缩CO₂中Co-N-C催化3-硝基苯乙烯选择性加氢反应动力学及相行为[J]. 催化学报, 2021, 42(9): 1617-1624.

Dan Zhou, Leilei Zhang, Wengang Liu, Gang Xu, Ji Yang, Qike Jiang, Aiqin Wang, Jianzhong Yin. Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3-nitrostyrene over Co-N-C single-atom catalyst in compressed CO₂[J]. Chinese Journal of Catalysis, 2021, 42(9): 1617-1624.

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图/表 8

Fig. 1. XRD pattern (a), low-magnification STEM (b) and high-resolution HAADF-STEM images (c) of the as-synthesized Co-N-C catalyst; HAADF-STEM image of the spent Co-N-C catalyst (d).

Fig. 2. The dependence of conversion and selectivity on H2 pressure (a), temperature (b) and CO2 pressure (c). Reaction conditions: 0.5 mmol 3-nitrostyrene, 30 mg Co-N-C catalyst, 60 °C (a,c), 3 MPa H2 (RT) (b,c), total pressure: 9.2 MPa (a,b), 8 h.

Fig. 3. Phase behaviour of 3-nitrostyrene (NS)-CO2-H2 ternary system: (a-d) visual observations, (e-h) images of the phase conditions when the view cell was irradiated by a laser beam, and (i-l) the corresponding illustration of the phases at the total pressure of 3.1 MPa (CO2-free), 8.1, 9.2 and 13.4 MPa, respectively. Other conditions: 0.5 mmol 3-nitrostyrene, 3 MPa H2 (RT), 60 °C.

Fig. 4. Photographs of volume expansion in CO2-nitrobenzene binary system taken at 60 °C under different pressures.

Fig. 5. Calculated H2 solubility in liquid substrate 3-nitrostyrene (NS) at 60 °C under different CO2 pressures.

Fig. 6. The dependence of reaction rate on the concentration of 3-nitrostyrene at total pressure of 8.1 (a) and 11.2 (b) MPa. Reaction conditions: Ptotal = 8.1 MPa, PH2 = 3.0 MPa (RT), 30 mg catalyst, 60 °C, reaction time was varied between 0.5-1 h to maintain the conversions below 30%.

Fig. 7. The dependence of reaction rate on the pressure of H2 at (a) CO2-free condition; (b) total pressure of 8.1 MPa; (c) total pressure of 11.2 MPa. Reaction conditions: 0.5 mmol 3-NS, 0.25 mmol o-xylene, 30 mg catalyst, 60 °C, and the reaction time was varied between 1?3 h to maintain the conversion below 30%.

Fig. 8. Durability of the Co-N-C catalyst. Condition: 3-nitrostyrene (0.5 mmol), Co-N-C catalysts (30 mg), o-xylene (0.25 mmol, as the internal standard), 60 °C, total pressure of 8.1MPa and H2 pressure of 3.0 MPa (RT), 8 h.

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压缩CO₂中Co-N-C催化3-硝基苯乙烯选择性加氢反应动力学及相行为

Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3-nitrostyrene over Co-N-C single-atom catalyst in compressed CO₂

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