原位合成氮掺杂石墨烯负载钯纳米颗粒用于催化香兰素高选择性加氢反应

doi:10.6023/A22120481

摘要/Abstract

通过原位合成法制备了氮掺杂石墨烯负载钯纳米颗粒催化剂Pd@N/C-2, 用于催化香兰素选择性加氢反应. 采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等方法对Pd@N/C-2催化剂进行结构与性能的表征, 分析表明石墨烯层在活性钯纳米颗粒表面起到了保护作用, 提高了催化剂在反应条件下的稳定性, 在五次循环回收实验后催化剂仍保持很高的反应活性. 通过对石墨烯掺杂氮原子引入了催化反应的化学活性中心和金属纳米颗粒沉积的锚定中心, 从而使石墨烯在加氢催化反应中的性能得到进一步提高. 并且通过对溶剂的调控实现了香兰素分别高选择性生成香草醇和对甲基愈创木酚, 在优化的反应条件下, 香草醇和对甲基愈创木酚的产率分别为89%和99%.

关键词: 香兰素, 香草醇, 对甲基愈创木酚, 均相催化剂, 选择性加氢

As the only natural and sustainable carbon source, biomass shows great potential in solving current environmental and energy problems and creating a carbon-neutral society. Selective hydrogenation is a kind of important reaction. Various unsaturated functional groups in biomass are typical targets of selective hydrogenation. Therefore, selectivity is the key index to measure the efficiency of the hydrogenation reaction. Vanillin is an important platform compound in biomass conversion. In recent years, selective hydrogenation of vanillin to biofuels and other high-value-added chemicals has received widespread attention. Because vanillin has different reducible functional groups (aldehyde group, methoxy group, and hydroxyl group), it is very important to control the selectivity of vanillin hydrogenation. Vanillyl alcohol has long-lasting sweetness and nutty aromas and is used in the food and perfume industries. 2-Methoxy-4-methylphenol (MMP) is also an important biofuel. Therefore, selective hydrogenation of vanillin to vanillyl alcohol or MMP is an important synthesis route. Here, we propose a strategy to introduce the chemical active center of catalytic reaction and the anchoring center of metal nanoparticle deposition by doping nitrogen atoms of graphene, which makes the application of graphene in hydrogenation catalysis obtain better performance. In this work, we report a simple method for in-situ synthesis of nitrogen-doped graphene-supported palladium nanoparticles Pd@N/C-2 catalyst and its application in selective hydrogenation of the C=O bond. The prepared catalyst has good catalytic activity and product selectivity for the hydrogenation of vanillin and has the advantages of simple preparation, high activity and stable performance. It is easy to be separated from organic reaction conditions and can be reused many times. Under relatively mild reaction conditions, Pd@N/C-2 catalyzed the complete conversion of vanillin to vanillyl alcohol and MMP, and the yields were 89% and 99%, respectively. It is worth noting that through the regulation of solvents, we achieved highly selective hydrogenation of vanillin to vanillyl alcohol and MMP, respectively.

Key words: vanillin, vanillyl alcohol, 2-methoxy-4-methylphenol, homogeneous catalyst, selective hydrogenation

引用此文

徐斌, 韦秀芝, 孙江敏, 刘建国, 马隆龙. 原位合成氮掺杂石墨烯负载钯纳米颗粒用于催化香兰素高选择性加氢反应[J]. 化学学报, 2023, 81(3): 239-245.

Bin Xu, Xiuzhi Wei, Jiangmin Sun, Jianguo Liu, Longlong Ma. In-situ Synthesis of Nitrogen-doped Graphene Layer Encapsulated Palladium Nanoparticles for Highly Selective Hydrogenation of Vanillin[J]. Acta Chimica Sinica, 2023, 81(3): 239-245.

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图/表 8

图1. (a) Pd@N/C-2、(b) Pd@N/C-9、(c) 商业Pd@N/C的SEM图像; (d, g) Pd@N/C-2、(e) Pd@N/C-9、(f) 商业Pd@N/C的高分辨扫描透射电镜(HAADF-TEM)图像; (h) Pd@N/C-2的能量分布面扫描分析(EDS mapping)图像

Figure 1. Representative SEM images of Pd@N/C-2 (a), Pd@N/C-9 (b), purchased Pd@N/C (c); representative HAADF-TEM images of Pd@N/C-2 (d, g), Pd@N/C-9 (e), purchased Pd@N/C (f); EDS elemental mapping of Pd@N/C-2 (h)

图2. Pd@N/C-2、Pd@N/C-9和商业Pd@N/C催化剂的XRD谱图

Figure 2. XRD patterns of Pd@N/C-2, Pd@N/C-9 and purchased Pd@N/C

图3. Pd@N/C-2催化剂的N2吸附-脱附等温曲线

Figure 3. N2 adsorption-desorption isotherms of Pd@N/C-2

图4. Pd@N/C-2催化剂的XPS谱图

Figure 4. XPS spectra of Pd@N/C-2

图5. (a) 溶剂、(b) 温度、(c) 压力和(d) 时间对Pd@N/C-2催化苯甲醛选择性加氢反应的影响

Figure 5. Effects of (a) solvent, (b) temperature, (c) pressure and (d) time on the selective hydrogenation of benzaldehyde catalyzed by Pd@N/C-2

Entry	Condition	Conversion^b/%	Selectivity^b/%
1	Standard condition	92.8	93.4
2	N₂	trace	trace
3	No catalyst	trace	trace
4	Purchased Pd@C	>99	trace
5	Purchased Pd@N/C	11.3	65.4
6	Pd@N/C-9	79.7	85.6

表1. 苯甲醛选择性加氢对照实验a

Table 1. Control experiments for selective hydrogenation of benzaldehyde

Entry	Conversion^b/%	Selectivity^b/%
1	96.1	97.4
2	>99	98.0
3	97.5	96.2
4	85.9	95.3
5	>99	93.3
6	84.4	86.4
7^c	78.7	>99

表2. Pd@N/C-2催化剂对醛类底物的加氢还原活性a

Table 2. Hydrogenation reduction of various aldehyde by catalyst Pd@N/C-2

图6. (a)香草醛选择性加氢反应条件优化及(b) Pd@N/C-2催化剂的循环使用性能

Figure 6. Optimization of reaction conditions for hydrogenation of vanillin (a) and cycle performance (b) of Pd@N/C-2 catalyst

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