磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧

doi:10.16085/j.issn.1000-6613.2022-2107

化工进展 ›› 2023, Vol. 42 ›› Issue (10): 5179-5190.DOI: 10.16085/j.issn.1000-6613.2022-2107

磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧

杨程瑞雪¹(), 黄琪媛¹, 冉建速¹, 崔耘通¹, 王健健¹^,²()

^1.重庆大学化学化工学院&前沿交叉学科研究院跨尺度多孔材料研究中心，重庆 400045
^2.重庆大学煤矿灾害动力学与控制国家重点实验室，重庆 400044

收稿日期:2022-11-14 修回日期:2023-04-03 出版日期:2023-10-15 发布日期:2023-11-11
通讯作者: 王健健
作者简介:杨程瑞雪（1998—），女，硕士研究生，研究方向为木质素加氢脱氧。E-mail：1195505692@qq.com。
基金资助:
重庆自然科学基金(CSTB2022NSCQ-MSX0458);国家自然科学基金(21902016);中央高校基本科研业务费(2019CDQYHG026)

Palladium nanoparticles supported by phosphoric acid-modified SiO₂ as efficient catalysts for low-temperature hydrodeoxygenation of vanillin in water

YANG Chengruixue¹(), HUANG Qiyuan¹, RAN Jiansu¹, CUI Yuntong¹, WANG Jianjian¹^,²()

^1.Multi-scale Porous Materials Center, School of Chemistry and Chemical Engineering & Institute of Advanced Interdisciplinary Studies, Chongqing University, Chongqing 400045, China
^2.State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing 400044, China

Received:2022-11-14 Revised:2023-04-03 Online:2023-10-15 Published:2023-11-11
Contact: WANG Jianjian

摘要/Abstract

摘要：

选择性加氢脱氧（hydrodeoxygenation，HDO）木质素衍生物是一种生产生物基化学品和生物燃料的重要方法，然而这一过程在水相低温条件下较难实现。本文以磷酸修饰的二氧化硅纳米球（phosphoric acid modified silica nanospheres，PSNs）为载体，经负载Pd纳米颗粒（Pd NPs）后，合成了一系列Pd/PSNs催化剂。实验结果表明，该催化剂在香草醛（VAN）水相低温HDO转化中显示出优异的催化性能，45℃反应8h后，VAN完全转化，产物2-甲氧基-4-甲基苯酚（MMP）的选择性达到95.5%。深入分析发现，该催化剂表面的P物种和Pd NPs均是反应的活性位，且P物种加速反应中间体香草醇（VAL）通过自由基过程转化为产物MMP。此外，底物拓展实验表明，该催化剂在催化转化其他木质素衍生物过程中也显示出较好的催化活性。综上所述，本研究为水相低温选择性催化转化木质素衍生物制备高附加值化学品和生物燃料提供了一个新尝试，以期加快生物质高值化利用的研究进程。

关键词: 催化, 可再生能源, 生物质, 木质素衍生物, 二氧化硅

Abstract:

Selective hydrodeoxygenation (HDO) of lignin derivatives is regarded as an important route to produce high value-added biochemicals and biofuels. However, the low-temperature HDO process performed in water is still of challenge. In this study, a series of Pd/PSNs catalysts was prepared via a facile impregnation method where phosphoric acid-modified silica nanospheres (PSNs) were used as the support and then Pd nanoparticles (Pd NPs) were uniformly dispersed on them. The as-prepared catalysts showed high activities in low-temperature HDO of vanillin (VAN) to 2-methoxy-4-methylphenol (MMP) in water. VAN could be fully converted after reaction at 45℃ for 8h in water and the corresponding yield of MMP was up to 95.5%. Detailed experimental studies demonstrated that both P species and Pd NPs on the surface of Pd/PSNs catalyst were active sites for the HDO of VAN and the presence of P species could accelerate the selective conversion of the intermediate (vanillyl alcohol, VAL) to MMP via a free-radical process, resulting in the superior catalytic performances. Besides, Pd/PSNs catalysts also exhibited excellent catalytic performances in HDO of other lignin derivatives with different functional groups to the corresponding products. This work provides a new idea for the selective production of high value-added biochemicals and biofuels from lignin derivatives.

Key words: catalysis, renewable energy, biomass, lignin derivatives, silica

中图分类号:

杨程瑞雪, 黄琪媛, 冉建速, 崔耘通, 王健健. 磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧[J]. 化工进展, 2023, 42(10): 5179-5190.

YANG Chengruixue, HUANG Qiyuan, RAN Jiansu, CUI Yuntong, WANG Jianjian. Palladium nanoparticles supported by phosphoric acid-modified SiO₂ as efficient catalysts for low-temperature hydrodeoxygenation of vanillin in water[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5179-5190.

图/表 9

参考文献 28

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样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	Pd负载量 /%	P负载量 /%
Pd/SNs	<10	<0.1	1.1	0
Pd/PSNs	<10	<0.1	1.2	1.3
Pd/PSNs（反应后）	<10	<0.1	1.1	0.6

样品	比表面积 /m²·g^-1	孔容 /cm³·g^-1	Pd负载量 /%	P负载量 /%
Pd/SNs	<10	<0.1	1.1	0
Pd/PSNs	<10	<0.1	1.2	1.3
Pd/PSNs（反应后）	<10	<0.1	1.1	0.6

催化剂	反应条件	Pd负载量/%	VAN转化率/%	MMP选择性/%	参考文献
Pd₁@WO_2.72	40℃、15min、乙醇	0.6	>99	>99	[23]
Pd/PSNs	45℃、8h、水	1.2	>99	95.5	本文工作
ClMPA@Pd/Al₂O₃	50℃、1h、乙醇	1.0	>99	87.0	[24]
Pd/CFR	70℃、1h、正丁醇	0.5	>99	>99	[15]
Pd_SA+C/SAPO-31	80℃、30min、乙醇	0.4	>99	>99	[16]
Pd@UiO-66(Hf)	90℃、2h、水	5.2	>99	>99	[20]
Pd/biochar	100℃、3h、水	2.0	>99	92.0	[21, 25]
Pd/NH₂-UiO-66	100℃、1h、水	2.0	>99	>99	[14]
Pd/MSMF	110℃、2h、水	4.5	>99	>99	[17]

催化剂	反应条件	Pd负载量/%	VAN转化率/%	MMP选择性/%	参考文献
Pd₁@WO_2.72	40℃、15min、乙醇	0.6	>99	>99	[23]
Pd/PSNs	45℃、8h、水	1.2	>99	95.5	本文工作
ClMPA@Pd/Al₂O₃	50℃、1h、乙醇	1.0	>99	87.0	[24]
Pd/CFR	70℃、1h、正丁醇	0.5	>99	>99	[15]
Pd_SA+C/SAPO-31	80℃、30min、乙醇	0.4	>99	>99	[16]
Pd@UiO-66(Hf)	90℃、2h、水	5.2	>99	>99	[20]
Pd/biochar	100℃、3h、水	2.0	>99	92.0	[21, 25]
Pd/NH₂-UiO-66	100℃、1h、水	2.0	>99	>99	[14]
Pd/MSMF	110℃、2h、水	4.5	>99	>99	[17]

序号	反应条件	转化率/%	选择性/%
1	45℃、8h、水	>99	94.4
2	45℃、8h、水	>99	96.9
3	45℃、8h、水	>99	>99
4	45℃、8h、水	>99	>99
5	45℃、8h、乙醇	>99	86.8
6	60℃、8h、乙醇	>99	93.9
7	45℃、8h、乙醇	>99	78.8
8	60℃、8h、乙醇	>99	98.4

磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧

Palladium nanoparticles supported by phosphoric acid-modified SiO₂ as efficient catalysts for low-temperature hydrodeoxygenation of vanillin in water

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磷酸修饰二氧化硅负载钯催化剂用于木质素衍生物高效水相低温加氢脱氧

Palladium nanoparticles supported by phosphoric acid-modified SiO2 as efficient catalysts for low-temperature hydrodeoxygenation of vanillin in water

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Palladium nanoparticles supported by phosphoric acid-modified SiO₂ as efficient catalysts for low-temperature hydrodeoxygenation of vanillin in water