Ti掺杂SBA-15负载Ni基催化剂用于木质素衍生物定向加氢脱氧转化

张鸿科; 汪炜琛; 向治宇; 周方圆; 朱万斌; 王洪亮

doi:10.1016/S1872-5813(23)60387-1

Ti掺杂SBA-15负载Ni基催化剂用于木质素衍生物定向加氢脱氧转化

doi: 10.1016/S1872-5813(23)60387-1

中国农业大学农学院生物质工程中心, 北京 100193

基金项目: 该工作得到了国家重点研发计划（2018YFB1501500）、中国农业大学基金2115人才培养计划（1011-00109018）、北京市现代农业产业技术体系创新团队BAIC08-2022的支持

详细信息

通讯作者:
Tel: 18518958285，E-mail: hlwang@cau.edu.cn

中图分类号: TK6
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出版历程
- 收稿日期: 2023-07-12
- 修回日期: 2023-08-28
- 录用日期: 2023-09-13
- 网络出版日期: 2023-11-10

Ni supported on Ti-doped SBA-15 catalyst for the selective hydrodeoxygenation conversion of lignin derivatives

Biomass Engineering Center, College of Agriculture, China Agricultural University, Beijing 100193, China

Funds: This work was supported by the National Key Research and Development Program (2018YFB1501500), the China Agricultural University Foundation 2115 Talent Training Program (1011-00109018), and the Beijing Modern Agricultural Industry Technology System Innovation Team BAIC08-2022.

摘要

摘要: 开发廉价高效催化剂用于木质素衍生物的选择性加氢脱氧制备先进燃料和精细化学品对木质素增值转化具有重要意义。本研究通过在SBA-15分子筛骨架内掺杂Ti物种并负载Ni纳米颗粒合成了“金属-酸”双功能催化剂（Ni/Ti-SBA-15）。Ti的掺杂不仅提高了催化剂酸性位点的数量，还促进了Ni纳米颗粒在载体上的高度分散。在绿色、温和条件下实现了香兰素到2-甲氧基-4-甲基苯酚（MMP）高效转化，目标产物选择性高达96.46%。此外，Ni/Ti-SBA-15催化剂价格低廉，制备工艺简单，这项工作为制备廉价高效催化剂提供了新的思路，有利于实现生物质衍生物的绿色、低成本升级转化。
- 香兰素 /
- 加氢脱氧 /
- 双功能催化剂 /
- 木质素
Abstract: The development of cost-effective and efficient catalysts plays a critical role in the selective hydrodeoxygenation of lignin derivatives for lignin valorization. Herein, we reported “metal-acid” bifunctional catalysts (Ni/Ti-SBA-15) consist of Ni nanoparticles highly dispersed on Ti doped SBA-15, which achieved 100% vanillin conversion and 96.46% selectivity of 2-methoxy-4-methylphenol (MMP) under mild conditions. Characterizations were employed to reveal the morphology and physicochemical properties of the catalysts. The results indicated that doping of Ti species not only increased the number of acidic sites but also promoted the high dispersion of Ni nanoparticles on the support. This research provides a novel concept for the synthesis of cost-effective and efficient catalysts, which contributes to the environmentally friendly and economical conversion of biomass derivatives.
- vanillin /
- hydrodeoxygenation /
- bifunctional catalyst /
- lignin

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图 1 操作流程简图

Figure 1 Operation flow sketch

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图 2 (a) 载体和催化剂的N₂吸附-脱附曲线；(b) 载体和催化剂的孔径分布；(c) 载体和催化剂的XRD谱图；(d) 催化剂的NH₃-TPD曲线

Figure 2 (a) N₂ adsorption-desorption curves of the carrier and catalyst; (b) pore size distribution of the carrier and catalyst; (c) XRD spectra of the carrier and catalyst; (d) NH₃-TPD curves of the catalyst

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图 3 催化剂Ni/Ti₇-SBA-15的TEM图像

Figure 3 TEM images of catalyst Ni/Ti₇-SBA-15

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图 4 Ni/Ti₇-SBA-15催化剂在Ni 2p、O 1s和Ti 2p的 XPS分析谱图

Figure 4 XPS spectra of Ni/Ti₇-SBA-15 catalyst in the Ni 2p、O 1s and Ti 2p region

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图 5 (a) 载体Ti₇-SBA-15和Ti掺杂量不同的系列催化剂的催化活性；(b) 催化剂Ni/Ti₇-SBA-15在不同温度下的催化活性；(c) 催化剂Ni/Ti₇-SBA-15在不同氢压下的催化活性；(d) 催化剂Ni/Ti₇-SBA-15催化反应过程的时间曲线

Figure 5 (a) Catalytic activity of the carrier Ti₇-SBA-15 and the series catalysts with different Ti doping; (b) Catalytic activity of catalyst Ni/Ti₇-SBA-15 at different temperatures; (c) Catalytic activity of catalyst Ni/Ti₇-SBA-15 at different hydrogen pressures; (d) Time profile of the catalytic reaction process of catalyst Ni/Ti₇-SBA-15

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图 6 催化剂Ni/Ti-SBA-15催化香兰素加氢脱氧生成MMP的作用机理

Figure 6 Mechanism of catalyst Ni/Ti-SBA-15 catalyzed hydrodeoxygenation of vanillin to generate MMP

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表 1 BET和ICP-OES测量结果

Table 1 BET and ICP-OES measurement results

Samples	S_BET (m²·g⁻¹)	V_t (cm³·g⁻¹)	Pore size (nm)	Ni (wt%)	Ti (wt%)
SBA-15	970.4	0.49	2.46	-	-
Ti₇-SBA-15	828.1	0.46	2.61	-	-
Ni/SBA-15	521.0	0.23	2.57	10.0	-
Ni/Ti₇-SBA-15	425.0	0.26	3.37	9.9	7.46

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表 2 已报道的香兰素加氢脱氧制MMP的催化剂和Ni/Ti₇-SBA-15的催化效果

Table 2 Catalytic effects of reported catalysts for the hydrodeoxygenation of vanillin to MMP and Ni/Ti₇-SBA-15

Catalyst	Reaction conditions	Conv.（%）	Sel.（%）	Ref.
Pd/ZrO₂(x)	Ethanol、Polymethylhydrosiloxane、25 ℃、1 h	>99	>99	[5]
Pd/Ru@GO	Methanol、1 MPa H₂、25 ℃、12 h	>99	>99	[6]
Au/Co₃O₄ NRs-OVs	2-Propanol、0.1 MPa N₂、240 ℃、3 h	>99	>99	[7]
Co@NC-700	H₂O、Formic acid、180 ℃、4 h	95.7	>99	[9]
Cu-Ga/HNZY	Methanol、1 MPa H₂、160 ℃、2 h	>99	99	[10]
Ni/ZrP	Isopropanol、0.5 MPa H₂、220 ℃、0.5 h	95	85	[11]
HD-Ni/N-CMS	H₂O、2 MPa H₂、130 ℃、10 h	>99	>99	[12]
Ni/Nb₂O₅	H₂O、1 MPa H₂、180 ℃、1 h	96	79	[13]
Ni_0.5Zn_1.5Al₁-MMO	H₂O、1 MPa H₂、130 ℃、2 h	99	56	[14]
Ni/Ti₇-SBA-15	H₂O、1 MPa H₂、140 ℃、2 h	99	96	-

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表 3 Ni/Ti-SBA-15对多种木质素衍生物的加氢脱氧催化效果

Table 3 HDO of various substrates catalyzed by Ni/Ti-SBA-15

Entry	Substrate	Product	Conv. （%）	Sel. （%）
1			100	96.46
2			100	>99
3			100	>99
4			100	>99
反应条件：50 mg催化剂，1 mmol 底物，20 mL H₂O，140 ℃，1 MPa H₂，2 hReaction condition: 50 mg catalyst, 1 mmol substrate, 20 mL H₂O, 140 ℃, 1 MPa H₂, 2 h.

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