直接合成Beta沸石封装Pt纳米粒子用于5-羟甲基糠醛合成2,5-呋喃二甲酸

doi:10.1016/S1872-2067(20)63720-2

催化学报 ›› 2021, Vol. 42 ›› Issue (6): 994-1003.DOI: 10.1016/S1872-2067(20)63720-2

直接合成Beta沸石封装Pt纳米粒子用于5-羟甲基糠醛合成2,5-呋喃二甲酸

刘晓玲, 陈磊, 许红中, 蒋师, 周瑜^*(), 王军^#()

南京工业大学化工学院, 材料化学国家重点实验室, 江苏南京210009

收稿日期:2020-07-18 接受日期:2020-08-31 出版日期:2021-06-18 发布日期:2021-01-30
通讯作者: 周瑜,王军
基金资助:
国家自然科学基金(22072065);国家自然科学基金(U1662107);国家自然科学基金(21476109);国家自然科学基金(21303084);江苏省“六大人才高峰”项目(JNHB-035);江苏省自然科学青年基金(SBK2020044703);江苏省高等学校优势学科项目(PAPD)

Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid

Xiaoling Liu, Lei Chen, Hongzhong Xu, Shi Jiang, Yu Zhou^*(), Jun Wang^#()

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China

Received:2020-07-18 Accepted:2020-08-31 Online:2021-06-18 Published:2021-01-30
Contact: Yu Zhou,Jun Wang
About author:^#E-mail: junwang@njtech.edu.cn
^*Tel/Fax: +86-25-58139803; E-mail: njutzhouyu@njtech.edu.cn;
Supported by:
National Natural Science Foundation of China(22072065);National Natural Science Foundation of China(U1662107);National Natural Science Foundation of China(21476109);National Natural Science Foundation of China(21303084);Six talent peaks project in Jiangsu Province(JNHB-035);Jiangsu Provincial Science Foundation for Youths(SBK2020044703);Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)

摘要/Abstract

摘要：

生物质是唯一的碳基可再生资源, 具有种类丰富、廉价易得、来源广泛等特点, 将生物质资源转化为高附加值化学品对于可持续生产, 缓解全球性能源和环境危机具有重要意义. 5-羟甲基糠醛(HMF)是广泛研究的生物质平台分子, 可以转化为多种高附加值化学品, 其中氧化产物2,5-呋喃二甲酸(FDCA)有望作为对苯二甲酸的潜在替代物生产聚酯, 因而备受关注. 然而如何设计合成高性能的多相催化剂一直是个挑战. 以氧气为氧化剂, 负载型贵金属纳米粒子作为多相催化剂是目前广为研究的体系, 但是面临贵金属利用率低, 稳定性不佳等不足. 将贵金属纳米粒子封装于沸石骨架, 不仅能通过沸石孔壁的物理隔离效应增加纳米粒子的稳定性, 同时基于沸石孔道对于底物、中间生成物、产物等特有的传质限域效应, 可能会进一步提高活性和选择性. 由于沸石晶体一般在碱性水热条件下晶化得到, 易导致贵金属物种的快速沉积而难以获得高分散贵金属纳米粒子的沸石催化剂. 因此这类催化剂的直接水热合成以及在生物质平台分子转化中的应用至今少有报道. 本文设计合成了一种封装铂(Pt)纳米粒子的Beta沸石(Pt@Beta), 应用于催化HMF合成FDCA的反应, 以常压氧气为氧源, 水作为溶剂, 获得了高活性和稳定性以及极高的Pt原子利用率.
我们采用一种不同以往的酸水解路径合成Pt@Beta沸石. 首先将Pt前驱体、硅源(正硅酸四乙酯)和有机配体(3-巯丙基甲氧基硅氧烷)在弱酸性条件下水解缩合, 增强了硅物种与Pt物种的相互作用, 有效避免了贵金属氢氧化物的形成, 这种特殊的预水解缩合环节有效促进了后续碱性环境水热合成中的Pt物种进入沸石晶内的过程, 最终形成较为稳定和均匀分散的Pt纳米粒子. 系统考察了配体种类、配体用量、配体加料顺序等合成条件对于催化剂制备的影响规律, 获得了高分散Pt纳米粒子的适宜合成条件, 结果表明, 在酸水解过程中加入适量的有机配体, 对于最终催化剂中Pt的高度分散至关重要. 将不同Pt含量的Pt@Beta和后负载方法制备的Pt/Beta进行细致对比, XPS和TEM表征结果发现, 只有直接水热合成法能够将Pt较好地封装在沸石晶体内. 封装较低含量Pt的样品(0.2%Pt@Beta)在HMF氧化制FDCA反应中表现出高的收率和良好的复用稳定性. 为探究其高活性缘由, 测试了不同催化剂对底物、中间体以及产物的吸附性能, 结果表明, 0.2%Pt@Beta对于中间体2-甲酰呋喃甲酸(FFCA)吸附能力较强, 能有效加速FFCA到FDCA这一决速步的反应, 从而促进了FDCA的生成. 此外, 0.2%Pt@Beta中贵金属物种位于沸石晶内, 得益于沸石刚性无机骨架的稳定化作用, 该催化剂能有效阻止Pt纳米粒子在苛刻条件下的聚集, 避免液固相反应体系中的溶脱流失, 从而表现出优良的催化复用稳定性.

关键词: 水热合成, 沸石, 贵金属纳米粒子, 多相催化, 生物质转化

Abstract:

Encapsulating noble metal nanoparticles (NPs) within the zeolite framework enhances the stability and accessibility of active sites; however, direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions. Herein, beta zeolite-encapsulated Pt NPs (Pt@Beta) were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step. The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species. Thus, the resultant 0.2%Pt@Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDCA) under atmospheric O₂ conditions by using water as the solvent while stably evincing a high yield (90%) associated with a large turnover number of 176. The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.

Key words: Hydrothermal synthesis, Zeolite, Noble metal nanoparticles, Heterogeneous catalysis, Biomass conversion

刘晓玲, 陈磊, 许红中, 蒋师, 周瑜, 王军. 直接合成Beta沸石封装Pt纳米粒子用于5-羟甲基糠醛合成2,5-呋喃二甲酸[J]. 催化学报, 2021, 42(6): 994-1003.

Xiaoling Liu, Lei Chen, Hongzhong Xu, Shi Jiang, Yu Zhou, Jun Wang. Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid[J]. Chinese Journal of Catalysis, 2021, 42(6): 994-1003.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63720-2

https://www.cjcatal.com/CN/Y2021/V42/I6/994

图/表 8

Scheme 1. Schematic diagram for the preparation of Pt@Beta.

Fig. 1. SEM (A), and TEM(B) images of 0.2%Pt@Beta; (C) HAADF-STEM, and corresponding elemental mapping images for Si, Al, O, and Pt elements of 0.2%Pt@Beta.

Fig. 2. (A-C) powder XRD patterns; (D) N2 sorption isotherms (the inset is the pore size dispersion curves); (E) FTIR spectra; (F) Survey scan; (G) Pt 4d XPS spectra.

Table 1 Textual properties.

Sample	S_BET ^a(m² g^-1)	Vp^b (cm³ g^-1)	D_av ^c(nm)	Pt^d (wt%)	Unit cell parameters ^e(Å)
Sample	S_BET ^a(m² g^-1)	Vp^b (cm³ g^-1)	D_av ^c(nm)	Pt^d (wt%)	a	b	c
Beta	511	0.31	2.5	0	12.66	12.65	26.41
0.2%Pt@Beta	497	0.28	2.2	0.20	12.65	12.56	26.69
0.5%Pt@Beta	509	0.27	2.1	0.41	12.69	12.57	26.49
0.2%Pt/Beta	468	0.25	2.1	0.20	12.66	12.66	26.40

Scheme 2. Typical reaction pathways for the oxidation of HMF into FDCA in the presence and absence of the base.

Table 2 Oxidation of HMF to FDCA a.

Entry	Sample	Conversion^b (%)	Yield^c (%)			Selectivity^d (%)	TON ^e
Entry	Sample	Conversion^b (%)	HMFCA	FFCA	FDCA	Selectivity^d (%)	TON ^e
1	0.2%Pt@Beta	>99	0	0	99	99	97
2	Beta	12	5	1	1	8	—
3	0.2%Pt/Beta	96	18	34	37	39	36
4	0.5%Pt@Beta	97	12	36	44	45	43
5	0.2%Pt@Beta-OH^f	86	15	12	50	58	49
6	0.2%Pt/Beta-OH^f	82	12	14	14	17	14
7	Pt/C	>99	0	25	32	32	31

Fig. 3. (A) Kinetic profile and (B) reusability of 0.2%Pt@Beta in the oxidation of HMF into FDCA. Reaction conditions: 0.1 mmol HMF, 100 mg catalyst, Na2CO3/HMF molar ratio = 6, 4 mL water, 90 °C, 24 h for (B) O2 balloon.

Fig. 4. Adsorption amount of HMF, HMFCA, FFCA, and FDCA on 0.2%Pt@Beta (A), 0.2%Pt/Beta (C), 0.5%Pt@Beta (D), and 0.2%Pt@Beta-OH (E). Adsorption conditions: 0.01 mmol adsorbate (Diagonal stripe) or 0.01 mmol adsorbate in the presence of 0.06 mmol Na2CO3 (Blank), 20 mg 0.2%Pt@Beta, 1 mL water, room temperature, 24 h. (B) Zeta potentials of 0.2%Pt@Beta colloidal particles from an emulsion with an aqueous solution of adsorbate (1 mmol L-1) (Blue diamond) or an aqueous solution of adsorbate (1 mmol L-1) in the presence of Na2CO3 (6 mmol L-1) (Black square). (F) The changing trend of the yield with the adsorption amount of FFCA.

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直接合成Beta沸石封装Pt纳米粒子用于5-羟甲基糠醛合成2,5-呋喃二甲酸

Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid

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