铜镍双金属催化剂上糠醛水相选择性偶联加氢-重排制环戊酮

doi:10.1016/S1872-2067(21)63842-1

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2216-2224.DOI: 10.1016/S1872-2067(21)63842-1

铜镍双金属催化剂上糠醛水相选择性偶联加氢-重排制环戊酮

张树静^a^,^b^,^c, 马红^a^,^c^,^#(), 孙玉霞^a^,^b^,^c, 刘鑫^a^,^b^,^c, 张美云^a^,^b^,^c, 罗杨^a^,^b^,^c, 高进^a^,^c, 徐杰^a^,^c^,^*()

^a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, 大连116023
^b中国科学院大学, 北京100049
^c中国科学院洁净能源创新研究院, 辽宁大连116023

收稿日期:2021-04-02 接受日期:2021-04-02 出版日期:2021-12-18 发布日期:2021-05-19
通讯作者: 马红,徐杰
基金资助:
国家自然科学基金(21790331);国家自然科学基金(21872138);国家自然科学基金(21690084);中国科学院战略性先导科技专项(XDA21030400);中国科学院战略性先导科技专项(XDB17020300)

Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water

Shujing Zhang^a^,^b^,^c, Hong Ma^a^,^c^,^#(), Yuxia Sun^a^,^b^,^c, Xin Liu^a^,^b^,^c, Meiyun Zhang^a^,^b^,^c, Yang Luo^a^,^b^,^c, Jin Gao^a^,^c, Jie Xu^a^,^c^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cDalian National Laboratory for Clean Energy, Dalian 116023, Liaoning, China

Received:2021-04-02 Accepted:2021-04-02 Online:2021-12-18 Published:2021-05-19
Contact: Hong Ma,Jie Xu
About author:# Tel/Fax: +86-411-84379278; E-mail: mahong@dicp.ac.cn
* Tel/Fax: +86-411-84379245; E-mail: xujie@dicp.ac.cn;
Supported by:
National Natural Science Foundation of China(21790331);National Natural Science Foundation of China(21872138);National Natural Science Foundation of China(21690084);Strategic Priority Research Program of Chinese Academy of Sciences(XDA21030400);Strategic Priority Research Program of Chinese Academy of Sciences(XDB17020300)

摘要/Abstract

摘要：

生物质资源高效催化转化制备高附加值化学品具有重要的科学意义与工业应用潜力. 生物质基糠醛催化加氢-重排制备环戊酮是一条具有吸引力的“非石油”制备路线, 但该过程面临副产物多、环戊酮选择性难以提高等难题, 除糠醛外, 中间物种也很容易发生多种聚合副反应. 因此, 探索中间物种聚合副反应的条件和作用机制, 是提高目标产物环戊酮的选择性和收率的关键.

本文制备了CuNi/Al-MCM-41双金属纳米过渡金属催化剂, 通过精确调控介质水的pH值和原料浓度, 实现了糠醛加氢-重排耦合制备环戊酮的高选择性和高收率. 在2.0 MPa H₂, 160^oC和近中性条件下反应5 h, 糠醛的转化率为99.0%, 环戊酮的选择性达到97.7%; 其催化性能远远高于单组份铜或镍催化剂以及其它分子筛载体(MCM-41, SBA-15, HY, ZSM-5)负载的CuNi双金属催化剂. 研究结果表明, 高度分散在MCM-41上的少量Al组分, 有利于Cu, Ni金属组分相互均匀分散. XPS结果表明, 双金属催化剂CuNi/Al-MCM-41中Cu和Ni具有明显的电子结合能偏移, 表明Ni向Cu转移电子; 耦合催化反应性能的提高可能与CuNi双金属协同作用及电荷转移效应有关. 傅立叶变换红外光谱和质谱结果表明, 聚合副反应对反应体系的pH值敏感. 在酸性条件下, 中间产物糠醇在反应体系中容易发生聚合, 导致糠醇重排生成3-羟基环戊烯酮的选择性降低; 在碱性条件下, 3-羟基环戊烯酮转化为4-羟基-环戊-2-烯酮后, 容易进一步发生聚合副反应. 在近中性条件下可有效避免中间体的聚合, 提高加氢重排生成环戊酮的选择性. 此外,降低原料糠醛的初始浓度,有利于降低聚合等副反应,能够进一步提高目标产物环戊酮的收率.

本文为研制双金属纳米过渡金属催化剂以及利用双金属协同作用等方面提供新的启示, 为解决生物质原料转化过程中普遍存在的聚合副反应和碳平衡降低等问题提供了新思路

关键词: 偶联催化, 双金属协同效应, 环戊酮, 糠醛, 加氢-重排

Abstract:

Tandem catalysis for the hydrogenation rearrangement of furfural (FA) provides an attractive solution for manufacturing cyclopentanone (CPO) from renewable biomass resources. The CuNi/Al-MCM-41 catalyst was synthesized and afforded excellent catalytic performance with 99.0% conversion and 97.7% selectivity to CPO in a near-neutral solution under 2.0 MPa H₂ at 160 °C for 5 h, much higher than those on other molecular sieve supports including MCM-41, SBA-15, HY, and ZSM-5. A small amount of Al highly dispersed in MCM-41 plays an anchoring role and ensures the formation of highly dispersed CuNi bimetallic nanoparticles (NPs). The remarkably improved catalytic performance may be attributed to the bimetallic synergistic and charge transfer effects. In addition, the initial FA concentration and the aqueous system pH required precise control to minimize polymerization and achieve high selectivity of CPO. Fourier transform infrared spectroscopy and mass spectra results indicated that polymerization was sensitive to pH values. Under acidic conditions, FA and intermediate furfuryl alcohol polymerize, while the intermediate 4-hydroxy-2-cyclopentenone mainly polymerizes under alkaline conditions, blocking the cascade of multiple reactions. Therefore, near-neutral conditions are most suitable for minimizing the impact of polymerization. This study provides a useful solution for the current universal problems of polymerization side reactions and low carbon balance for biomass conversion.

Key words: Tandem catalysis, Bimetallic synergic effect, Cyclopentanone, Furfural, Hydrogenation-rearrangement

张树静, 马红, 孙玉霞, 刘鑫, 张美云, 罗杨, 高进, 徐杰. 铜镍双金属催化剂上糠醛水相选择性偶联加氢-重排制环戊酮[J]. 催化学报, 2021, 42(12): 2216-2224.

Shujing Zhang, Hong Ma, Yuxia Sun, Xin Liu, Meiyun Zhang, Yang Luo, Jin Gao, Jie Xu. Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water[J]. Chinese Journal of Catalysis, 2021, 42(12): 2216-2224.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63842-1

https://www.cjcatal.com/CN/Y2021/V42/I12/2216

图/表 11

Fig. 1. (a) Schematic illustration of the synthesis route for the CuNi/Al-MCM-41 catalyst; TEM images of Cu/Al-MCM-41 (b), Ni/Al-MCM-41 (c), and CuNi/Al-MCM-41 (d,f,g); (e,h) HRTEM images of CuNi/Al-MCM-41; (i) XRD patterns of CuNi/Al-MCM-41 (1), Cu/Al-MCM-41 (2), and Ni/Al-MCM-41 (3).

Fig. 2. Scanning TEM high angle annular dark field (STEM-HAADF) image, the corresponding EDX elemental mapping of the O, Si, Al, Ni, and Cu, and line-scanning profiles recorded along the line marked for CuNi/Al-MCM-41 catalyst.

Fig. 3. Hydrogenation rearrangement of FA over CuNi bimetallic catalysts. Reaction condition: 0.5 g FA, 0.0625 g catalysts, 160 °C, 2.0 MPa H2, 5 h, 5 mL H2O. a: 10 mL H2O.

Fig. 4. XRD patterns of different CuNi bimetallic catalysts.

Fig. 5. XPS spectra of different catalysts. (a) Ni 2p of Ni/Al-MCM-41 and CuNi/Al-MCM-41; (b) Cu 2p of Cu/Al-MCM-41 and CuNi/Al-MCM-41; (c) Cu Auger 2p of Cu/Al-MCM-41 and CuNi/Al-MCM-41.

Table 1 Catalytic performance of the FA hydrogenation rearrangement with different catalysts.

Entry	Catalyst	Conversion (mol%)	Product yield (mol%)
Entry	Catalyst	Conversion (mol%)	FAL	CPO	CPL	THFA	Others
1	CuNi/Al-MCM-41	98.3	1.5	67.7	1.7	8.0	19.4
2	Ni/Al-MCM-41	66.8	2.6	16.8	n.d.	2.6	44.8
3	Cu/Al-MCM-41	49.6	5.3	1.2	n.d.	0.9	42.2
4	Cu/Al-MCM-41+ Ni/Al-MCM-41 Ni/Al-MCM-41	63.9	7.0	38.8	n.d.	3.0	15.1

Fig. 6. Relevance of pH and catalytic performance of CuNi/Al-MCM-41. Reaction condition: 0.5 g FA, 0.0625 g CuNi/Al-MCM-41, 160 °C, 2.0 MPa, 5 h, 10 mL H2O (regulated by H2SO4 and NaOH).

Fig. 7. Comparison of reactions in solutions at different pH values without catalysts using starting substrates of FA (a), FAL (b), and HCP (c), respectively, and the corresponding typical IR spectraofpolymers extracted from reaction of FA (d), FAL (e), and HCP (f) at the pH of 11.45. Reaction conditions: 0.5 g substrate, 2.0 MPa H2, 160 °C, and 10 mL H2O with initial pH of 2.81, 7.05, 11.45 (regulated by H2SO4 and NaOH).

Fig. 8. MALDI-TOF characteristic of polymer extracted from spent catalysts at pH = 2.86 (a) and 11.13 (b).

Table 2 Influence of FA concentration and temperature on hydrogenation rearrangement over CuNi/Al-MCM-41.

Entry	FA:H₂O (wt%)	Temperature (°C)	Conversion (mol%)	Selectivity (mol%)
Entry	FA:H₂O (wt%)	Temperature (°C)	Conversion (mol%)	FAL	CPO	CPL	THFA	Others	Excessive hydrogenation
1	5	80	38.1	64.7	n.d.	2.4	3.3	29.6	5.7
2	5	120	83.3	45.0	14.7	1.1	1.5	37.7	2.6
3	5	140	89.6	7.3	53.6	0.3	2.8	36.1	3.1
4	5	160	96.4	2.1	83.6	2.4	6.2	5.7	8.6
5	5	180	97.7	0.6	60.7	1.2	6.1	31.3	7.4
6	20	160	96.0	2.7	44.2	2.2	9.9	41.0	12.1
7	10	160	94.5	1.1	59.2	1.3	6.3	32.1	7.6
8	2.5	160	96.6	1.3	91.1	3.2	1.2	3.1	4.4
9 ^a	1.2	160	99.0	n.d.	97.7	0.6	n.d.	1.7	0.6
10 ^b	5	160	99.6	0.6	37.0	15.2	21.0	26.2	36.2
11 ^c	5	160	99.7	0.5	42.4	9.3	4.4	43.4	13.7

Scheme 1. Mechanism of the FA hydrogenation rearrangement and side reactions without the presence of a catalyst.

参考文献

[1]	S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau, S. Royer, Chem. Rev., 2018, 118, 11023-11117.
[2]	Y. Nakagawa, M. Tamura, K. Tomishige, ACS Catal., 2013, 3, 2655-2668.
[3]	Y. Deng, R. Gao, L. Lin, T. Liu, X. D. Wen, S. Wang, D. Ma, J. Am. Chem. Soc., 2018, 140, 14481-14489.
[4]	A. J. Kumalaputri, G. Bottari, P. M. Erne, H. J. Heeres, K. Barta, ChemSusChem, 2014, 7, 2266-2275.
[5]	P. Jia, X. Lan, X. Li, T. Wang, ACS Sustain. Chem. Eng., 2019, 7, 15221-15229.
[6]	J. Guo, G. Xu, Z. Han, Y. Zhang, Y. Fu, Q. Guo, ACS Sustain. Chem. Eng., 2014, 2, 2259-2266.
[7]	M. Hronec, K. Fulajtarová, Catal. Commun., 2012, 24, 100-104.
[8]	T. V. Bui, T. Sooknoi, D. E. Resasco, ChemSusChem, 2017, 10, 1631-1639.
[9]	R. Wang, G. Li, H. Tang, A. Wang, G. Xu, Y. Cong, X. Wang, T. Zhang, N. Li, ACS Sustain. Chem. Eng., 2019, 7, 17354-17361.
[10]	T. Omotoso, L. V. Herrera, T. Vann, N. M. Briggs, L. A. Gomez, L. Barrett, D. Jones, T. Pham, B. Wang, S. P. Crossley, Appl. Catal. B, 2019, 254, 491-499.
[11]	L. Wang, Y. Weng, X. Wang, H. Yin, F. Wang, X. Xue, X. Liu, F. Wang, P. Duan, Y. Zhang, Catal. Commun., 2019, 129, 105745.
[12]	G. S. Zhang, M.-M. Zhu, Q. Zhang, Y. M. Liu, H. Y. He, Y. Cao, Green Chem., 2016, 18, 2155-2164.
[13]	X. Li, Q. Deng, S. Zhou, J. Zou, J. Wang, R. Wang, Z. Zeng, S. Deng, J. Catal., 2019, 378, 201-208.
[14]	N. S. Date, S. E. Kondawar, R. C. Chikate, C. V. Rode, ACS Omega, 2018, 3, 9860-9871.
[15]	S. Zhang, H. Ma, Y. Sun, Y. Luo, X. Liu, M. Zhang, J. Gao, J. Xu, Green Chem., 2019, 21, 1702-1709.
[16]	Y. Luo, H. Ma, S. Zhang, D. Zheng, P. Che, X. Liu, M. Zhang, J. Gao, J. Xu, J. Am. Chem. Soc., 2020, 142, 6085-6092.
[17]	Y. Yang, Z. Du, Y. Huang, F. Lu, F. Wang, J. Gao, J. Xu, Green Chem., 2013, 15, 1932-1940.
[18]	P. A. Lin, R. M. Sankaran, Angew. Chem. Int. Ed., 2011, 50, 10953-10956.
[19]	K. Song, M. Lu, S. Xu, C. Chen, Y. Zhan, D. Li, C. Au, L. Jiang, K. Tomishige, Appl. Catal. B, 2018, 239, 324-333.
[20]	C. Verrier, S. Moebs-Sanchez, Y. Queneau, F. Popowycz, Org. Biomol. Chem., 2018, 16, 676-687.
[21]	X. Si, J. Chen, F. Lu, X. Liu, Y. Ren, R. Lu, H. Jiang, H. Liu, S. Miao, Y. Zhu, X. Luo, J. Xu, ACS Sustain. Chem. Eng., 2019, 7, 19034-19041.
[22]	Y. Liu, J. Zhao, J. Feng, Y. He, Y. Du, D. Li, J. Catal., 2018, 359, 251-260.
[23]	D. Spanu, S. Recchia, S. Mohajernia, O. Tomanec, S. Kment, R. Zboril, P. Schmuki, M. Altomare, ACS Catal., 2018, 8, 5298-5305.
[24]	W. Kang, H. Guo, A. Varma, Appl. Catal. B, 2019, 249, 54-62.
[25]	H. Yang, Y. Chen, X. Cui, G. Wang, Y. Cen, T. Deng, W. Yan, J. Gao, S. Zhu, U. Olsbye, J. Wang, W. Fan, Angew. Chem. Int. Ed., 2018, 57, 1836-1840.
[26]	A. R. Naghash, T. H. Etsell, S. Xu, Chem. Mater., 2006, 18, 2480-2488.
[27]	F. Gao, D. W. Goodman, Chem. Soc. Rev., 2012, 41, 8009-8020.
[28]	X. Zhu, Q. Guo, Y. Sun, S. Chen, J. Q. Wang, M. Wu, W. Fu, Y. Tang, X. Duan, Chen, Y. Wan, Nat. Commun., 2019, 10, 1428.
[29]	F. Tang, L. Wang, M. Dessie Walle, A. Mustapha, Y.-N. Liu, J. Catal., 2020, 383, 172-180.
[30]	S. J. Dee, A. T. Bell, ChemSusChem, 2011, 4, 1166-1173.
[31]	T. M. C Hoang, E. R. H. van Eck, W. P. Bula, J. G. E. Gardeniers, L. Lefferts, K. Seshan, Green Chem., 2015, 17, 959-972.
[32]	Z. Cheng, J. L. Everhart, G. Tsilomelekis, V. Nikolakis, B. Saha, D. G. Vlachos, Green Chem., 2018, 20, 997-1006.
[33]	J. Liu, H. Wang, S. Cheng, K. Y. Chan, Chem. Commun., 2004, 10, 728-729.
[34]	R. Gonzalez, J. M. Figueroa, H. Gonzalez, Eur. Polym. J., 2002, 38, 287-297.
[35]	Z. Wang, Z. Lu, X. Huang, R. Xue, L. Chen, Carbon, 1998, 36, 51-59.
[36]	N. Perret, A. Grigoropoulos, M. Zanella, T. D. Manning, J. B. Claridge, M. J. Rosseinsky, ChemSusChem, 2016, 9, 521-531.
[37]	I. van Zandvoort, Y. Wang, C. B. Rasrendra, E. R. van Eck, P. C. Bruijnincx, H. J. Heeres, B. M. Weckhuysen, ChemSusChem, 2013, 6, 1745-1758.

铜镍双金属催化剂上糠醛水相选择性偶联加氢-重排制环戊酮

Selective tandem hydrogenation and rearrangement of furfural to cyclopentanone over CuNi bimetallic catalyst in water

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 11

参考文献

相关文章 15

编辑推荐

Metrics

[1]	王洪芳, 徐雷涛, 吴景程, 周鹏, 陶沙沙, 逯宇轩, 吴贤文, 王双印, 邹雨芹. 通过TEMPO增强脱氢和OH吸附促进中性电解质中5-羟甲基糠醛的电催化氧化[J]. 催化学报, 2023, 46(3): 148-156.
[2]	张鹏业, 董文锦, 张媛媛, 赵立楠, 苑华磊, 王传军, 王文硕, 王含笑, 张洪禹, 刘健. 具有电子转移路径的金属化氮化碳选择性再生NADH和光酶偶联CO₂还原[J]. 催化学报, 2023, 54(11): 188-198.
[3]	李诗浩, 石家福, 刘书松, 李文萍, 陈裕, 单慧婷, 程雨晴, 吴洪, 姜忠义. 酶-光偶联催化系统中分子-电子-质子传递过程与机制[J]. 催化学报, 2023, 44(1): 96-110.
[4]	张姜, 王子剑, 陈慕耕, 朱义峰, 刘永梅, 贺鹤勇, 曹勇, 包信和. 氮掺杂碳层包覆纳米金催化5-羟甲基糠醛非临氢转化制5-甲基糠醛[J]. 催化学报, 2022, 43(8): 2212-2222.
[5]	李振宇, 淮丽媛, 郝盼盼, 赵玺, 王永钊, 张炳森, 谌春林, 张建. 碳纳米管负载钯基催化剂催化氧化2,5-呋喃二甲醇合成2,5-呋喃二甲酸[J]. 催化学报, 2022, 43(3): 793-801.
[6]	张文彪, 石杨豪, 杨洋, 谭静雯, 高庆生. 电催化糠醛加氢反应中钯纳米晶的晶面效应[J]. 催化学报, 2022, 43(12): 3116-3125.
[7]	郭斌, 贺露露, 唐钢锋, 张丽, 叶林, 岳斌, 曾适之, 贺鹤勇. 氧化钽及钽钨复合氧化物固体酸催化己糖脱水制备5-羟甲基糠醛以及非等计量比的甲酸和乙酰丙酸[J]. 催化学报, 2020, 41(8): 1248-1260.
[8]	霍娜, 马红, 王新红, 王天龙, 王刚, 王婷, 候磊磊, 高进, 徐杰. 非贵金属Co-N-C/MgO高效催化糠醛氧化酯化制糠酸甲酯[J]. 催化学报, 2017, 38(7): 1148-1154.
[9]	Sanjay Srivastava, G.C.Jadeja, Jigisha Parikh. 载体对其负载的Cu-Co双金属催化剂上5-羟甲基糠醛氢解选择性生成2,5-二甲基呋喃的影响[J]. 催化学报, 2017, 38(4): 699-709.
[10]	申越, 康玉茹, 孙建奎, 王超, 王波, 许凤, 孙润仓. 双相体系中凹土负载型固体酸SO₄^2-/In₂O₃-ATP催化己糖降解5-羟甲基糠醛[J]. 催化学报, 2016, 37(8): 1362-1368.
[11]	董静, 朱明明, 张高硕, 刘永梅, 曹勇, 刘苏, 王仰东. 水相介质中负载纳米金催化CO高选择性还原糠醛[J]. 催化学报, 2016, 37(10): 1669-1675.
[12]	李昌志, 蔡海乐, 张波, 李为臻, 裴广贤, 代弢, 王爱琴, 张涛. 果糖一步转化制备呋喃基燃料:溶剂效应及离子液体修饰活性金属对产物选择性的决定作用[J]. 催化学报, 2015, 36(9): 1638-1646.
[13]	李良, 丁姜宏, 蒋金刚, 朱治国, 吴鹏. 双功能[Sn,Al]-Beta分子筛一步催化葡萄糖生成5-羟甲基糠醛[J]. 催化学报, 2015, 36(6): 820-828.
[14]	解佳翰, 聂俊芳, 刘海超. 碱性条件下Ru/C催化5-羟甲基糠醛选择氧化反应[J]. 催化学报, 2014, 35(6): 937-944.
[15]	张晓辰, 王敏, 王业红, 张超峰, 张哲, 王峰, 徐杰. 磺酸官能化的磁性核壳结构的纳米材料用于果糖脱水制备5-羟甲基糠醛[J]. 催化学报, 2014, 35(5): 703-708.