具有超低镍负载的Ni-C3N4高效催化5-羟甲基糠醛氢解制2,5-二甲基呋喃

doi:10.1016/S1872-2067(24)60017-3

催化学报 ›› 2024, Vol. 60: 253-261.DOI: 10.1016/S1872-2067(24)60017-3

具有超低镍负载的Ni-C₃N₄高效催化5-羟甲基糠醛氢解制2,5-二甲基呋喃

曲虹宇^a, 胡文德^b, 李相呈^b^,^*(), 徐睿^b, 韩笑^b, 李俊杰^b, 陆怡卿^b, 叶迎春^b, 王传明^b^,^*(), 王振东^b, 杨为民^a^,^b^,^*()

^a华东理工大学化工学院, 上海 200237
^b中石化(上海)石油化工研究院有限公司, 绿色化工与工业催化全国重点实验室, 上海 201208

收稿日期:2024-01-05 接受日期:2024-02-28 出版日期:2024-05-18 发布日期:2024-05-20
通讯作者: *电子信箱: lixch.sshy@sinopec.com (李相呈), wangcm.sshy@sinopec.com (王传明), yangwm.sshy@sinopec.com (杨为民).
作者简介:第一联系人：¹共同第一作者.
基金资助:
国家自然科学基金(21972168);国家自然科学基金(U22B6011);上海市科委启明星项目(23YF1459500)

Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C₃N₄ catalysts with ultra-low Ni loading

Hongyu Qu^a, Wende Hu^b, Xiangcheng Li^b^,^*(), Rui Xu^b, Xiao Han^b, Junjie Li^b, Yiqing Lu^b, Yingchun Ye^b, Chuanming Wang^b^,^*(), Zhendong Wang^b, Weimin Yang^a^,^b^,^*()

^aSchool of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^bState Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Sinopec Shanghai Research Institute of Petrochemical Technology Co., Ltd., Shanghai 201208, China

Received:2024-01-05 Accepted:2024-02-28 Online:2024-05-18 Published:2024-05-20
Contact: *E-mail: lixch.sshy@sinopec.com (X. Li), wangcm.sshy@sinopec.com (C. Wang), yangwm.sshy@sinopec.com (W. Yang).
About author:First author contact:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21972168);National Natural Science Foundation of China(U22B6011);Shanghai Science and Technology Committee Rising-Star Program(23YF1459500)

摘要/Abstract

摘要：

生物质平台化合物的选择性氢解对生产可持续化学品和燃料具有重要意义. 2,5-二甲基呋喃(DMF)是一种重要的生物基化学品, 其不仅可作为汽油添加剂, 还可与乙烯发生Diels-Alder环加成脱水反应直接合成生物基对二甲苯. DMF主要通过5-羟甲基糠醛(HMF)氢解制备. 当以氢气为氢源时, 常用的催化剂体系包括贵金属(如Ru, Pt, Pd)及多种非贵金属(如Ni, Cu, Co)复合催化剂体系. 虽然上述催化剂表现出良好的催化性能, 但是贵金属的高成本以及非贵金属复合催化剂的回收难等问题阻碍了其工业应用. 因此, 利用单一非贵金属催化剂实现高效HMF氢化制DMF具有重要意义.

本文采用简单的配位-浸渍-热解法制备了超低Ni负载的非贵金属Ni-C₃N₄/HC催化剂, Ni负载量低至0.86 wt%. 在190 °C及1.5 MPa氢气条件下, 经过4 h反应, HMF完全转化, DMF产率达到94.2%, DMF生产能力可达12.8 mmol_DMF mmol_Ni^‒1 h^‒1, 在已报道的Ni, Co和Cu基催化剂中处于较高水平. 此外, Ni-C₃N₄/HC催化剂表现出良好的稳定性, 在固定床反应器中连续反应120 h未见明显失活. 透射电镜结果表明, Ni物种高度分散在活性炭载体上, 其平均粒径约为2.6 nm. Ni纳米颗粒被约1.3 nm厚的C₃N₄壳层紧密包裹, 有效稳定了Ni纳米颗粒并抑制了其在反应过程中团聚. X射线能谱分析显示, Ni和N元素呈现均匀分布, 表明可能形成了Ni₃N物种. X射线光电子能谱和电子能量损失谱结果进一步证实了Ni₃N物种的存在. 密度泛函理论计算结果表明, Ni₃N是氢解反应的本征活性组分, 它表现出良好的C‒O键活化性能. 推测反应主要遵循HMF先转化为MF(5-甲基糠醛), 再转化为MFA(5-甲基-2-呋喃甲醇), 最终生成DMF的路线进行.

鉴于Ni-C₃N₄/HC催化剂中的Ni₃N物种表现出了较好的C‒O键活化性能, 进一步考察了该催化剂对木质素衍生单体和木质素模型化合物的催化性能. 实验结果表明, Ni-C₃N₄/HC催化剂在C‒O键活化断裂加氢反应中表现出广泛的适用性. 另外, H₂处理的活性炭载体也发挥了重要作用: (1) 降低了活性炭的含氧量, 提高载体热稳定性, 并减弱了载体的酸性, 从而有效避免了底物的HMF聚合; (2) 有助于Ni物种的均匀分散, 减少了NiO物种的生成, 增加了Ni₃N活性物种的含量, 从而提升了催化剂的性能.

综上, 本文制备了超低Ni负载的非贵金属Ni-C₃N₄/HC催化剂, 其表现出高效的HMF氢解制DMF性能及良好的稳定性. 同时, 该催化剂对木质素衍生单体和木质素模型化合物也有广泛的适用性. 本研究为开发用于生物质加氢和氢解反应的单一非贵金属催化剂提供了新思路.

关键词: 生物质, 5-羟甲基糠醛, 2,5-二甲基呋喃, 氢解, Ni₃N

Abstract:

Selective hydrogenolysis of biomass-based platform compounds is of great importance for the production of chemicals and fuels. Herein, we reported that the catalyst of Ni-C₃N₄ supported on H₂ activated carbon (HC) synthesized by a simple coordination-impregnation-pyrolysis method is efficient for the hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF); the yield of 94.2% can be obtained in a batch reactor and the lifetime of greater than 120 h can be achieved in fixed-bed experiment. It is demonstrated that Ni nanoparticles coated by graphitic C₃N₄ shell were highly dispersed on the surface of HC and the Ni loading is as low as 0.86 wt%, beneficial to the anti-sintering of Ni nanoparticles during the reaction. Both XPS characterizations and theoretical calculations reveal that Ni₃N is the intrinsic active component for the hydrogenolysis, which exhibits efficient activity for the dissociation of C‒O bond. This work opens up a new avenue to develop catalysts with single non-noble metal component for the efficient conversion of biomass-based chemicals.

Key words: Biomass, 5-Hydroxymethylfurfural, 2,5-Dimethylfuran, Hydrogenolysis, Ni₃N

曲虹宇, 胡文德, 李相呈, 徐睿, 韩笑, 李俊杰, 陆怡卿, 叶迎春, 王传明, 王振东, 杨为民. 具有超低镍负载的Ni-C₃N₄高效催化5-羟甲基糠醛氢解制2,5-二甲基呋喃[J]. 催化学报, 2024, 60: 253-261.

Hongyu Qu, Wende Hu, Xiangcheng Li, Rui Xu, Xiao Han, Junjie Li, Yiqing Lu, Yingchun Ye, Chuanming Wang, Zhendong Wang, Weimin Yang. Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C₃N₄ catalysts with ultra-low Ni loading[J]. Chinese Journal of Catalysis, 2024, 60: 253-261.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60017-3

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图/表 7

Table 1 Hydrogenolysis of HMF to DMF over various catalysts a.

Entry	Catalyst	HMF Conv. (mol%)	Product selectivity (mol%)						Carbon balance (%) ^c
Entry	Catalyst	HMF Conv. (mol%)	DMF	MF	MFA	DHMF	THFDM	Others ^b	Carbon balance (%) ^c
1	Ni-C₃N₄/HC	>99	94.2	3.1	0	0	1.9	0.5	99.7
2	Ni-C₃N₄/C	>99	87.3	0.2	0.2	0	1.4	4.3	93.4
3	Ni/HC	57.4	47.3	43.3	1.2	0.7	1.5	2.1	96.1
4	Ni/HC ^d	98.8	81.6	1.7	0.1	0.1	3.9	3.7	91.1
5	Ni-C₃N₄	9.7	0	19.6	0	69.3	0	2.0	90.9

Scheme 1. Possible reaction pathway for the hydrogenation of HMF.

Fig. 1. TEM (a), HAADF-STEM (b,d), particle size distribution (c) and the corresponding EDX mapping images (e) of Ni-C3N4/HC sample after reduction at 500 °C.

Fig. 2. XPS spectra in Ni 2p3/2 region of Ni-C3N4/HC (a), Ni-C3N4/C (b), Ni/HC-unreduced (c) and Ni/HC (d) samples.

Fig. 3. (a) Adsorption structures and energies of HMF on Ni(111), Ni3N(11-0) and NiO(110) (associative and dissociative) surfaces. (b) Energy profiles of HMF hydrogenation to DMF on Ni3N(11-0) surface at 0 K. (c) Optimized structures of key intermediates and transition states during the hydrogenolysis of HMF to DMF on Ni3N(11-0) surface.

Fig. 4. The reusability of Ni-C3N4/HC catalyst for the conversion of HMF. (a) Reaction conditions in batch reactor: HMF 0.1 g, Ni-C3N4/HC catalyst 0.1 g, THF 20 g, 190 °C, H2 1.5 Mpa, 4 h. (b) Reaction conditions in fixed-bed reactor: 0.5 wt% HMF in THF, Ni-C3N4/HC catalyst 2.75 g, 160 °C, H2 1.5 Mpa, WHSV = 9.7 h?1, gas flow rate 20 mL min?1.

Table 2 Hydrogenolysis of different lignin-derived species catalyzed by Ni-C3N4/HC.

参考文献

[1]	M. Antar, D. Lyu, M. Nazari, A. Shah, X. Zhou, D. L. Smith, Renewable Sustainable Energy Rev., 2021, 139, 110691.
[2]	L. Lin, X. Han, B. Han, S. Yang, Chem. Soc. Rev., 2021, 50, 11270-11292.
[3]	Z. Xia, L. Niu, Y. An, G. Bian, T. Li, G. Bai, Green Chem., 2021, 23, 7763-7772.
[4]	J. Tuteja, H. Choudhary, S. Nishimura, K. Ebitani, ChemSusChem, 2014, 7, 96-100.
[5]	J. Kim, H. B. Bathula, S. Yun, Y. Jo, S. Lee, J. H. Baik, Y.-W. Suh, J. Ind. Eng. Chem., 2021, 102, 186-194.
[6]	W. Zhao, Z. Huang, L. Yang, X. Liu, H. Xie, Z. Liu, Appl. Surf. Sci., 2022, 577, 151869.
[7]	X. Wang, X. Liang, J. Li, Q. Li, Appl. Catal. A, 2019, 576, 85-95.
[8]	C. Chen, L. Wang, B. Zhu, Z. Zhou, S. I. El-Hout, J. Yang, J. Zhang, J. Energy Chem., 2021, 54, 528-554.
[9]	H. Yuan, H. Liu, J. Du, K. Liu, T. Wang, L. Liu, Appl. Microbiol. Biotechnol., 2020, 104, 527-543.
[10]	H. Weerathunga, S. Sarina, H.-Y. Zhu, E. R. Waclawik, ACS Omega, 2021, 6, 4740-4748.
[11]	T. Rui, G.-P. Lu, X. Zhao, X. Cao, Z. Chen, Chin. Chem. Lett., 2021, 32, 685-690.
[12]	Z. Xu, P. Yan, W. Xu, X. Liu, Z. Xia, B. Chung, S. Jia, Z. C. Zhang, ACS Catal., 2015, 5, 788-792.
[13]	A. T. Hoang, S. Nižetić, A. I. Ölçer, Fuel, 2021, 285, 119140.
[14]	J. Gulbinski, L. Ren, V. Vattipalli, H. Chen, J. Delaney, P. Bai, P. Dauenhauer, M. Tsapatsis, O. A. Abdelrahman, W. Fan, Ind. Eng. Chem. Res., 2020, 59, 22049-22056.
[15]	C. L. Williams, C.-C. Chang, P. Do, N. Nikbin, S. Caratzoulas, D. G. Vlachos, R. F. Lobo, W. Fan, P. J. Dauenhauer, ACS Catal., 2012, 2, 935-939.
[16]	H. Kim, J. Jae, Catalysts, 2021, 11, 1074.
[17]	J. Yu, S. Zhu, P. J. Dauenhauer, H. J. Cho, W. Fan, R. Gorte, Catal. Sci. Technol., 2016, 6, 5729-5736.
[18]	Y. Shao, M. Guo, M. Fan, K. Sun, G. Gao, C. Li, F. M. B. Kontchouo, L. Zhang, S. Zhang, X. Hu, Renewable Energy, 2023, 208, 105-118.
[19]	Y. Zu, P. Yang, J. Wang, X. Liu, J. Ren, G. Lu, Y. Wang, Appl. Catal. B, 2014, 146, 244-248.
[20]	X. Wang, Y. Liu, X. Liang, Green Chem., 2018, 20, 2894-2902.
[21]	D. S. Pisal, G. D. Yadav, Fuel, 2021, 290, 119947.
[22]	Y. Li, R. Wang, B. Huang, L. Zhang, X. Ma, S. Zhang, Z. Zhu, H. Lü, K. Yang, Appl. Surf. Sci., 2022, 604, 154579.
[23]	X. Chen, J. Wang, Z. Du, H. Cai, Y. Huang, G. Chen, C. Tang, Y. Fang, ChemistrySelect, 2023, 8, e202300862.
[24]	P. Hao, J. Zuo, W. Tong, J. Lin, Q. Wang, Z. Liu, Front. Chem., 2022, 10, 882670.
[25]	B. Hu, L. Warczinski, X. Li, M. Lu, J. Bitzer, M. Heidelmann, T. Eckhard, Q. Fu, J. Schulwitz, M. Merko, Angew. Chem. Int. Ed., 2021, 60, 6807-6815.
[26]	W. Liao, Z. Zhu, N. Chen, T. Su, C. Deng, Y. Zhao, W. Ren, H. Lu, Mol. Catal., 2020, 482, 110756.
[27]	Z. Gao, C. Li, G. Fan, L. Yang, F. Li, Appl. Catal. B, 2018, 226, 523-533.
[28]	Y. Liu, X. Shi, J. Hu, K. Liu, M. Zeng, Y. Hou, Z. Wei, ChemSusChem, 2022, 15, e202200193.
[29]	K. Zhang, Q. Meng, H. Wu, M. He, B. Han, ACS Sustainable Chem. Eng., 2022, 10, 10286-10293.
[30]	D. Guo, X. Liu, F. Cheng, W. Zhao, S. Wen, Y. Xiang, Q. Xu, N. Yu, D. Yin, Fuel, 2020, 274, 117853.
[31]	N. Chen, Z. Zhu, H. Ma, W. Liao, H. Lü, Mol. Catal., 2020, 486, 110882.
[32]	L. Feng, X. Li, Y. Lin, Y. Liang, Y. Chen, W. Zhou, Renewable Energy, 2020, 160, 261-268.
[33]	A. S. Nagpure, N. Lucas, S. V. Chilukuri, ACS Sustainable Chem. Eng., 2015, 3, 2909-2916.
[34]	S. Xiang, L. Dong, Z.-Q. Wang, X. Han, L. L. Daemen, J. Li, Y. Cheng, Y. Guo, X. Liu, Y. Hu, Nat. Commun., 2022, 13, 3657.
[35]	Y. B. Huang, M. Y. Chen, L. Yan, Q. X. Guo, Y. Fu, ChemSusChem, 2014, 7, 1068-1072.
[36]	N. Chen, Z. Zhu, T. Su, W. Liao, C. Deng, W. Ren, Y. Zhao, H. Lü, Chem. Eng. J., 2020, 381, 122755.
[37]	S. Shin, J. Jang, S.-H. Yoon, I. Mochida, Carbon, 1997, 35, 1739-1743.
[38]	S. Biniak, G. Szymański, J. Siedlewski, A. Świątkowski, Carbon, 1997, 35, 1799-1810.
[39]	R. Jiang, X. Song, S. Chen, Y. Chang, Z. Xie, Chem. React. Eng. Technol., 2007, 23, 375.
[40]	J. Wang, Z. Zhao, C. Shen, H. Liu, X. Pang, M. Gao, J. Mu, F. Cao, G. Li, Catal. Sci. Technol., 2021, 11, 2480-2490.
[41]	F. Song, W. Li, J. Yang, G. Han, P. Liao, Y. Sun, Nat. Commun., 2018, 9, 4531.
[42]	M.-S. Balogun, Y. Zeng, W. Qiu, Y. Luo, A. Onasanya, T. K. Olaniyi, Y. Tong, J. Mater. Chem. A, 2016, 4, 9844-9849.
[43]	J. Duan, S. Chen, M. Jaroniec, S. Z. Qiao, ACS Nano, 2015, 9, 931-940.
[44]	J. Li, H. Liu, Z. An, Y. Kong, L. Huang, D. Duan, R. Long, P. Yang, Y.-Y. Jiang, J. Liu, J. Catal., 2023, 417, 396-407.
[45]	S. Lambert, C. Cellier, P. Grange, J.-P. Pirard, B. t. Heinrichs, J. Catal., 2004, 221, 335-346.
[46]	Y. Wang, Z.-W. Fu, X.-L. Yue, Q.-Z. Qin, J. Electrochem. Soc., 2004, 151, E162-E167.
[47]	D. Gao, J. Zhang, T. Wang, W. Xiao, K. Tao, D. Xue, J. Ding, J. Mater. Chem. A, 2016, 4, 17363-17369.
[48]	I. Preda, R. Mossanek, M. Abbate, L. Alvarez, J. Méndez, A. Gutiérrez, L. Soriano, Surf. Sci., 2012, 606, 1426-1430.
[49]	H. Jin, X. Wang, C. Tang, A. Vasileff, L. Li, A. Slattery, S. Z. Qiao, Adv. Mater., 2021, 33, 2007508.
[50]	T. Wang, M. Wang, H. Yang, M. Xu, C. Zuo, K. Feng, M. Xie, J. Deng, J. Zhong, W. Zhou, Energy Environ. Sci., 2019, 12, 3522-3529.
[51]	L. Zhao, W. Wang, X. Zhao, Z. Hou, X. Fan, Y. Liu, Z. Quan, ACS Appl. Energy Mater., 2019, 2, 2692-2698.
[52]	Q. Liu, L. Xie, F. Qu, Z. Liu, G. Du, A.M. Asiri, X. Sun, Inorg. Chem. Front., 2017, 4, 1120-1124.
[53]	X. Zhao, X. Li, L. An, L. Zheng, J. Yang, D. Wang, Angew. Chem. Int. Ed., 2022, 61, e202206588.
[54]	S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau, S. b. Royer, Chem. Rev., 2018, 118, 11023-11117.
[55]	R. Gerardy, D. P. Debecker, J. Estager, P. Luis, J.-C. M. Monbaliu, Chem. Rev., 2020, 120, 7219-7347.

具有超低镍负载的Ni-C₃N₄高效催化5-羟甲基糠醛氢解制2,5-二甲基呋喃

Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-C₃N₄ catalysts with ultra-low Ni loading

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