镍铁双金属催化剂中铁对糠醛选择性加氢的促进作用

doi:10.1016/S1872-2067(26)64959-5

催化学报 ›› 2026, Vol. 83: 411-418.DOI: 10.1016/S1872-2067(26)64959-5

镍铁双金属催化剂中铁对糠醛选择性加氢的促进作用

刘鑫^a, 杨烨舟^b, 杨敬茹^b, 王茂弟^b^,^*(), 杨启华^b^,^*()

^a中国科学院大连化学物理研究所, 能源催化转化全国重点实验室, 辽宁大连 116023
^b浙江师范大学先进催化材料教育部重点实验室, 浙江省先进催化与吸附材料重点实验室, 浙江金华 321004

收稿日期:2025-08-12 接受日期:2025-10-30 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: qhyang@zjnu.cn (杨启华), maodiwang@zjnu.edu.cn (王茂弟).
基金资助:
国家自然科学基金(22272164);国家自然科学基金(22332002);浙江省创新创业领军人才引进项目(2022R01007)

Promotion effect of Fe in the selective hydrogenation of furfural with bimetallic NiFe catalysts

Xin Liu^a, Yezhou Yang^b, Jingru Yang^b, Maodi Wang^b^,^*(), Qihua Yang^b^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bKey Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory of Advanced Catalysis and Adsorption Materials, Zhejiang Normal University, Jinhua 321004, Zhejiang, China

Received:2025-08-12 Accepted:2025-10-30 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: qhyang@zjnu.cn (Q. Yang),maodiwang@zjnu.edu.cn (M. Wang).
Supported by:
National Natural Science Foundation of China(22272164);National Natural Science Foundation of China(22332002);Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2022R01007)

摘要/Abstract

摘要：

糠醛(FAL)选择性加氢制糠醇(FOL)是生物质资源利用的重要反应之一, 其关键在于实现高活性的同时获得高选择性. 但是FAL作为一种高度不饱和化合物, 其具有多种潜在的加氢反应途径, 因此实现羰基的选择性加氢是一项具有挑战性的任务. 迄今为止, 用于该反应的贵金属催化剂虽活性较高, 但却存在成本昂贵且选择性有限的问题; 而非贵金属如Ni催化剂成本低廉, 但其表面连续的Ni位点易导致FOL深度加氢为四氢糠醇, 因此其选择性通常也较低. 受自然界中的酶通过多位点协同实现精准催化的启发, 合理设计具有功能互补活性位点的催化剂, 以调控反应物吸附、活化路径并抑制副反应, 是实现高效选择性转化的有效策略. 但如何在非贵金属体系中有效整合并协调不同活性位点的功能, 以同时提升活性和选择性, 并明确其反应机理, 仍面临一些挑战.
本文报道了一种通过Fe掺杂对Ni/TiO₂催化剂进行改性的策略, 成功构建了NiFe双金属催化剂, 其中Fe和Ni位点功能互补, 协同作用于FAL选择性加氢过程. 在FAL加氢反应中, Ni/Fe-TiO₂催化剂表现出优异的催化性能: 当Fe含量≥4.9 wt%时, 在接近100%转化率下, 目标产物FOL选择性> 90%, 显著优于未改性的Ni/TiO₂催化剂(相同条件下选择性仅38%). 同时, 优化后的Ni/Fe_6.9-TiO₂催化剂的转化频率达到13.2 h^‒1, 高于Ni/TiO₂ (11.2 h^‒1), 实现了适量Fe掺杂的Ni催化剂在该反应中活性和选择性的同时提升. 为进一步探究Fe的促进机制, 进行了一系列机理研究. 结果表明, NiFe双金属协同效应是性能突破的核心: Fe位点对FAL分子中的羰基(C=O)基团表现出更强的亲和力, 主要负责吸附和活化底物; 而相邻的Ni位点则高效解离H₂分子产生活性氢原子, 并通过氢溢流作用传递至吸附有FAL的Fe位点完成对羰基的选择性加氢. 此外, Fe的引入形成NiFe合金, 稀释了连续的Ni位点, 有效削弱了产物FOL的吸附强度, 从而抑制了呋喃环的深度加氢. 该Ni/Fe-TiO₂催化剂展现出良好的循环稳定性, 连续使用5次后活性和选择性(> 90%)均未发生明显下降.
综上, 本文成功构建了一种NiFe双金属协同催化剂, 将其用于糠醛选择性加氢反应中, 表现出优异的催化性能. 催化性能的显著增强主要来源于Fe位点对羰基底物的特异性吸附活化与Ni位点对H₂的高效解离活化之间的协同作用, 以及Fe对连续Ni位点的稀释效应. 本文为设计高效、高选择性的非贵金属加氢催化剂提供了一种有效策略.

关键词: 双金属催化剂, 协同效应, 选择性加氢, 羰基

Abstract:

The selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) over Ni catalysts offers a sustainable route for biomass valorization. However, the conventional Ni catalysts suffer from poor selectivity in FAL hydrogenation. Herein, we report that the moderate Fe doping in Ni/TiO₂ significantly enhances selectivity without compromising catalytic activity for the selective hydrogenation of FAL to FOL. Notably, Ni/Fe-TiO₂ catalyst with Fe content ≥ 4.9 wt% maintained > 90% selectivity toward FOL at nearly 100% conversion, whereas Ni/TiO₂ achieved only 38% under the identical condition. Combined experimental and theoretical studies revealed that the enhanced catalytic performance of Ni/Fe-TiO₂ originates from the dilution of contiguous Ni sites by Fe, which suppresses the further hydrogenation of FOL. Moreover, Fe sites exhibited a stronger affinity for carbonyl groups compared to Ni(0), indicating complementary role where Ni(0) primarily facilitates H₂ dissociation, while Fe sites play a critical role in carbonyl activation. These findings underscore the superior synergistic effect of bimetallic systems in promoting selective functional group transformation.

Key words: Bimetallic catalysts, Synergistic effect, Selective hydrogenation, Carbonyl groups

刘鑫, 杨烨舟, 杨敬茹, 王茂弟, 杨启华. 镍铁双金属催化剂中铁对糠醛选择性加氢的促进作用[J]. 催化学报, 2026, 83: 411-418.

Xin Liu, Yezhou Yang, Jingru Yang, Maodi Wang, Qihua Yang. Promotion effect of Fe in the selective hydrogenation of furfural with bimetallic NiFe catalysts[J]. Chinese Journal of Catalysis, 2026, 83: 411-418.

×
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(26)64959-5

https://www.cjcatal.com/CN/Y2026/V83/I4/411

图/表 5

Fig. 1. HAADF-STEM images, Ni NPs size distributions (inset) and EDS mapping of Ni/TiO2 (a), Ni/Fe6.9-TiO2 (b). H2-TPR profiles (c), XPS spectra of Ni 2p3/2 (d), and Fe 2p3/2 (e) of Ni/TiO2 and Ni/Fe-TiO2 catalysts.

Fig. 2. Conversion of furfural (a) and selectivity to furfuryl alcohol (b) as a function of reaction time over Ni/TiO2 and Ni/Fe-TiO2. (c) Apparent TOF of furfural hydrogenation: (I) Ni/TiO2; (II) Ni/Fe2.2-TiO2; (III) Ni/Fe4.9-TiO2; (IV) Ni/Fe6.9-TiO2; (V) Ni/Fe8.4-TiO2 (Data was from the kinetic curve after the induction period). Reaction conditions: 100 °C, 2 MPa H2, 0.2 mmol furfural, 20 mg catalysts, 2 mL isopropyl alcohol.

Fig. 3. The effect of furfural concentration (a) and H2 pressure (b) for furfural hydrogenation over Ni/TiO2 and Ni/Fe6.9-TiO2. (c) The apparent activation barriers of Ni/TiO2 and Ni/Fe6.9-TiO2 for furfural hydrogenation.

Fig. 4. The potential energy surface diagrams of carbonyl hydrogenation of furfural on Ni (111) (a) and NiFe (111) (b).

Fig. 5. (a) Recycling stability of Ni/Fe6.9-TiO2 in furfural hydrogenation. Reaction conditions: 100 °C, 2 MPa H2, 0.2 mmol furfural, 20 mg catalysts, 2 mL isopropyl alcohol, t = 4 h. The PXRD patterns (b), the XPS spectra of Ni 2p3/2 (c), and the XPS spectra of Fe 2p3/2 (d) of Ni/Fe6.9-TiO2 after 5 cycles.

参考文献

[1]	V. R. Madduluri, K. K. Mandari, V. Velpula, M. Varkolu, S. R. R. Kamaraju, M. Kang, Fuel, 2020, 261, 116339.
[2]	J. Chheda, G. Huber, J. Dumesic, Angew. Chem. Int. Ed., 2007, 46, 7164-7183.
[3]	A. Corma, S. Iborra, A. Velty, Chem. Rev., 2007, 107, 2411-2502.
[4]	M. Besson, P. Gallezot, C. Pinel, Chem. Rev., 2014, 114, 1827-1870.
[5]	L. Ruan, A. Pei, H. Zhang, T. Zheng, L. Zhu, Ind. Catal., 2019, 27(9), 1-7.
[6]	X. Li, P. Jia, T. Wang, ACS Catal., 2016, 6, 7621-7640.
[7]	S. Chen, R. Wojcieszak, F. Dumeignil, E. Marceau, S. Royer, Chem. Rev., 2018, 118, 11023-11117.
[8]	W. S. Putro, T. Hara, N. Ichikuni, S. Shimazu, Chem. Lett., 2017, 46, 149-151.
[9]	K. Yan, G. Wu, T. Lafleur, C. Jarvis, Renew. Sustain. Energy Rev., 2014, 38, 663-676.
[10]	M. J. Taylor, L. J. Durndell, M. A. Isaacs, C. M. A. Parlett, K. Wilson, A. F. Lee, G. Kyriakou, Appl. Catal. B, 2016, 180, 580-585.
[11]	Q. Yuan, D. Zhang, L. van Haandel, F. Ye, T. Xue, E. J. M. Hensen, Y. Guan, J. Mol. Catal. A, 2015, 406, 58-64.
[12]	S. Bhogeswararao, D. Srinivas, J. Catal., 2015, 327, 65-77.
[13]	X. Wang, T. Song, G. Fu, Y. Yang, ACS Catal., 2023, 13, 11634-11643.
[14]	S. Sitthisa, D. E. Resasco, Catal. Lett., 2011, 141, 784-791.
[15]	Y. Nakagawa, H. Nakazawa, H. Watanabe, K. Tomishige, ChemCatChem, 2012, 4, 1791-1797.
[16]	A. Corma, P. Serna, Science, 2006, 313, 332-334.
[17]	L. Liu, A. Corma, Nat. Catal., 2021, 4, 453-456.
[18]	C. Vogt, B. M. Weckhuysen, Nat. Rev. Chem., 2022, 6, 89-111.
[19]	F. Zaera, Chem. Rev., 2022, 122, 8594-8757.
[20]	X. Liu, M. Wang, X. Ren, M. Guo, C. Li, H. Li, Q. Yang, ACS Catal., 2022, 12, 6618-6627.
[21]	S. Fan, Z. Yao, W. Cheng, X. Zhou, Y. Xu, X. Qin, S. Yao, X. Liu, J. Wang, X. Li, L. Lin, ACS Catal., 2023, 13, 757-765.
[22]	X. Liu, Y. Ren, M. Wang, X. Ren, J. Liu, Q. Yang, ACS Catal., 2022, 12, 11369-11379.
[23]	S. Wang, Y. Lv, J. Ren, Z. Xu, Q. Yang, H. Zhao, D. Gao, G. Chen, ACS Catal., 2023, 13, 8720-8730.
[24]	F. Meemken, K. Hungerbühler, A. Baiker, Angew. Chem. Int. Ed., 2014, 53, 8640-8644.
[25]	M. Zhao, K. Yuan, Y. Wang, G. Li, J. Guo, L. Gu, W. Hu, H. Zhao, Z. Tang, Nature, 2016, 539, 76-80.
[26]	F. Jiao, B. Bai, G. Li, X. Pan, Y. Ye, S. Qu, C. Xu, J. Xiao, Z. Jia, W. Liu, T. Peng, Y. Ding, C. Liu, J. Li, X. Bao, Science, 2023, 380, 727-730.
[27]	X. Ren, H. Dai, X. Liu, Q. Yang, Chin. J. Catal., 2024, 62, 108-123.
[28]	A. Halilu, T. H. Ali, A. Y. Atta, P. Sudarsanam, S. K. Bhargava, S. B. Abd Hamid, Energy Fuels, 2016, 30, 2216-2226.
[29]	Z. Zhao, X. Li, X. Liu, H. Gao, A. Jia, S. Xie, X. Song, X. Liu, F. Yang, Q. Yang, ACS Catal., 2024, 14, 4478-4488.
[30]	W. S. Putro, T. Kojima, T. Hara, N. Ichikuni, S. Shimazu, Catal. Sci. Technol., 2017, 7, 3637-3646.
[31]	D. Vargas-Hernández, J. M. Rubio-Caballero, J. Santamaría-González, R. Moreno-Tost, J. M. Mérida-Robles, M. A. Pérez-Cruz, A. Jiménez-López, R. Hernández-Huesca, P. Maireles-Torres, J. Mol. Catal. A, 2014, 383- 384, 106-113.
[32]	M. G. Prakash, R. Mahalakshmy, K. R. Krishnamurthy, B. Viswanathan, Catal. Today, 2016, 263, 105-111.
[33]	C. Dong, Y. Li, D. Cheng, M. Zhang, J. Liu, Y.-G. Wang, D. Xiao, D. Ma, ACS Catal., 2020, 10, 11011-11045.
[34]	Q. Sun, N. Wang, J. Yu, Adv. Mater., 2021, 33, 2104442.
[35]	F. Long, S. Wu, H. Chen, S. Jia, X. Cao, P. Liu, Y. Lu, J. Jiang, X. Zhang, J. Xu, J. Catal., 2023, 428, 115171.
[36]	R. Insyani, M.-K. Kim, J.-W. Choi, C.-J. Yoo, D. Jin Suh, H. Lee, C. Soo Kim, K. Ho Kim, K. Kim, J.-M. Ha, Chem. Eng. J., 2022, 446, 136578.
[37]	D. Han, W. Yin, S. Wang, S. Xia, ACS Sustainable Chem. Eng., 2021, 9, 15027-15041.
[38]	W. Lin, Y. Chen, Y. Zhang, Y. Zhang, J. Wang, L. Wang, C. C. Xu, R. Nie, ACS Catal., 2023, 13, 11256-11267.
[39]	C. Cheng, D. Shen, R. Xiao, C. Wu, Fuel, 2017, 189, 419-427.
[40]	F. He, T. Wang, X. Zhang, Q. Zhang, Y. Gong, H. Wei, K. Ren, Z. Men, Low-Carbon Chem. Chem. Eng., 2023, 48(6), 17-23.
[41]	O. J. Wimmers, P. Arnoldy, J. A. Moulijn, J. Phys. Chem., 1986, 90, 1331-1337.

镍铁双金属催化剂中铁对糠醛选择性加氢的促进作用

Promotion effect of Fe in the selective hydrogenation of furfural with bimetallic NiFe catalysts

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 15

编辑推荐

Metrics

[1]	李金河, 姚霞喜, 于晓慧, 周小松, 任伟, 王乐乐, 王伟康, 刘芹芹. Mo₂N QDs/ZnIn₂S₄异质结中的等离激元-激子-声子协同作用实现光生电子与空穴的同步高值化利用[J]. 催化学报, 2026, 83(4): 219-230.
[2]	刘畅, 王梅, 梁向明, 鲁统部. 碳载体上银双原子与银纳米颗粒的耦合用于高效电还原氮气制氨[J]. 催化学报, 2026, 82(3): 135-143.
[3]	高杰, 刘静, 王梦迪, 孙诺, 胡皓, 崔学晶, 周新, 姜鲁华. 构建锐钛矿-金红石TiO₂异质结构调控竞争吸附以缓解Ru在碱性氢氧化反应中的羟基毒化效应[J]. 催化学报, 2026, 82(3): 74-83.
[4]	韩贝, 靳宸, 罗翠红, 刘云焘, 戴志超, 孙运强, 甘自保, 王崇臣, 郑秀文, 胡尊富. 铁镍纳米颗粒与单原子位点协同驱动非自由基类芬顿催化反应: 单线态氧和电子转移途径主导的高效水净化[J]. 催化学报, 2026, 82(3): 187-200.
[5]	戚克振, 程蓓, Mahboobeh Setayeshmehr, Alireza Z. Moshfegh. 通过S型光催化与串联羰基化相结合实现太阳光驱动CO₂到化学品转化[J]. 催化学报, 2026, 81(2): 1-4.
[6]	马毅, 葛欢, 章勇, 简宁, 唐嘉陵, 胡宗坤, 于静, 李灿煌, 李露明, 李军山. 基于Ag与NiFe-LDH协同作用实现电催化PET碱性水解产物选择性制备甲酸盐与乙醇酸盐[J]. 催化学报, 2026, 80(1): 282-292.
[7]	梁婉滢, 许光月, 傅尧. 分子筛限域铜基催化剂上糠醛的精确受限过渡态构型选择性加氢[J]. 催化学报, 2025, 74(7): 71-81.
[8]	曹彦伟, 曲芸豪, 苏彬, 王功伟, 黄洋, 罗振敏, 庄林, 何林. CO-H₂O共电解制CO/O₂用于本质安全的乙烯/乙炔氧化双羰基化反应[J]. 催化学报, 2025, 74(7): 202-210.
[9]	张佳骏, 吴小锋. 铜催化的烷基溴和芳基硼酸酯的羰基化的铃木-宫浦反应[J]. 催化学报, 2025, 73(6): 146-152.
[10]	詹钰捷, 钟承钦, 毕明莉, 梁亚飞, 祁玉基, 陈家琪, 刘家旭, 张新党, 张帅, 王业红, 王峰. 催化甲醇选择性氧化制甲醛的铁钒催化剂活性位点的识别[J]. 催化学报, 2025, 72(5): 334-343.
[11]	冯超, 邵佳新, 吴汉洋, 杨恒攀, 蔚佳莹, 胡琪, 何传新. 超高过电位诱导NiS₂深度重构显著提高HER性能[J]. 催化学报, 2025, 72(5): 230-242.
[12]	刘奕, 周树清, 牛成功, 塔伊尔詹•泰勒•伊西姆詹, 朱永法, 王定胜, 杨秀林, 邱介山, 武斌. 稀CuRu合金与Cu/Ru双单原子的协同耦合加速碱性氢氧化的Volmer动力学[J]. 催化学报, 2025, 72(5): 266-276.
[13]	曹新诚, 赵佳平, 龙锋, 刘朋, 董煜国, 陈祖鹏, 徐俊明, 蒋剑春. 高分散MoO_x-Ru/C双金属催化剂催化酯类化合物高效氢解制备烷烃[J]. 催化学报, 2025, 71(4): 256-266.
[14]	贺捷婷, 梁瑜, 赵斌彬, 刘雷, 何迁, 王定胜, 董晋湘. CaAl-LDH层板金属元素同晶取代构建高密度单原子催化剂用于N-杂芳烃选择性加氢[J]. 催化学报, 2025, 70(3): 353-362.
[15]	姜建伟, Vinothkumar Ganesan, 崔仁洛, 申庭澈, 尹城镐, 朴纪映. 酰基钴基催化剂用于高活性高稳定性环氧化物羰基化制备β-内酯[J]. 催化学报, 2025, 68(1): 336-344.