Citation: Rui HUANG, Shengjie LIU, Qingyuan WU, Nanfeng ZHENG. Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(1): 201-212. doi: 10.11862/CJIC.20240356 shu

Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects

Rui HUANG ¹ ,
Shengjie LIU ^{1, 2} ,
Qingyuan WU ^{1, 2,,} ,
Nanfeng ZHENG ^{1, 2,,}

1.
New Cornerstone Science Laboratory, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
2.
Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, Fujian 361002, China

Corresponding author: Qingyuan WU, qywu@xmu.edu.cn Nanfeng ZHENG, nfzheng@xmu.edu.cn
Received Date: 1 October 2024
Revised Date: 25 November 2024

Figures(5)

The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd-based catalysts that were co-modified with organic and inorganic ligands. It was demonstrated that the catalysts contained Pd species in mixed valence states, with high valence Pd at the metal-support interface and zero valence Pd at the metal surface. While the strong coordination of triphenylphosphine (PPh₃) to Pd⁰ on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation, the coordination of sodium metavanadate (NaVO₃) to high-valence Pd sites at the interface helps to activate H₂ in a heterolytic pathway for the selective hydrogenation of nitro-groups. The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
- halogenated nitroaromatic,
- heterogeneous catalysis,
- hydrogenation,
- selectivity control,
- interfacial effect
1. [1]
  CORMA A, SERNA P, CONCEPCIóN P, CALVINO J J. Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics[J]. J. Am. Chem. Soc., 2008,130(27):8748-8753. doi: 10.1021/ja800959g
2. [2]
  WU Q Y, SU W, HUANG R, SHEN H, QIAO M F, QIN R X, ZHENG N F. Full selectivity control over the catalytic hydrogenation of nitroaromatics into six products[J]. Angew. Chem.‒Int. Edit., 2024,63(38)e202408731. doi: 10.1002/anie.202408731
3. [3]
  SERNA P, CORMA A. Transforming nano metal nonselective particulates into chemoselective catalysts for hydrogenation of substituted nitrobenzenes[J]. ACS Catal., 2015,5(12):7114-7121. doi: 10.1021/acscatal.5b01846
4. [4]
  SUN X L, WANG Y C, WU Q Y, HAN Y Z, GONG X K, TANG X K, AIKENS C M, SHEN H, ZHENG N F. Cu₆₆ nanoclusters from hierarchical square motifs: Synthesis, assembly, and catalysis[J]. Aggregate, 2024e651. doi: 10.1002/agt2.651
5. [5]
  BLASER H U, STEINER H, STUDER M. Selective catalytic hydrogenation of functionalized nitroarenes: An update[J]. ChemCatChem, 2009,1(2):210-221. doi: 10.1002/cctc.200900129
6. [6]
  LI K J, QIN R X, LIU K L, ZHOU W T, LIU N, ZHANG Y Z, LIU S J, CHEN J, FU G, ZHENG N F. Carbon deposition on heterogeneous Pt catalysts promotes the selective hydrogenation of halogenated nitroaromatics[J]. ACS Appl. Mater. Interfaces, 2021,13(44):52193-52201. doi: 10.1021/acsami.1c11548
7. [7]
  FORMENTI D, FERRETTI F, SCHARNAGL F K, BELLER M. Reduction of nitro compounds using 3d-non-noble metal catalysts[J]. Chem. Rev., 2019,119(4):2611-2680. doi: 10.1021/acs.chemrev.8b00547
8. [8]
  SHEN H, WU Q Y, MALOLA S, HAN Y Z, XU Z, QIN R X, TANG X K, CHEN Y B, TEO B K, HÄKKINEN H, ZHENG N F. N-heterocyclic carbene-stabilized gold nanoclusters with organometallic motifs for promoting catalysis[J]. J. Am. Chem. Soc., 2022,144(24):10844-10853. doi: 10.1021/jacs.2c02669
9. [9]
  MITCHELL S, QIN R X, ZHENG N F, PEREZ-RAMIREZ J. Nanoscale engineering of catalytic materials for sustainable technologies[J]. Nat. Nanotechnol., 2021,16(2):129-139. doi: 10.1038/s41565-020-00799-8
10. [10]
  QIN R X, LIU K L, WU Q Y, ZHENG N F. Surface coordination chemistry of atomically dispersed metal catalysts[J]. Chem. Rev., 2020,120(21):11810-11899. doi: 10.1021/acs.chemrev.0c00094
11. [11]
  GUO M, LI H, REN Y Q, REN X M, YANG Q H, LI C. Improving catalytic hydrogenation performance of Pd nanoparticles by electronic modulation using phosphine ligands[J]. ACS Catal., 2018,8(7):6476-6485. doi: 10.1021/acscatal.8b00872
12. [12]
  MAKOSCH M, LIN W I, BUMBáLEK V, Sá J, MEDLIN J W, HUNGERBüHLER K, VAN BOKHOVEN J A. Organic thiol modified Pt/TiO₂ catalysts to control chemoselective hydrogenation of substituted nitroarenes[J]. ACS Catal., 2012,2(10):2079-2081. doi: 10.1021/cs300378p
13. [13]
  ZHAO X J, ZHOU L Y, ZHANG W Y, HU C Y, DAI L, REN L T, WU B H, FU G, ZHENG N F. Thiol treatment creates selective palladium catalysts for semihydrogenation of internal alkynes[J]. Chem, 2018,4(5):1080-1091. doi: 10.1016/j.chempr.2018.02.011
14. [14]
  WU Q Y, ZHOU W T, SHEN H, QIN R X, HONG Q M, YI X D, ZHENG N F. Surface coordination decouples hydrogenation catalysis on supported metal catalysts[J]. CCS Chem., 2022,5(5):1215-1224.
15. [15]
  WANG W, XU W L, THAPA K B, YANG X R, LIANG J H, ZHU L Y, ZHU J L. Morpholine-modified Pd/γ-Al₂O₃@ASMA pellet catalyst with excellent catalytic selectivity in the hydrogenation of p-chloronitrobenzene to p-chloroaniline[J]. Catalysts, 2017,7(10)292. doi: 10.3390/catal7100292
16. [16]
  MARSHALL S T, O'BRIEN M, OETTER B, CORPUZ A, RICHARDS R M, SCHWARTZ D K, MEDLIN J W. Controlled selectivity for palladium catalysts using self-assembled monolayers[J]. Nat. Mater., 2010,9(10):853-858. doi: 10.1038/nmat2849
17. [17]
  SCHOENBAUM C A, SCHWARTZ D K, MEDLIN J W. Controlling the surface environment of heterogeneous catalysts using self-assembled monolayers[J]. Acc. Chem. Res., 2014,47(4):1438-1445. doi: 10.1021/ar500029y
18. [18]
  WU B H, HUANG H Q, YANG J, ZHENG N F, FU G. Selective hydrogenation of α, β-unsaturated aldehydes catalyzed by amine-capped platinum-cobalt nanocrystals[J]. Angew. Chem.‒Int. Edit., 2012,51(14):3440-3443. doi: 10.1002/anie.201108593
19. [19]
  RUAN P P, CHEN B L, ZHOU Q, ZHANG H S, WANG Y H, LIU K L, ZHOU W T, QIN R X, LIU Z, FU G, ZHENG N F. Upgrading heterogeneous Ni catalysts with thiol modification[J]. The Innovation, 2023,4(1)100362. doi: 10.1016/j.xinn.2022.100362
20. [20]
  LU L F, ZOU S H, FANG B Z. The critical impacts of ligands on heterogeneous nanocatalysis: A review[J]. ACS Catal., 2021,11(10):6020-6058. doi: 10.1021/acscatal.1c00903
21. [21]
  CARGNELLO M, CHEN C, DIROLL B T, DOAN-NGUYEN V V, GORTE R J, MURRAY C B. Efficient removal of organic ligands from supported nanocrystals by fast thermal annealing enables catalytic studies on well-defined active phases[J]. J. Am. Chem. Soc., 2015,137(21):6906-6911. doi: 10.1021/jacs.5b03333
22. [22]
  BAUMEISTER P, BLASER H U, STUDER M. Strong reduction of hydroxylamine accumulation in the catalytic hydrogenation of nitroarenes by vanadium promoters[J]. Catal. Lett., 1997,49:219-222. doi: 10.1023/A:1019034128024
23. [23]
  STUDER M, NETO S, BLASER H U. Modulating the hydroxylamine accumulation in the hydrogenation of substituted nitroarenes using vanadium-promoted RNi catalysts[J]. Top. Catal., 2000,13:205-212. doi: 10.1023/A:1009050804228
24. [24]
  ZHANG L, WANG L, JIANG Z Y, XIE Z X. Synthesis of size-controlled monodisperse Pd nanoparticles via a non-aqueous seed-mediated growth[J]. Nanoscale Res. Lett., 2012,7312. doi: 10.1186/1556-276X-7-312
25. [25]
  ZHANG J, WANG L, SHAO Y, WANG Y Q, GATES B C, XIAO F S. A Pd@zeolite catalyst for nitroarene hydrogenation with high product selectivity by sterically controlled adsorption in the zeolite micropores[J]. Angew. Chem.‒Int. Edit., 2017,56(33):9747-9751. doi: 10.1002/anie.201703938
26. [26]
  LIU P X, ZHAO Y, QIN R X, MO S G, CHEN G X, GU L, CHEVRIER D M, ZHANG P, GUO Q, ZANG D D, WU B H, FU G, ZHENG N F. Photochemical route for synthesizing atomically dispersed palladium catalysts[J]. Science, 2016,352(6287):797-801. doi: 10.1126/science.aaf5251
27. [27]
  SCHALOW T, BRANDT B, STARR D E, LAURIN M, SHAIKHUTDINOV S K, SCHAUERMANN S, LIBUDA J, FREUND H J. Size-dependent oxidation mechanism of supported Pd nanoparticles[J]. Angew. Chem.‒Int. Edit., 2006,45(22):3693-3697. doi: 10.1002/anie.200504253
28. [28]
  YOU P Y, ZHAN S Q, RUAN P P, QIN R X, MO S G, ZHANG Y Z, LIU K L, ZHENG L S, ZHENG N F. Interfacial oxidized Pd species dominate catalytic hydrogenation of polar unsaturated bonds[J]. Nano Res., 2024,17:228-234. doi: 10.1007/s12274-023-5538-9
29. [29]
  CHEN G X, ZHAO Y, FU G, DUCHESNE P N, GU L, ZHENG Y P, WENG X F, CHEN M S, ZHANG P, PAO C W, LEE J F, ZHENG N F. Interfacial effects in iron-nickel hydroxide-platinum nanoparticles enhance catalytic oxidation[J]. Science, 2014,344(6183):495-499. doi: 10.1126/science.1252553
30. [30]
  ZHANG W Y, QIN Q, DAI L, QIN R X, ZHAO X J, CHEN X M, OU D H, CHEN J, CHUONG T T, WU B H, ZHENG N F. Electrochemical reduction of carbon dioxide to methanol on hierarchical Pd/SnO₂ nanosheets with abundant Pd-O-Sn interfaces[J]. Angew. Chem.‒Int. Edit., 2018,57(30):9475-9479. doi: 10.1002/anie.201804142
31. [31]
  WANG Y, QIN R X, WANG Y K, REN J, ZHOU W T, LI L Y, MING J, ZHANG W Y, FU G, ZHENG N F. Chemoselective hydrogenation of nitroaromatics at the nanoscale iron(Ⅲ)-OH-platinum interface[J]. Angew. Chem.‒Int. Edit.., 2020,59(31):12736-12740. doi: 10.1002/anie.202003651
32. [32]
  WU Q Y, QIN R X, ZANG D D, ZHANG W Y, WU B H, ZHENG N F. Stabilizing catalytic Pt-OH-Fe(Ⅲ) interfaces by mesoporous TiO₂ with rich surface hydroxyl groups[J]. Acta Chim. Sin., 2018,76(8):617-621.
33. [33]
  HE Y F. Morphology of vanadium(Ⅴ) and (Ⅳ) in water and vanadium(Ⅳ) complexes[J]. Chemical Engineering of Oil & Gas, 1983(3):5-13.
34. [34]
  SCHOISWOHL J, SURNEV S, NETZER F P, KRESSE G. Vanadium oxide nanostructures: From zero- to three-dimensional[J]. J. Phys.: Condens. Matter, 2006,18:R1-R14. doi: 10.1088/0953-8984/18/4/R01
35. [35]
  WU Q Y, QIN R X, ZHU M S, SHEN H, YU S S, ZHONG Y Y, FU G, YI X D, ZHENG N F. Frustrated Lewis pairs on pentacoordinated Al³⁺-enriched Al₂O₃ promote heterolytic hydrogen activation and hydrogenation[J]. Chem. Sci., 2024,15(9):3140-3147. doi: 10.1039/D3SC06425E
36. [36]
  SHEN H, WU Q Y, HAZER M S, TANG X K, HAN Y Z, QIN R X, MA C X, MALOLA S, TEO B K, HÄKKINEN H, ZHENG N F. Regioselective hydrogenation of alkenes over atomically dispersed Pd sites on NHC-stabilized bimetallic nanoclusters[J]. Chem, 2022,8(9):2380-2392. doi: 10.1016/j.chempr.2022.04.017
1. [1]
  Shaoming Dong , Yiming Niu , Yinghui Pu , Yongzhao Wang , Bingsen Zhang . Subsurface carbon modification of Ni-Ga for improved selectivity in acetylene hydrogenation reaction. Chinese Chemical Letters, 2024, 35(12): 109525-. doi: 10.1016/j.cclet.2024.109525
2. [2]
  Sanmei Wang , Dengxin Yan , Wenhua Zhang , Liangbing Wang . Graphene-supported isolated platinum atoms and platinum dimers for CO₂ hydrogenation: Catalytic activity and selectivity variations. Chinese Chemical Letters, 2025, 36(4): 110611-. doi: 10.1016/j.cclet.2024.110611
3. [3]
  Wenjiang LI , Pingli GUAN , Rui YU , Yuansheng CHENG , Xianwen WEI . C₆₀-MoP-C nanoflowers van der Waals heterojunctions and its electrocatalytic hydrogen evolution performance. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 771-781. doi: 10.11862/CJIC.20230289
4. [4]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
5. [5]
  Ming Huang , Xiuju Cai , Yan Liu , Zhuofeng Ke . Base-controlled NHC-Ru-catalyzed transfer hydrogenation and α-methylation/transfer hydrogenation of ketones using methanol. Chinese Chemical Letters, 2024, 35(7): 109323-. doi: 10.1016/j.cclet.2023.109323
6. [6]
  Min Chen , Boyu Peng , Xuyun Guo , Ye Zhu , Hanying Li . Polyethylene interfacial dielectric layer for organic semiconductor single crystal based field-effect transistors. Chinese Chemical Letters, 2024, 35(4): 109051-. doi: 10.1016/j.cclet.2023.109051
7. [7]
  Dongmei Yao , Junsheng Zheng , Liming Jin , Xiaomin Meng , Zize Zhan , Runlin Fan , Cong Feng , Pingwen Ming . Effect of surface oxidation on the interfacial and mechanical properties in graphite/epoxy composites composite bipolar plates. Chinese Chemical Letters, 2024, 35(11): 109382-. doi: 10.1016/j.cclet.2023.109382
8. [8]
  Jianing He , Xiao Wang , Zijian Wang , Ruize Jiang , Ke Wang , Rui Zhang , Huilin Wang , Baokang Geng , Hongyi Gao , Shuyan Song , Hongjie Zhang . Investigation on Cu promotion effect on Ce-based solid solution-anchored Rh single atoms for three-way catalysis. Chinese Chemical Letters, 2025, 36(2): 109640-. doi: 10.1016/j.cclet.2024.109640
9. [9]
  Minghui Zhang , Na Zhang , Qian Zhao , Chao Wang , Alexander Steiner , Jianliang Xiao , Weijun Tang . Cobalt pincer complex-catalyzed highly enantioselective hydrogenation of quinoxalines. Chinese Chemical Letters, 2025, 36(4): 110081-. doi: 10.1016/j.cclet.2024.110081
10. [10]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
11. [11]
  Jinyuan Cui , Tingting Yang , Teng Xu , Jin Lin , Kunlong Liu , Pengxin Liu . Hydrogen spillover enhances the selective hydrogenation of α,β-unsaturated aldehydes on the Cu-O-Ce interface. Chinese Journal of Structural Chemistry, 2025, 44(1): 100438-100438. doi: 10.1016/j.cjsc.2024.100438
12. [12]
  Yuan Teng , Zichun Zhou , Jinghua Chen , Siying Huang , Hongyan Chen , Daibin Kuang . Dual atom-bridge effect promoting interfacial charge transfer in 2D/2D Cs₃Bi₂Br₉/BiOBr epitaxial heterojunction for efficient photocatalysis. Chinese Chemical Letters, 2025, 36(2): 110430-. doi: 10.1016/j.cclet.2024.110430
13. [13]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
14. [14]
  Ruixue Liu , Xiaobing Ding , Qiwei Lang , Gen-Qiang Chen , Xumu Zhang . Enantioselective and divergent construction of chiral amino alcohols and oxazolidin-2-ones via Ir-f-phamidol-catalyzed dynamic kinetic asymmetric hydrogenation. Chinese Chemical Letters, 2025, 36(3): 110037-. doi: 10.1016/j.cclet.2024.110037
15. [15]
  Zhongjie Li , Xiangyue Kong , Yuhao Liu , Huayu Qiu , Lingling Zhan , Shouchun Yin . Progress of additives for morphology control in organic photovoltaics. Chinese Chemical Letters, 2024, 35(6): 109378-. doi: 10.1016/j.cclet.2023.109378
16. [16]
  Conghui Wang , Lei Xu , Zhenhua Jia , Teck-Peng Loh . Recent applications of macrocycles in supramolecular catalysis. Chinese Chemical Letters, 2024, 35(4): 109075-. doi: 10.1016/j.cclet.2023.109075
17. [17]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
18. [18]
  Lin Zhang , Chaoran Li , Thongthai Witoon , Xingda An , Le He . Nano-thermometry in photothermal catalysis. Chinese Journal of Structural Chemistry, 2025, 44(4): 100456-100456. doi: 10.1016/j.cjsc.2024.100456
19. [19]
  Huangjie Lu , Yingzhe Du , Peng Lin , Jian Lin . Separation of americium from lanthanides based on oxidation state control. Chinese Journal of Structural Chemistry, 2024, 43(10): 100344-100344. doi: 10.1016/j.cjsc.2024.100344
20. [20]
  Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443

Get Citation

PDF

XML

Metrics

PDF Downloads(20)
Abstract views(435)
HTML views(68)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142