Zinc modification of Ni-Ti as efficient Ni_xZn_yTi₁ catalysts with both geometric and electronic improvements for hydrogenation of nitroaromatics

Abstract

The catalytic hydrogenation of nitroaromatics is an environmentally friendly technology for aniline production, and it is crucial to develop noble-metal-free catalysts that can achieve chemoselective hydrogenation of nitroaromatics under mild reaction conditions. In this work, zinc-modified Ni-Ti catalysts (Ni_xZn_yTi₁) were fabricated and applied for the hydrogenation of nitroaromatics hydrogenation. It was found that the introduction of zinc effectively increases the surface Ni density, enhances the electronic effect, and improves the interaction between Ni and TiO₂, resulting in smaller Ni particle size, more oxygen vacancies, higher dispersion and greater concentration of Ni on the catalyst surface. Furthermore, the electron-rich Ni^δ– obtained by electron transfer from Zn and Ti to Ni effectively adsorbs and dissociates hydrogen. The results reveal that Ni_xZn_yTi₁ (Ni_0.5Zn_0.5Ti₁) shows excellent catalytic performance under mild conditions (70 °C and 6 bar). These findings provide a rational strategy for the development of highly active non-noble-metal hydrogenation catalysts.

Graphical abstract

Keywords

bimetal strategy / oxygen vacancy / non-noble metal catalyst / hydrogenation / aromatic nitro compounds

References

[1] Formenti D, Ferretti F, Scharnagl F K, Beller M. Reduction of nitro compounds using 3d-non-noble metal catalysts. Chemical Reviews, 2019, 119(4): 2611–2680

[2] Xiong W, Wang Z, He S, Hao F, Yang Y, Lv Y, Zhang W, Liu P, Luo H. Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for nitrobenzene hydrogenation. Applied Catalysis B: Environmental, 2019, 260: 118105–118114

[3] Xiong W, Wang K, Liu X, Hao F, Xiao H, Liu P, Luo H. 1,5-Dinitronaphthalene hydrogenation to 1,5-diaminonaphthalene over carbon nanotube supported non-noble metal catalysts under mild conditions. Applied Catalysis A, General, 2016, 514: 126–134

[4] Huang L, Lv Y, Wu S, Liu P, Xiong W, Hao F, Luo H. Activated carbon supported bimetallic catalysts with combined catalytic effects for aromatic nitro compounds hydrogenation under mild conditions. Applied Catalysis A, General, 2019, 577: 76–85

[5] Amali A J, Rana R K. Trapping Pd (0) in nanoparticle-assembled microcapsules: an efficient and reusable catalyst. Chemical Communications, 2008, (35): 4165–4167

[6] Visentin F, Puxty G, Kut O M, Hungerbühler K. Study of the hydrogenation of selected nitro compounds by simultaneous measurements of calorimetric, FT-IR, and gas-uptake signals. Industrial & Engineering Chemistry Research, 2006, 45(13): 4544–4553

[7] Corma A, Concepcion P, Serna P. A different reaction pathway for the reduction of aromatic nitro compounds on gold catalysts. Angewandte Chemie International Edition, 2007, 46(38): 7266–7269

[8] Peng Z, Li W, Miao Y, Chen S, Liu G, Liu S, Gao J, Li B, Liu Z. Ru nanospheres in water drops for enhanced catalytic performances in selective hydrogenation. ACS Applied Energy Materials, 2018, 1(8): 4277–4284

[9] Jagadeesh R V, Stemmler T, Surkus A, Junge H, Junge K, Beller M. Hydrogenation using iron oxide-based nanocatalysts for the synthesis of amines. Nature Protocols, 2015, 10(4): 548–557

[10] Wei Z, Wang J, Mao S, Su D, Jin H, Wang Y, Xu F, Li H, Wang Y. In situ-generated Co⁰-Co₃O₄/N-doped carbon nanotubes hybrids as efficient and chemoselective catalysts for hydrogenation of nitroarenes. ACS Catalysis, 2015, 5(8): 4783–4789

[11] Liu Y, Huang C, Chen Y. Hydrogenation of p-chloronitrobenzene on Ni-B nanometal catalysts. Journal of Nanoparticle Research, 2006, 8(2): 223–234

[12] Ye T N, Lu Y, Li J, Nakao T, Yang H, Tada T, Kitano M, Hosono H. Copper-based intermetallic electride catalyst for chemoselective hydrogenation reactions. Journal of the American Chemical Society, 2017, 139(47): 17089–17097

[13] Tauster S. Strong metal-support interactions. Accounts of Chemical Research, 1987, 20(11): 389–394

[14] Tauster S, Fung S, Garten R L. Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide. Journal of the American Chemical Society, 1978, 100(1): 170–175

[15] Yu K, Lou L L, Liu S, Zhou W. Asymmetric oxygen vacancies: the intrinsic redox active sites in metal oxide catalysts. Advancement of Science, 2019, 7(2): 1901970

[16] Tang H, Liu F, Wei J, Qiao B, Zhao K, Su Y, Jin C, Li L, Liu J J, Wang J, . Ultrastable hydroxyapatite/titanium-dioxide-supported gold nanocatalyst with strong metal-support interaction for carbon monoxide oxidation. Angewandte Chemie International Edition, 2016, 55(36): 10606–10611

[17] Li J, Guan Q, Wu H, Liu W, Lin Y, Sun Z, Ye X, Zheng X, Pan H, Zhu J, . Highly active and stable metal single-atom catalysts achieved by strong electronic metal-support interactions. Journal of the American Chemical Society, 2019, 141(37): 14515–14519

[18] Zhang S, Xia Z, Ni T, Zhang Z, Ma Y, Qu Y. Strong electronic metal-support interaction of Pt/CeO₂ enables efficient and selective hydrogenation of quinolines at room temperature. Journal of Catalysis, 2018, 359: 101–111

[19] Rodriguez J A, Liu P, Wang X, Wen W, Hanson J, Hrbek J, Pérez M, Evans J. Water-gas shift activity of Cu surfaces and Cu nanoparticles supported on metal oxides. Catalysis Today, 2009, 143(1–2): 45–50

[20] Gao T, Chen J, Fang W, Cao Q, Su W, Dumeignil F. Ru/Mn_xCe₁O_y catalysts with enhanced oxygen mobility and strong metal-support interaction: exceptional performances in 5-hydroxymethylfurfural base-free aerobic oxidation. Journal of Catalysis, 2018, 368: 53–68

[21] Xiong J, Chen J, Zhang J. Liquid-phase hydrogenation of o-chloronitrobenzene over supported nickel catalysts. Catalysis Communications, 2007, 8(3): 345–350

[22] Armbruster M, Kovnir K, Friedrich M, Teschner D, Wowsnick G, Hahne M, Gille P, Szentmiklosi L, Feuerbacher M, Heggen M, . Al₁₃Fe₄ as a low-cost alternative for palladium in heterogeneous hydrogenation. Nature Materials, 2012, 11(8): 690–693

[23] Yu J, Yang Y, Chen L, Li Z, Liu W, Xu E, Zhang Y, Hong S, Zhang X, Wei M. NiBi intermetallic compounds catalyst toward selective hydrogenation of unsaturated aldehydes. Applied Catalysis B: Environmental, 2020, 277: 119273–119281

[24] Wong F H, Tiong T J, Leong L K, Lin K, Yap Y H. Effects of ZnO on characteristics and selectivity of coprecipitated Ni/ZnO/Al₂O₃ catalysts for partial hydrogenation of sunflower oil. Industrial & Engineering Chemistry Research, 2018, 57(9): 3163–3174

[25] Yarulin A, Berguerand C, Yuranov I, Cárdenas L F, Prokopyeva I, Kiwi M L. Pt-Zn nanoparticles supported on porous polymeric matrix for selective 3-nitrostyrene hydrogenation. Journal of Catalysis, 2015, 321: 7–12

[26] Kumar R, Pant K K. Promotional effects of Cu and Zn in hydrotalcite-derived methane tri-reforming catalyst. Applied Surface Science, 2020, 515: 146010

[27] Belskaya O B, Stepanova L N, Gulyaeva T I, Erenburg S B, Trubina S V, Kvashnina K, Nizovskii A I, Kalinkin A V, Zaikovskii V I, Bukhtiyarov V I, . Zinc influence on the formation and properties of Pt/Mg(Zn)AlO_x catalysts synthesized from layered hydroxides. Journal of Catalysis, 2016, 341: 13–23

[28] Chen M, Li X, Wang Y, Wang C, Liang T, Zhang H, Yang Z, Zhou Z, Wang J. Hydrogen generation by steam reforming of tar model compounds using lanthanum modified Ni/sepiolite catalysts. Energy Conversion and Management, 2019, 184: 315–326

[29] Baamran K S, Tahir M. Ni-embedded TiO₂-ZnTiO₃ reducible perovskite composite with synergistic effect of metal/support towards enhanced H₂ production via phenol steam reforming. Energy Conversion and Management, 2019, 200: 112064–112079

[30] Pan Z, Wang R, Chen J. Deoxygenation of methyl laurate as a model compound on Ni-Zn alloy and intermetallic compound catalysts: geometric and electronic effects of oxophilic Zn. Applied Catalysis B: Environmental, 2018, 224: 88–100

[31] Jansi Rani B, Ravi G, Yuvakkumar R, Ravichandran S, Ameen F, AlNadhary S. Sn doped α-Fe₂O₃ (Sn= 0, 10, 20, 30 wt-%) photoanodes for photoelectrochemical water splitting applications. Renewable Energy, 2019, 133: 566–574

[32] Miao C, Zhou G, Chen S, Xie H, Zhang X. Synergistic effects between Cu and Ni species in NiCu/γ-Al₂O₃ catalysts for hydrodeoxygenation of methyl laurate. Renewable Energy, 2020, 153: 1439–1454

[33] Hidalgo J J, Wang Q, Edalati K, Cubero S J M, Razavi K H, Ikoma Y, Gutiérrez F D, Dittel M F A, Rodríguez R J C, Fuji M, . Phase transformations, vacancy formation and variations of optical and photocatalytic properties in TiO₂-ZnO composites by high-pressure torsion. International Journal of Plasticity, 2020, 124: 170–185

[34] Liu D, Wang C, Yu Y, Zhao B, Wang W, Du Y, Zhang B. Understanding the nature of ammonia treatment to synthesize oxygen vacancy-enriched transition metal oxides. Chem, 2019, 5(2): 376–389

[35] Yang F, Yang R, Yan L, Liu X, Luo X, Zhang L. In situ growth of porous TiO₂ with controllable oxygen vacancies on an atomic scale for highly efficient photocatalytic water splitting. Catalysis Science & Technology, 2020, 10(16): 5659–5665

[36] Kumar C P, Gopal N O, Wang T C, Wong M, Ke S C. EPR investigation of TiO₂ nanoparticles with temperature-dependent properties. Journal of Physical Chemistry B, 2006, 110(11): 5223–5229

[37] Wang D, Kang X, Gu Y, Zhang H, Liu J, Wu A, Yan H, Tian C, Fu H. Electronic tuning of Ni by Mo species for highly efficient hydroisomerization of n-alkanes comparable to Pt-based catalysts. ACS Catalysis, 2020, 10(18): 10449–10458

[38] Liang G, He L, Cheng H, Zhang C, Li X, Fujita S, Zhang B, Arai M, Zhao F. ZSM-5-supported multiply-twinned nickel particles: formation, surface properties, and high catalytic performance in hydrolytic hydrogenation of cellulose. Journal of Catalysis, 2015, 325: 79–86

[39] Zhao J, Chen C, Xing C, Jiao Z, Yu M, Mei B, Yang J, Zhang B, Jiang Z, Qin Y. Selectivity regulation in Au-catalyzed nitroaromatic hydrogenation by anchoring single-site metal oxide promoters. ACS Catalysis, 2020, 10(4): 2837–2844

[40] Hussain I, Jalil A A, Hassan N S, Hambali H U, Jusoh N W C. Fabrication and characterization of highly active fibrous silica-mordenite (FS@SiO₂-MOR) cockscomb shaped catalyst for enhanced CO₂ methanation. Chemical Engineering Science, 2020, 228: 115978

[41] Zhang S, Chang C, Huang Z, Li J, Wu Z, Ma Y, Zhang Z, Wang Y, Qu Y. High catalytic activity and chemoselectivity of sub-nanometric Pd clusters on porous nanorods of CeO₂ for hydrogenation of nitroarenes. Journal of the American Chemical Society, 2016, 138(8): 2629–2637

[42] Wang L, Guan E, Zhang J, Yang J, Zhu Y, Han Y, Yang M, Cen C, Fu G, Gates B C, Xiao F S. Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation. Nature Communications, 2018, 9(1): 1–8

[43] Niu H, Lu J, Song J, Pan L, Zhang X, Wang L, Zou J. Iron oxide as a catalyst for nitroarene hydrogenation: important role of oxygen vacancies. Industrial & Engineering Chemistry Research, 2016, 55(31): 8527–8533

[44] Yang L, Jiang Z, Fan G, Li F. The promotional effect of ZnO addition to supported Ni nanocatalysts from layered double hydroxide precursors on selective hydrogenation of citral. Catalysis Science & Technology, 2014, 4(4): 1123–1131

[45] Zhang L, Zhou M, Wang A, Zhang T. Selective hydrogenation over supported metal catalysts: from nanoparticles to single atoms. Chemical Reviews, 2020, 120(2): 683–733

[46] MacQueen B, Royko M, Crandall B S, Heyden A, Pagán-Torres Y J, Lauterbach J. Kinetics study of the hydrodeoxygenation of xylitol over a ReO_x-Pd/CeO₂ catalyst. Catalysts, 2021, 11(1): 108–124

[47] Banu I, Bumbac G, Bombos D, Velea S, Gălan A, Bozga G. Glycerol acetylation with acetic acid over Purolite CT-275. Product yields and process kinetics. Renewable Energy, 2020, 148: 548–557

[48] Gao R, Pan L, Wang H, Zhang X, Wang L, Zou J. Ultradispersed nickel phosphide on phosphorus-doped carbon with tailored d-band center for efficient and chemoselective hydrogenation of nitroarenes. ACS Catalysis, 2018, 8(9): 8420–8429

[49] Lin W, Cheng H, Ming J, Yu Y, Zhao F. Deactivation of Ni/TiO₂ catalyst in the hydrogenation of nitrobenzene in water and improvement in its stability by coating a layer of hydrophobic carbon. Journal of Catalysis, 2012, 291: 149–154

[50] Millán R, Liu L, Boronat M, Corma A. A new molecular pathway allows the chemoselective reduction of nitroaromatics on non-noble metal catalysts. Journal of Catalysis, 2018, 364: 19–30

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Grant Nos. 22078277 and 21908185), Project of Hunan Provincial Education Department (Grant Nos. 19B572 and 20B547), the Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization, and the National Department of Education Engineering Research Centre for Chemical Process Simulation and Optimization.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-021-2072-8 and is accessible for authorized users.

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