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Enhanced synergy between Cu0 and Cu+ on nickel doped copper catalyst for gaseous acetic acid hydrogenation

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Abstract

As the substitution of common noble catalysts in the hydrogenation of carboxylic acid, a highly effective Cu-Ni/SiO2 catalyst was prepared by a novel stepwise ammonia evaporation method. Its performance in the gasphase hydrogenation of acetic acid was further examined. With the introduction of Ni dopant, more stable Cuδ+ sites, which can adsorb more acetic acid, were formed due to the electron transfer from Cu to Ni. This makes more Cu0 sites available for hydrogen adsorption, which was suggested as the rate-determining step in acetic acid hydrogenation. A conversion of 99.6% was successfully achieved on this new Cu/SiO2-0.5Ni catalyst, accompanied by the ethanol selectivity of 90%. The incorporation of nickel between copper nanoparticles enhances the synergistic effect between Cu0 and Cu+. It also helps mitigate the aggregation of copper nanoparticles due to the Ostwald ripening effect induced by acetic acid and enhance the stability of copper catalyst in the conversion of carboxylic acid.

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References

  1. Lynd L, Laser M, Bransby D, Dale B, Davison B, Hamilton R, Himmel M, Keller M, McMillan J, Sheehan J, Wyman C E. How biotech can transform biofuels. Nature Biotechnology, 2008, 26(2): 169–172

    CAS  PubMed  Google Scholar 

  2. Hu C, Yang Y, Luo J, Pan P, Tong D, Li G. Recent advances in the catalytic pyrolysis of biomass. Frontiers of Chemical Science and Engineering, 2010, 5(2): 188–193

    Google Scholar 

  3. Kan T, Strezov V, Evans T. Lignocellulosic biomass pyrolysis: a review of product properties and effects of pyrolysis parameters. Renewable & Sustainable Energy Reviews, 2016, 57: 1126–1140

    CAS  Google Scholar 

  4. Deng L, Kang B, Englert U, Klankermayer J, Palkovits R. Direct hydrogenation of biobased carboxylic acids mediated by a nitrogen-centered tridentate phosphine ligand. ChemSusChem, 2016, 9(2): 177–180

    CAS  PubMed  Google Scholar 

  5. Czernik S, Johnson D, Black S. Stability of wood fast pyrolysis oil. Biomass and Bioenergy, 1994, 7(1): 187–192

    CAS  Google Scholar 

  6. Pinzi S, Gandia L, Arzamendi G, Ruiz J, Dorado M. Influence of vegetable oils fatty acid composition on reaction temperature and glycerides conversion to biodiesel during transesterification. Bioresource Technology, 2011, 102(2): 1044–1050

    CAS  PubMed  Google Scholar 

  7. Akinfalabi S, Rashid U, Yunus R, Taufiq-Yap Y. Synthesis of biodiesel from palm fatty acid distillate using sulfonated palm seed cake catalyst. Renewable Energy, 2017, 111: 611–619

    CAS  Google Scholar 

  8. Encinar J, Sanchez N, Martinez G, Garcia L. Study of biodiesel production from animal fats with high free fatty acid content. Bioresource Technology, 2011, 102(23): 10907–10914

    CAS  PubMed  Google Scholar 

  9. Suwito S, Dragone G, Sulistyo H, Murachman B, Purwono S, Teixeira J. Optimization of pretreatment of Jatropha oil with high free fatty acids for biodiesel production. Frontiers of Chemical Science and Engineering, 2012, 6(2): 210–215

    CAS  Google Scholar 

  10. Pritchard J, Filonenko G, van Putten R, Hensen E, Pidko E. Heterogeneous and homogeneous catalysis for the hydrogenation of carboxylic acid derivatives: history, advances and future directions. Chemical Society Reviews, 2015, 44(11): 3808–3833

    CAS  PubMed  Google Scholar 

  11. Lawal A, Hart A, Daly H, Hardacre C, Wood J. Catalytic hydrogenation of short chain carboxylic acids typical of model compound found in bio-oils. Industrial & Engineering Chemistry Research, 2019, 58(19): 7998–8008

    CAS  Google Scholar 

  12. Rachmady W, Vannice M. Acetic acid hydrogenation over supported platinum catalysts. Journal of Catalysis, 2000, 192(2): 322–334

    CAS  Google Scholar 

  13. Pallassana V, Neurock M. Reaction paths in the hydrogenolysis of acetic acid to ethanol over Pd(111), Re(0001), and PdRe Alloys. Journal of Catalysis, 2002, 209(2): 289–305

    CAS  Google Scholar 

  14. Rachmady W, Vannice M. Acetic acid reduction by H2 on bimetallic Pt-Fe catalysts. Journal of Catalysis, 2002, 209(1): 87–98

    CAS  Google Scholar 

  15. Rachmady W, Vannice M. Acetic acid reduction by H2 over supported Pt catalysts: a DRIFTS and TPD/TPR study. Journal of Catalysis, 2002, 207(2): 317–330

    CAS  Google Scholar 

  16. Zhang K, Zhang H, Ma H, Ying W, Fang D. Effect of Snadditionin gas phase hydrogenation of acetic acid on alumina supported PtSn catalysts. Catalysis Letters, 2014, 144(4): 691–701

    CAS  Google Scholar 

  17. Zhang S, Duan X, Ye L, Lin H, Xie Z, Yuan Y. Production of ethanol by gas phase hydrogenation of acetic acid over carbon nanotube-supported Pt-Sn nanoparticles. Catalysis Today, 2013, 215: 260–266

    CAS  Google Scholar 

  18. Xu G, Zhang J, Wang S, Zhao Y, Ma X. A well fabricated PtSn/SiO2 catalyst with enhanced synergy between Pt and Sn for acetic acid hydrogenation to ethanol. RSC Advances, 2016, 6(56): 51005–51013

    CAS  Google Scholar 

  19. Li W, Ye L, Chen J, Duan X, Lin H, Yuan Y. FeSBA-15-supported ruthenium catalyst for the selective hydrogenolysis of carboxylic acids to alcoholic chemicals. Catalysis Today, 2015, 251: 53–59

    CAS  Google Scholar 

  20. Tamura M, Nakagawa Y, Tomishige K. Recent developments of heterogeneous catalysts for hydrogenation of carboxylic acids to their corresponding alcohols. Asian Journal of Organic Chemistry, 2020, 9(2): 126–143

    CAS  Google Scholar 

  21. Xu G, Zhang J, Wang S, Zhao Y, Ma X. Effect of thermal pretreatment on the surface structure of PtSn/SiO2 catalyst and its performance in acetic acid hydrogenation. Frontiers of Chemical Science and Engineering, 2016, 10(3): 417–424

    CAS  Google Scholar 

  22. Li W, Ye L, Long P, Chen J, Ariga H, Asakura K, Yuan Y. Efficient Ru-Fe catalyzed selective hydrogenolysis of carboxylic acids to alcoholic chemicals. RSC Advances, 2014, 4(55): 29072–29082

    CAS  Google Scholar 

  23. Onyestyák G. Non-precious metal catalysts for acetic acid reduction. Periodica Polytechnica. Chemical Engineering, 2017, 61(4): 270–277

    Google Scholar 

  24. Choi J, Schwartz V, Santillan-Jimenez E, Crocker M, Lewis S Sr, Lance M, Meyer H III, More K. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid. Catalysts, 2015, 5 (1): 406–423

    CAS  Google Scholar 

  25. Dong X, Lei J, Chen Y, Jiang H, Zhang M. Selective hydrogenation of acetic acid to ethanol on Cu-In catalyst supported by SBA-15. Applied Catalysis B: Environmental, 2019, 244: 448–458

    CAS  Google Scholar 

  26. Onyestyák G, Harnos S, Kalló D. Improving the catalytic behavior of Ni/Al2O3 by indium in reduction of carboxylic acid to alcohol. Catalysis Communications, 2011, 16(1): 184–188

    Google Scholar 

  27. Onyestyák G, Harnos S, Klébert S, Štolcová M, Kaszonyi A, Kalló D. Selective reduction of acetic acid to ethanol over novel Cu2In/Al2O3 catalyst. Applied Catalysis A, General, 2013, 464–465: 313–321

    Google Scholar 

  28. Han Y, Wang Y, Ma T, Li W, Zhang J, Zhang M. Mechanistic understanding of Cu-based bimetallic catalysts. Frontiers of Chemical Science and Engineering, 2020, 14(5): 689–748

    CAS  Google Scholar 

  29. Upare P, Jeong M, Hwang Y, Kim D, Kim Y, Hwang D, Lee U, Chang J. Nickel-promoted copper-silica nanocomposite catalysts for hydrogenation of levulinic acid to lactones using formic acid as a hydrogen feeder. Applied Catalysis A, General, 2015, 491: 127–135

    CAS  Google Scholar 

  30. Studt F, Abild-Pedersen F, Wu Q, Jensen A, Temel B, Grunwaldt J, Nørskov J. CO hydrogenation to methanol on Cu-Ni catalysts: theory and experiment. Journal of Catalysis, 2012, 293: 51–60

    CAS  Google Scholar 

  31. Bridier B, Pérez-Ramírez J. Cooperative effects in ternary Cu-Ni-Fe catalysts lead to enhanced alkene selectivity in alkyne hydrogenation. Journal of the American Chemical Society, 2010, 132(12): 4321–4327

    CAS  PubMed  Google Scholar 

  32. Tu C, Tsou Y, To T, Chen C, Lee J, Huber G, Lin Y. Phyllosilicate-derived CuNi/SiO2 catalysts in the selective hydrogenation of adipic acid to 1,6-hexanediol. ACS Sustainable Chemistry & Engineering, 2019, 7(21): 17872–17881

    CAS  Google Scholar 

  33. Jiang J, Tu C, Chen C, Lin Y. Highly selective silica-supported copper catalysts derived from copper phyllosilicates in the hydrogenation of adipic acid to 1,6-hexanediol. ChemCatChem, 2018, 10(23): 5449–5458

    CAS  Google Scholar 

  34. Van Der Grift C, Wielers A, Jogh B, Van Beunum J, De Boer M, Versluijs-Helder M, Geus J. Effect of the reduction treatment on the structure and reactivity of silica-supported copper particles. Journal of Catalysis, 1991, 131(1): 178–189

    CAS  Google Scholar 

  35. Wang C, Tian Y, Wu R, Li H, Yao B, Zhao Y, Xiao T. Bimetallic synergy effects of phyllosilicate-derived NiCu@SiO2 catalysts for 1,4-butynediol direct hydrogenation to 1,4-butanediol. ChemCatChem, 2019, 11(19): 4777–4787

    Google Scholar 

  36. Sun Y, Hu J, An S, Zhang Q, Guo Y, Song D, Shang Q. Selective esterification of glycerol with acetic acid or lauric acid over rod-like carbon-based sulfonic acid functionalized ionic liquids. Fuel, 2017, 207: 136–145

    CAS  Google Scholar 

  37. Chen L, Guo P, Qiao M, Yan S, Li H, Shen W, Xu H, Fan K. Cu/SiO2 catalysts prepared by the ammonia-evaporation method: texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol. Journal of Catalysis, 2008, 257 (1): 172–180

    CAS  Google Scholar 

  38. Zhang C, Wang D, Zhu M, Yu F, Dai B. Effect of different nano-sized silica sols as supports on the structure and properties of Cu/SiO2 for hydrogenation of dimethyl oxalate. Catalysts, 2017, 7(12): 75–87

    Google Scholar 

  39. Ding J, Zhang J, Zhang C, Liu K, Xiao H, Kong F, Chen J. Hydrogenation of diethyl oxalate over Cu/SiO2 catalyst with enhanced activity and stability: contribution of the spatial restriction by varied pores of support. Applied Catalysis A, General, 2015, 508: 68–79

    CAS  Google Scholar 

  40. Yin A, Wen C, Guo X, Dai W, Fan K. Influence of Ni species on the structural evolution of Cu/SiO2 catalyst for the chemoselective hydrogenation of dimethyl oxalate. Journal of Catalysis, 2011, 280 (1): 77–88

    CAS  Google Scholar 

  41. Zhang Z, Yang Q, Chen H, Chen K, Lu X, Ouyang P, Fu J, Chen J. In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu-Ni alloy catalyst using methanol as a hydrogen carrier. Green Chemistry, 2018, 20(1): 197–206

    CAS  Google Scholar 

  42. Li X, Xiang M, Wu D. Hydrogenolysis of glycerol over bimetallic Cu-Ni catalysts supported on hierarchically porous SAPO-11 zeolite. Catalysis Communications, 2019, 119: 170–175

    CAS  Google Scholar 

  43. Seemala B, Cai C, Kumar R, Wyman C, Christopher P. Effects of Cu-Ni bimetallic catalyst composition and support on activity, selectivity, and stability for furfural conversion to 2-methyfuran. ACS Sustainable Chemistry & Engineering, 2018, 6(2): 2152–2161

    CAS  Google Scholar 

  44. Chen K, Duan X, Fang H, Liang X, Yuan Y. Selective hydrogenation of CO2 to methanol catalyzed by Cu supported on rod-like La2O2CO3. Catalysis Science & Technology, 2018, 8(4): 1062–1069

    CAS  Google Scholar 

  45. Wang Y, Shen Y, Zhao Y, Lv J, Wang S, Ma X. Insight into the balancing effect of active Cu species for hydrogenation of carbon-oxygen bonds. ACS Catalysis, 2015, 5(10): 6200–6208

    CAS  Google Scholar 

  46. Yu X, Vest T A, Gleason-Boure N, Karakalos S, Tate G, Burkholder M, Monnier J, Williams C. Enhanced hydrogenation of dimethyl oxalate to ethylene glycol over indium promoted Cu/SiO2. Journal of Catalysis, 2019, 380: 289–296

    CAS  Google Scholar 

  47. Santiago M, Sánchez-Castillo M, Cortright R, Dumesic J. Catalytic reduction of acetic acid, methyl acetate, and ethyl acetate over silica-supported copper. Journal of Catalysis, 2000, 193(1): 16–28

    CAS  Google Scholar 

  48. Chen C, Chen C, Lai T, Wu J, Chen C, Lee J. Water adsorption and dissociation on Cu nanoparticles. Journal of Physical Chemistry C, 2011, 115(26): 12891–12900

    CAS  Google Scholar 

  49. Challa S, Delariva A, Hansen T, Helveg S, Sehested J, Hansen P, Garzon F, Datye A. Relating rates of catalyst sintering to the disappearance of individual nanoparticles during Ostwald ripening. Journal of the American Chemical Society, 2011, 133(51): 20672–20675

    CAS  PubMed  Google Scholar 

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Acknowledgements

We appreciate the National Natural Science Foundation of China for the financial support (Grant No. 21878227).

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Authors and Affiliations

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, Collaborative Innovation Center of Chemical Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China

    Jingwei Zhang, Lingxin Kong, Yao Chen, Huijiang Huang, Huanhuan Zhang, Yaqi Yao, Yuxi Xu, Yan Xu, Shengping Wang, Xinbin Ma & Yujun Zhao

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  1. Jingwei Zhang
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Correspondence to Yujun Zhao.

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Zhang, J., Kong, L., Chen, Y. et al. Enhanced synergy between Cu0 and Cu+ on nickel doped copper catalyst for gaseous acetic acid hydrogenation. Front. Chem. Sci. Eng. 15, 666–678 (2021). https://doi.org/10.1007/s11705-020-1982-1

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  • DOI: https://doi.org/10.1007/s11705-020-1982-1

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