In2O3 nanoparticle-reduced graphene oxide hybrid for electrocatalytic nitrogen fixation: Computational and experimental studies

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Electrocatalytic N2 reduction reaction (NRR) represents a very promising route for ambient NH3 synthesis, while the efficient NRR process necessitates active and robust catalysts. Herein, we explored the potential of In2O3 as an NRR catalyst from both theoretical and experimental perspectives. Density functional theory calculations revealed that In2O3 possessed the favorable N2 adsorption, low reaction overpotential and suppressed hydrogen evolution reaction. As a proof-of-concept example, we prepared In2O3 nanoparticle-reduced graphene oxide (In2O3/RGO) hybrid which exhibited attractive NRR performance with an NH3 yield of 18.4 μg h−1 mg−1 and a Faradaic efficiency of 8.1% at  − 0.6 V (RHE) in 0.1 M Na2SO4. Therefore, the combination of theoretical and experimental results demonstrated that In2O3-based materials could potentially serve as efficient NRR catalysts for electrocatalytic N2 fixation.

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  1. 1

    Jensen ES, Hauggaard-Nielsen H (2003) How can increased use of biological N2 fixation in agriculture benefit the environment? Plant Soil 252:177–186

  2. 2

    He T, Pachfule P, Wu H, Xu Q, Chen P (2016) Hydrogen carriers. Nat Rev Mater 1:16059

  3. 3

    Van der Ham CJ, Koper MT, Hetterscheid DG (2014) Challenges in reduction of dinitrogen by proton and electron transfer. Chem Soc Rev 43:5183–5191

  4. 4

    Guo C, Ran J, Vasileff A, Qiao S-Z (2018) Rational design of electrocatalysts and photo (electro) catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions. Energy Environ Sci 11:45–56

  5. 5

    Chen GF, Ren SY, Zhang LL et al (2019) Advances in electrocatalytic N2 reduction-strategies to tackle the selectivity challenge. Small Methods 3:1800337

  6. 6

    Deng J, Iñiguez JA, Liu C (2018) Electrocatalytic nitrogen reduction at low temperature. Joule 2:846–856

  7. 7

    Wang XH, Wang J, Li YB, Chu K (2019) Nitrogen-doped NiO nanosheet array for boosted electrocatalytic N2 reduction. ChemCatChem 11:4529–4536

  8. 8

    Li SJ, Bao D, Shi MM, Wulan BR, Yan JM, Jiang Q (2017) Amorphizing of Au nanoparticles by CeOx–RGO hybrid support towards highly efficient electrocatalyst for N2 reduction under ambient conditions. Adv Mater 29:1700001

  9. 9

    Shi MM, Bao D, Wulan BR et al (2017) Au sub-nanoclusters on TiO2 toward highly efficient and selective electrocatalyst for N2 conversion to NH3 at ambient conditions. Adv Mater 29:1606550

  10. 10

    Nazemi M, Panikkanvalappil SR, El-Sayed MA (2018) Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages. Nano Energy 49:316–323

  11. 11

    Xue Z-H, Zhang S-N, Lin Y-X et al (2019) Electrochemical reduction of N2 into NH3 by donor–acceptor couples of Ni and Au nanoparticles with a 67.8% Faradaic efficiency. J Am Chem Soc 141:14976–14980

  12. 12

    Foster SL, Bakovic SIP, Duda RD et al (2018) Catalysts for nitrogen reduction to ammonia. Nat Catal 1:490–500

  13. 13

    Xiaoxin Z, Yu Z (2015) Noble metal-free hydrogen evolution catalysts for water splitting. Chem Soc Rev 44:5148–5180

  14. 14

    Cui X, Tang C, Zhang Q (2018) A review of electrocatalytic reduction of dinitrogen to ammonia under ambient conditions. Adv Energy Mater 8:1800369

  15. 15

    Han J, Liu Z, Ma Y et al (2018) Ambient N2 fixation to NH3 at ambient conditions: Using Nb2O5 nanofiber as a high-performance electrocatalyst. Nano Energy 52:264–270

  16. 16

    Wang Y, Jia K, Pan Q et al (2019) Boron-doped TiO2 for efficient electrocatalytic N2 fixation to NH3 at ambient conditions. ACS Sustain Chem Eng 7:117–122

  17. 17

    Han J, Ji X, Ren X et al (2018) MoO3 nanosheets for efficient electrocatalytic N2 fixation to NH3. J Mater Chem A 6:12974–12977

  18. 18

    Zhang Y, Qiu W, Ma Y et al (2018) High-performance electrohydrogenation of N2 to NH3 catalyzed by multishelled hollow Cr2O3 microspheres under ambient conditions. ACS Catal 8:8540–8544

  19. 19

    Chu K, Liu Y, Li Y, Zhang H, Tian Y (2019) Efficient electrocatalytic N2 reduction on CoO quantum dots. J Mater Chem A 7:4389–4394

  20. 20

    Lemos SCS, Nossol E, Ferrari JL et al (2019) Joint theoretical and experimental study on the La doping process in In2O3: phase transition and electrocatalytic activity. Inorg Chem 58:11738–11750

  21. 21

    Zhang Z, Ahmad F, Zhao W et al (2019) Enhanced electrocatalytic reduction of CO2 via chemical coupling between indium oxide and reduced graphene oxide. Nano Lett 19:4029–4034

  22. 22

    Liu YP, Li YB, Huang DJ, Zhang H, Chu K (2019) ZnO quantum dots coupled with graphene toward electrocatalytic N2 reduction: experimental and DFT investigations. Chem Eur J 25:11933–11939

  23. 23

    Wang F, Liu YP, Zhang H, Chu K (2019) CuO/graphene nanocomposite for nitrogen reduction reaction. ChemCatChem 11:1441–1447

  24. 24

    Liu YP, Li YB, Zhang H, Chu K (2019) Boosted electrocatalytic N2 reduction on fluorine-doped SnO2 mesoporous nanosheets. Inorg Chem 58:10424–10431

  25. 25

    Li YB, Liu YP, Wang J, Guo YL, Chu K (2019) Plasma-engineered NiO nanosheets with enriched oxygen vacancies for enhanced electrocatalytic nitrogen fixation. Inorg Chem Front.

  26. 26

    Zhu D, Zhang L, Ruther RE, Hamers RJ (2013) Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. Nat Mater 12:836

  27. 27

    Watt GW, Chrisp JD (1952) Spectrophotometric method for determination of hydrazine. Anal Chem 24:2006–2008

  28. 28

    Chu K, Wang F, Wang XH et al (2018) Interface design of graphene/copper composites by matrix alloying with titanium. Mater Des 144:290–303

  29. 29

    Chu K, Wang F, Li YB, Wang XH, Huang DJ, Zhang H (2018) Interface structure and strengthening behavior of graphene/CuCr composites. Carbon 133:127–139

  30. 30

    Chu K, Wang XH, Li YB et al (2018) Thermal properties of graphene/metal composites with aligned graphene. Mater Des 140:85–94

  31. 31

    Clark SJ, Segall MD, Pickard CJ et al (2005) First principles methods using CASTEP. Z Kristallogr 220:567–570

  32. 32

    Peterson AA (2010) How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ Sci 3:1311–1315

  33. 33

    Zhao J, Chen Z (2017) Single Mo atom supported on defective boron nitride monolayer as an efficient electrocatalyst for nitrogen fixation: a computational study. J Am Chem Soc 139:12480–12487

  34. 34

    Chu K, Liu Y, Wang J, Zhang H (2019) NiO nanodots on graphene for efficient electrochemical N2 reduction to NH3. ACS Appl Energy Mater 2:2288–2295

  35. 35

    Wang Z, Gong F, Zhang L et al (2018) Electrocatalytic hydrogenation of N2 to NH3 by MnO: experimental and theoretical investigations. Adv Sci 6:1801182

  36. 36

    Chu K, Liu Y-p, Li Y-b, Wang J, Zhang H (2019) Electronically coupled SnO2 quantum dots and graphene for efficient nitrogen reduction reaction. ACS Appl Mater Interfaces 11:31806–31815

  37. 37

    Jin H, Guo C, Liu X et al (2018) Emerging two-dimensional nanomaterials for electrocatalysis. Chem Rev 118:6337–6408

  38. 38

    Chu K, Wang F, Wang XH, Huang DJ (2018) Anisotropic mechanical properties of graphene/copper composites with aligned graphene. Mater Sci Eng A 713:269–277

  39. 39

    Chu K, Wang F, Li YB, Wang XH, Huang DJ, Geng ZR (2018) Interface and mechanical/thermal properties of graphene/copper composite with Mo2C nanoparticles grown on graphene. Compos Part A 109:267–279

  40. 40

    Chu K, Wang XH, Wang F et al (2018) Largely enhanced thermal conductivity of graphene/copper composites with highly aligned graphene network. Carbon 127:102–112

  41. 41

    Xu X, Wu T, Xia F et al (2014) Redox reaction between graphene oxide and In powder to prepare In2O3/reduced graphene oxide hybrids for supercapacitors. J Power Sources 266:282–290

  42. 42

    Andre RS, Mercante LA, Facure MH, Mattoso LH, Correa DS (2019) Enhanced and selective ammonia detection using In2O3/reduced graphene oxide hybrid nanofibers. Appl Surf Sci 473:133–140

  43. 43

    Chu K, Wang J, Liu YP, Li YB, Jia CC, Zhang H (2019) Creating defects on graphene basal-plane toward interface optimization of graphene/CuCr composites. Carbon 143:85–96

  44. 44

    Chu K, Wang J, Liu YP, Geng ZR (2018) Graphene defect engineering for optimizing the interface and mechanical properties of graphene/copper composites. Carbon 140:112–123

  45. 45

    Wang J, Liu YP, Zhang H, Huang DJ, Chu K (2019) Ambient electrocatalytic nitrogen reduction on MoO2/graphene hybrid: experimental and DFT studies. Catal Sci Technol 9:4248–4254

  46. 46

    Andersen SZ, Čolić V, Yang S et al (2019) A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements. Nature 570:504–508

  47. 47

    Tang C, Qiao S-Z (2019) How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully. Chem Soc Rev 48:3166–3180

  48. 48

    Cheng H, Ding LX, Chen GF, Zhang LL, Xue J, Wang HH (2018) Molybdenum carbide nanodots enable efficient electrocatalytic nitrogen fixation under ambient conditions. Adv Mater 30:1803694

  49. 49

    Chen GF, Cao XR, Wu SQ et al (2017) Ammonia electrosynthesis with high selectivity under ambient conditions via a Li+ incorporation strategy. J Am Chem Soc 139:9771–9774

  50. 50

    Ren X, Zhao J, Wei Q et al (2019) High-performance N2-to-NH3 conversion electrocatalyzed by Mo2C Nanorod. ACS Central Sci 5:116–121

  51. 51

    Chu K, Liu YP, Li YB, Guo YL, Tian Y, Zhang H (2020) Multi-functional Mo-doping in MnO2 nanoflowers toward efficient and robust electrocatalytic nitrogen fixation. Appl Catal B 264:118525

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This work is supported by the Young Scholars Science Foundation of Lanzhou Jiaotong University (No. 2015006), the “Feitian Scholar” Program of Gansu Province, the CAS “Light of West China” Program and the Foundation of A Hundred Youth Talents Training Program of Lanzhou Jiaotong University.

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Correspondence to Ke Chu.

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Wang, P., Li, Q., Cheng, Y. et al. In2O3 nanoparticle-reduced graphene oxide hybrid for electrocatalytic nitrogen fixation: Computational and experimental studies. J Mater Sci 55, 4624–4632 (2020).

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