Photoelectrochemical Synthesis of Ammonia on the Aerophilic-Hydrophilic Heterostructure with 37.8% Efficiency

Summary Photoelectrochemical nitrogen reduction reaction can provide a useful source of ammonia and transportable carrier of hydrogen, but the process is limited by the photocathodes with poor conversion efficiency and low production rate. Here, we have designed a unique aerophilic-hydrophilic heterostructured Si-based photocathode for nitrogen-to-ammonia fixation in an acid electrolyte under mild conditions, achieving a high ammonia yield rate of ∼18.9 μg⋅cm−2⋅hr−1 and an excellent faradic efficiency of 37.8% at −0.2 V versus a reversible hydrogen electrode. The heterostructure based on the Au nanoparticles highly dispersed in poly(tetrafluoroethylene) porous framework enriches nitrogen molecular concentration at the Au active sites while manipulateing the proton activity with suppressed hydrogen evolution reactions. DFT calculation indicates that such heterostructure reduces the energy barrier for the nitrogen reduction reaction. The aerophilic-hydrophilic heterostructure provides a new insight on designing efficient and robust photocathodes for nitrogen fixation.

[1]  P. Silver,et al.  Ambient nitrogen reduction cycle using a hybrid inorganic–biological system , 2017, Proceedings of the National Academy of Sciences.

[2]  Marta C. Hatzell,et al.  Photon-Driven Nitrogen Fixation: Current Progress, Thermodynamic Considerations, and Future Outlook , 2017 .

[3]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[4]  Q. Jiang,et al.  Amorphizing of Au Nanoparticles by CeOx–RGO Hybrid Support towards Highly Efficient Electrocatalyst for N2 Reduction under Ambient Conditions , 2017, Advanced materials.

[5]  Xiaolin Zheng,et al.  Stabilizing Silicon Photocathodes by Solution-Deposited Ni–Fe Layered Double Hydroxide for Efficient Hydrogen Evolution in Alkaline Media , 2017 .

[6]  G. Watt,et al.  Spectrophotometric Method for Determination of Hydrazine , 1952 .

[7]  Jinling He,et al.  Superaerophobic Electrode with Metal@Metal‐Oxide Powder Catalyst for Oxygen Evolution Reaction , 2016 .

[8]  H. Jónsson,et al.  A theoretical evaluation of possible transition metal electro-catalysts for N2 reduction. , 2012, Physical chemistry chemical physics : PCCP.

[9]  Hiang Kwee Lee,et al.  Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach , 2018, Science Advances.

[10]  Fei Zhang,et al.  A physical catalyst for the electrolysis of nitrogen to ammonia , 2018, Science Advances.

[11]  Christine M. Gabardo,et al.  CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface , 2018, Science.

[12]  Hao Wang,et al.  Ultrahigh Hydrogen Evolution Performance of Under‐Water “Superaerophobic” MoS2 Nanostructured Electrodes , 2014, Advanced materials.

[13]  Yu Ding,et al.  An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions. , 2018, Angewandte Chemie.

[14]  J. Shang,et al.  Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets. , 2015, Journal of the American Chemical Society.

[15]  Xiaofeng Feng,et al.  Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential , 2018, Nature Communications.

[16]  L. Bourgeois,et al.  Nanostructured photoelectrochemical solar cell for nitrogen reduction using plasmon-enhanced black silicon , 2016, Nature Communications.

[17]  Kendra Letchworth-Weaver,et al.  Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. , 2013, The Journal of chemical physics.

[18]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[19]  R. Hamers,et al.  Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. , 2013, Nature materials.

[20]  Joseph H. Montoya,et al.  The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations. , 2015, ChemSusChem.

[21]  P. L. Searle.  The berthelot or indophenol reaction and its use in the analytical chemistry of nitrogen. A review , 1984 .

[22]  Lirong Zheng,et al.  Layered‐Double‐Hydroxide Nanosheets as Efficient Visible‐Light‐Driven Photocatalysts for Dinitrogen Fixation , 2017, Advanced materials.

[23]  Shi-Zhang Qiao,et al.  Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions , 2018 .

[24]  Douglas R. MacFarlane,et al.  Electro-synthesis of ammonia from nitrogen at ambient temperature and pressure in ionic liquids , 2017 .

[25]  Lei Jiang,et al.  Superaerophilic Carbon‐Nanotube‐Array Electrode for High‐Performance Oxygen Reduction Reaction , 2016, Advanced materials.

[26]  Shuangyin Wang,et al.  Defect‐Enhanced Charge Separation and Transfer within Protection Layer/Semiconductor Structure of Photoanodes , 2018, Advanced materials.

[27]  Stuart Licht,et al.  Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3 , 2014, Science.

[28]  S. Jiang,et al.  Crystalline TiO2 protective layer with graded oxygen defects for efficient and stable silicon-based photocathode , 2018, Nature Communications.

[29]  M. Kanatzidis,et al.  Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia , 2016, Proceedings of the National Academy of Sciences.

[30]  Lizhi Zhang,et al.  Solar Water Splitting and Nitrogen Fixation with Layered Bismuth Oxyhalides. , 2017, Accounts of chemical research.

[31]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[32]  Xiaoli Zhang,et al.  Pd–MgNix nanospheres/black-TiO2 porous films with highly efficient hydrogen production by near-complete suppression of surface recombination , 2016 .

[33]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[34]  Haihui Wang,et al.  Ammonia Electrosynthesis with High Selectivity under Ambient Conditions via a Li+ Incorporation Strategy. , 2017, Journal of the American Chemical Society.

[35]  Chong Liu,et al.  Electrocatalytic Nitrogen Reduction at Low Temperature , 2018 .

[36]  D. Cullen,et al.  Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N2 and H2O in alkaline electrolytes , 2018, Nano Energy.

[37]  Ping Jin,et al.  Natural hydrophobicity and reversible wettability conversion of flat anatase TiO₂ thin film. , 2014, ACS applied materials & interfaces.

[38]  Chaoyi Peng,et al.  All-organic superhydrophobic coatings with mechanochemical robustness and liquid impalement resistance , 2018, Nature Materials.

[39]  Yao Yao,et al.  A Spectroscopic Study on the Nitrogen Electrochemical Reduction Reaction on Gold and Platinum Surfaces. , 2018, Journal of the American Chemical Society.

[40]  R. Service.  Chemistry. New recipe produces ammonia from air, water, and sunlight. , 2014, Science.

[41]  Rajeev Dhiman,et al.  Hydrophobicity of rare-earth oxide ceramics. , 2013, Nature materials.

[42]  Rui Liu,et al.  Enhanced photoelectrochemical water-splitting performance of semiconductors by surface passivation layers , 2014 .

[43]  M. Koper,et al.  Challenges in reduction of dinitrogen by proton and electron transfer. , 2014, Chemical Society reviews.

[44]  Zhilin Yang,et al.  Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO2 Photoelectrodes. , 2018, Angewandte Chemie.

[45]  R. Bruce Lennox,et al.  Gold−Sulfur Bonding in 2D and 3D Self-Assembled Monolayers: XPS Characterization , 2000 .

[46]  Jijun Zhao,et al.  Facile Ammonia Synthesis from Electrocatalytic N2 Reduction under Ambient Conditions on N-Doped Porous Carbon , 2018 .