Corresponding Author

Pei-Kang Shen(pkshen@gxu.edu.cn);
Xin-Yi Zhang(zhangxinyi@gxu.edu.cn)


Ammonia is an important industrial raw material and a potential green energy. Using renewable energy to convert nitrogen into ammonia under ambient condition is an attractive method. However, the development of efficient photoelectrochemical ammonia synthesis catalysts remains a challenge. Perovskite such as BaSrTiO3 (BST) is a good photocatalytic material. However, BST is active under ultraviolet light and has a high recombination rate of photogenerated electron-hole pairs. By dispersing precious metals, it can effectively regulate the absorption of sunlight by BST. In this work, we used a two-step method to prepare BST. The H2PtCl6·6H2O solution was dispersed on the BST, and then followed by calcination in a tube furnace to obtain Pt@BaSrTiO3 (Pt@BST). X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were utilized to analyze the structures, morphologies, and surface chemical composition of the synthesized materials. Results showed that the well-crystallized Pt particles were successfully loaded onto the BST surface, and Pt and BST interacted to produce a metal-semiconductor heterojunction, improving the performance of N2 reduction. The N2 adsorption and desorption isotherms showed that the increase in the specific surface area helped the catalyst to adsorb N2, and the contact area with H2O also increased, which promotes the occurrence of NRR and thus produces more NH3. UV-Vis and PL spectroscopic techniques were used to characterize and analyze optical properties of the obtained catalyst. It is indicated that decoration of Pt reduces the band gap of the catalyst and increases the visible light absorption range, in addition, further enhances the charge separation and transfer, inhibits the recombination of electron-hole pairs, and improves the efficiency of charge separation. The performances of BST and Pt@BST for photoelectric catalytic synthesis of ammonia under ambient condition were studied. The yield of ammonia first increased and then decreased with the increase of Pt content. When the Pt content was 4wt%, the yield was the highest. The results showed that the ammonia yield of Pt@BST was 26.57 × 10-8 mol·h-1·mg-1 and Faraday efficiency (FE) was 5.43% at -0.3 V (vs. RHE) in 0.1 mol·L-1 Na2SO4 under natural conditions, suggesting that the ammonia yield of Pt@BST was twice that of pure BST (13.12 × 10-8 mol·h-1·mg-1). We conducted control experiments of 15N2 isotope and Ar in order to eliminate internal and external environmental pollution. Confirming that the detected NH3 was produced exclusively via nitrogen reduction reaction. After recycling the test six times at -0.3 V (vs. RHE), both FE and ammonia yield rate showed a slight variation, indicating the high stability of Pt@BST during N2 reduction process. This work provides a simple strategy for further designing the preparation of noble metal modified perovskite catalysts, and has promising application prospects in ammonia synthesis under ambient condition.

Graphical Abstract


ammonia synthesis, nitrogen reduction, Pt, BaSrTiO3

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[1] Ĉoriĉ I, Mercado B Q, Bill E, Vinyard D J, Holland P L. Binding of dinitrogen to an iron-sulfur-carbon site[J]. Nature, 2015, 526(7571): 96-99.
doi: 10.1038/nature15246 URL

[2] Jia H P, Quadrelli E A. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen[J]. Chem. Soc. Rev., 2014, 43(2): 547-564.
doi: 10.1039/C3CS60206K URL

[3] Erisman J W, Sutton M A, Galloway J, Klimont Z, Winiwarter W. How a century of ammonia synthesis changed the world[J]. Nat Geosci, 2008, 1(10): 636-639.
doi: 10.1038/ngeo325 URL

[4] Lv X W, Weng C C, Yuan Z Y. Ambient ammonia electrosynthesis: Current status, challenges, and perspectives[J]. ChemSusChem, 2020, 13(12): 3061-3078.
doi: 10.1002/cssc.202000670 URL

[5] Liu H Z. Ammonia synthesis catalyst 100 years: Practice, enlightenment and challenge[J]. Chinese J. Catal., 2014, 35(10): 1619-1640.
doi: 10.1016/S1872-2067(14)60118-2 URL

[6] Wang W, Xu M G, Xu X M, Zhou W, Shao Z P. Perovskite oxide based electrodes for high-performance photoelectrochemical water splitting[J]. Angew. Chem. Int. Edit., 2020, 59(1): 136-152.
doi: 10.1002/anie.201900292 URL

[7] Reddy C V, Reddy I N, Harish V V N, Reddy K R, Shetti N P, Shim J, Aminabhavi T M. Efficient removal of toxic organic dyes and photoelectrochemical properties of iron-doped zirconia nanoparticles[J]. Chemosphere, 2019, 239: 124766.
doi: 10.1016/j.chemosphere.2019.124766 URL

[8] Kumaravel V, Bartlett J, Pillai S C. Photoelectrochemical conversion of carbon dioxide (CO2) into fuels and value-added products[J]. ACS Energy Lett., 2020, 5(2): 486-519.
doi: 10.1021/acsenergylett.9b02585 URL

[9] Reddy C V, Reddy I N, Akkinepally B, Reddy K R, Shim J. Synthesis and photoelectrochemical water oxidation of (Y, Cu) codoped α-Fe2O3 nanostructure photoanode[J]. J. Alloy Compd., 2020, 814: 152349.
doi: 10.1016/j.jallcom.2019.152349 URL

[10] Liu D N, Wang J H, Bian S, Liu Q, Gao Y H, Wang X, Chu P K, Yu X F. Photoelectrochemical synthesis of ammonia with black phosphorus[J]. Adv. Funct. Mater., 2020, 30(24): 2002731.
doi: 10.1002/adfm.202002731 URL

[11] Vu M H, Nguyen C C, Do T O. Synergistic effect of Fe doping and plasmonic Au nanoparticles on W18O49 nano-rods for enhancing photoelectrochemical nitrogen reduction[J]. ACS Sustain. Chem. Eng., 2020, 8(32): 12321-12330.
doi: 10.1021/acssuschemeng.0c04662 URL

[12] Li M X, Lu Q J, Liu M L, Yin P, Wu C Y, Li H T, Zhang Y Y, Yao S Z. Photoinduced charge separation via the double-electron transfer mechanism in nitrogen vacancies g-C3N5/BiOBr for the photoelectrochemical nitrogen reduction[J]. ACS Appl. Mater. Inter., 2020, 12(34): 38266-38274.
doi: 10.1021/acsami.0c11894 URL

[13] Zhao J X, Zhang B P, Li Y, Yan L P, Wang S J. Optical and photocatalytic properties of TiO2/Ag-SiO2 nanocomposite thin films[J]. J. Alloy. Compd., 2012, 535: 21-26.
doi: 10.1016/j.jallcom.2012.04.089 URL

[14] Wang S J, Zhang B P. SPR propelled visible-active photo-catalysis on Au-dispersed Co3O4 films[J]. Appl. Catal. A-Gen., 2013, 467: 585-592.
doi: 10.1016/j.apcata.2013.07.021 URL

[15] Ren C L, Yang B F, Wu M, Xu J, Fu Z P, Lv Y, Guo T, Zhao Y X, Zhu C Q. Synthesis of Ag/ZnO nanorods array with enhanced photocatalytic performance[J]. J. Hazard. Mater., 2010, 182(1-3): 123-129.
doi: 10.1016/j.jhazmat.2010.05.141 URL

[16] Horiuchi Y, Kamei G, Saito M, Matsuoka M. Development of ruthenium-loaded alkaline-earth titanates as catalysts for ammonia synthesis[J]. Chem. Lett., 2013, 42(10): 1282-1284.
doi: 10.1246/cl.130574 URL

[17] Huang B M, Liu Y, Pang Q, Zhang X Y, Wang H T, Shen P K. Boosting the photocatalytic activity of mesoporous SrTiO3 for nitrogen fixation through multiple defects and strain engineering[J]. J. Mater.Chem. A, 2020, 8(42): 22251-22256.

[18] Selmi A, Mascot M, Jomni F, Carru J C. Investigation of interfacial dead layers parameters in Au/Ba0.85Sr0.15TiO3/Pt capacitor devices[J]. J. Alloy. Compd., 2020, 826: 154048.
doi: 10.1016/j.jallcom.2020.154048 URL

[19] Szafraniak B, Fušnik Ł, Xu J, Gao F, Brudnik A, Rydosz A. Semiconducting metal oxides: SrTiO3, BaTiO3 and BaSrTiO3 in gas-sensing applications: A review[J]. Coatings, 2021, 11(2): 185.
doi: 10.3390/coatings11020185 URL

[20] Nadaud K, Borderon C, Gillard R, Fourn E, Renoud R, Gundel H W. Temperature stable BaSrTiO3 thin films suitable for microwave applications[J]. Thin Solid Films, 2015, 591: 90-96.
doi: 10.1016/j.tsf.2015.08.019 URL

[21] Zhao Y X, Shi R, Bian X A, Zhou C, Zhao Y F, Zhang S, Wu F, Waterhouse G I N, Wu L Z, Tung C H, Zhang T R. Ammonia detection methods in photocatalytic and electrocatalytic experiments: How to improve the reliability of NH3 production rates?[J]. Adv. Sci., 2019, 6(8): 1802109.
doi: 10.1002/advs.201802109 URL

[22] Andersen S Z, Ĉoriĉ V, Yang S, Schwalbe J A, Nielander A C, McEnaney J M, Enemark-Rasmussen K, Baker J G, Singh A R, Rohr B A, Statt M J, Blair S J, Mezzavilla S, Kibsgaard J, Vesborg P C K, Cargnello M, Bent S F, Jaramillo T F, Stephens I E L, Nørskov J K, Chorkendorff I. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements[J]. Nature, 2019, 570(7762): 504-508.
doi: 10.1038/s41586-019-1260-x URL

[23] Rodrigues A, Bauer S, Baumbach T. Effect of post-annealing on the chemical state and crystalline structure of PLD Ba0.5Sr0.5TiO3 films analyzed by combined synchrotron X-ray diffraction and X-ray photoelectron spectroscopy[J]. Ceram. Int., 2018, 44(13): 16017-16024.
doi: 10.1016/j.ceramint.2018.06.038 URL

[24] Liao J X, Yang C R, Tian Z, Yang H G, Jin L. The influence of post-annealing on the chemical structures and dielectric properties of the surface layer of Ba0.6Sr0.4TiO3-films[J]. J. Phys. D Appl. Phys., 2006, 39(11): 2473-2479.
doi: 10.1088/0022-3727/39/11/024 URL

[25] Bulushev D A, Yuranov I, Suvorova E I, Buffat P A, Kiwi-Minsker L. Highly dispersed gold on activated carbon fibers for low-temperature CO oxidation[J]. J. Catal., 2004, 224(1): 8-17.
doi: 10.1016/j.jcat.2004.02.014 URL

[26] Vovk E I, Kalinkin A V, Smirnov M Y, Klembovskii I O, Bukhtiyarov V I. XPS study of stability and reactivity of oxidized Pt nanoparticles supported on TiO2[J]. J. Phys. Chem. C, 2017, 121(32): 17297-17304.
doi: 10.1021/acs.jpcc.7b04569 URL

[27] Li J J, Zhang M, Weng B, Chen J, Jia H P. Zero-degree photochemical synthesis of highly dispersed Pt/TiO2 for enhanced photocatalytic hydrogen generation[J]. J. Alloy Compd., 2020, 849: 156634.
doi: 10.1016/j.jallcom.2020.156634 URL

[28] Vu M H, Sakar M, Hassanzadeh-Tabrizi S A, Do T O. Photo(electro)catalytic nitrogen fixation: Problems and possibilities[J]. Adv. Mater. Interfaces, 2019, 6(12): 1900091.
doi: 10.1002/admi.201900091 URL



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