Abstract
Developing efficient electrocatalysts for selective nitrate contamination reduction into value-added ammonia is significant. Here, heterostructured Co/CoO nanosheet arrays (Co/CoO NSAs) exhibited excellent Faradaic efficiency (93.8%) and selectivity (91.2%) for nitrate electroreduction to ammonia, greatly outperforming Co NSAs. 15N isotope labeling experiments and 1H nuclear magnetic resonance (NMR) quantitative testing methods confirmed the origin of the produced ammonia. Electrochemical in situ Fourier transform infrared (FTIR) spectroscopy, online differential electrochemical mass spectrometry (DEMS) data and density functional theory (DFT) results revealed that the superior performances arose from the electron deficiency of Co induced by the rectifying Schottky contact in the Co/CoO heterostructures. The electron transfer from Co to CoO at the interface could not only suppress the competitive hydrogen evolution reaction, but also increase energy barriers for by-products, thus leading to high Faradaic efficiency and selectivity of ammonia.
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Tang C, Qiao SZ. Chem Soc Rev, 2019, 48: 3166–3180
Hao YC, Guo Y, Chen LW, Shu M, Wang XY, Bu TA, Gao WY, Zhang N, Su X, Feng X, Zhou JW, Wang B, Hu CW, Yin AX, Si R, Zhang YW, Yan CH. Nat Catal, 2019, 2: 448–456
Canfield DE, Glazer AN, Falkowski PG. Science, 2010, 330: 192–196
Fang Z, Yu G. Sci China Chem, 2018, 61: 1045–1046
Wang P, Chang F, Gao W, Guo J, Wu G, He T, Chen P. Nat Chem, 2016, 9: 64–70
Yang X, Kattel S, Nash J, Chang X, Lee JH, Yan Y, Chen JG, Xu B. Angew Chem Int Ed, 2019, 58: 13768–13772
Hill PJ, Doyle LR, Crawford AD, Myers WK, Ashley AE. J Am Chem Soc, 2016, 138: 13521–13524
Patil BS, Wang Q, Hessel V, Lang J. Catal Today, 2015, 256: 49–66
Liu Y, Cheng M, He Z, Gu B, Xiao C, Zhou T, Guo Z, Liu J, He H, Ye B, Pan B, Xie Y. Angew Chem Int Ed, 2019, 58: 731–735
Chen JG, Crooks RM, Seefeldt LC, Bren KL, Bullock RM, Darensbourg MY, Holland PL, Hoffman B, Janik MJ, Jones AK, Kanatzidis MG, King P, Lancaster KM, Lymar SV, Pfromm P, Schneider WF, Schrock RR. Science, 2018, 360: eaar6611
Comer BM, Fuentes P, Dimkpa CO, Liu YH, Fernandez CA, Arora P, Realff M, Singh U, Hatzell MC, Medford AJ. Joule, 2019, 3: 1578–1605
Lan R, Tao S. Front Energy Res, 2014, 2: 35
Wang Y, Shi M, Bao D, Meng F, Zhang Q, Zhou Y, Liu K, Zhang Y, Wang J, Chen Z, Liu D, Jiang Z, Luo M, Gu L, Zhang Q, Cao X, Yao Y, Shao M, Zhang Y, Zhang X, Chen JG, Yan J, Jiang Q. Angew Chem Int Ed, 2019, 58: 9464–9469
Andersen SZ, Čolić V, Yang S, Schwalbe JA, Nielander AC, McE-naney JM, Enemark-Rasmussen K, Baker JG, Singh AR, Rohr BA, Statt MJ, Blair SJ, Mezzavilla S, Kibsgaard J, Vesborg PCK, Cargnello M, Bent SF, Jaramillo TF, Stephens IEL, Nørskov JK, Chorkendorff I. Nature, 2019, 570: 504–508
Huang P, Liu W, He Z, Xiao C, Yao T, Zou Y, Wang C, Qi Z, Tong W, Pan B, Wei S, Xie Y. Sci China Chem, 2018, 61: 1187–1196
Wang L, Xia M, Wang H, Huang K, Qian C, Maravelias CT, Ozin GA. Joule, 2018, 2: 1055–1074
Légaré MA, Bélanger-Chabot G, Dewhurst RD, Welz E, Krummenacher I, Engels B, Braunschweig H. Science, 2018, 359: 896–900
Jia H, Du A, Zhang H, Yang J, Jiang R, Wang J, Zhang C. J Am Chem Soc, 2019, 141: 5083–5086
Gao X, An L, Qu D, Jiang W, Chai Y, Sun S, Liu X, Sun Z. Sci Bull, 2019, 64: 918–925
Hansen AT, Dolph CL, Foufoula-Georgiou E, Finlay JC. Nat Geosci, 2018, 11: 127–132
Heck KN, Garcia-Segura S, Westerhoff P, Wong MS. Acc Chem Res, 2019, 52: 906–915
Martínez J, Ortiz A, Ortiz I. Appl Catal B-Environ, 2017, 207: 42–59
González Pérez O, Bisang JM. Electrochim Acta, 2016, 194: 448–453
Garcia-Segura S, Lanzarini-Lopes M, Hristovski K, Westerhoff P. Appl Catal B-Environ, 2018, 236: 546–568
Stirling A, Pápai I, Mink J, Salahub DR. J Chem Phys, 1994, 100: 2910–2923
Carlson RM. Anal Chem, 1978, 50: 1528–1531
Wang Y, Yu Y, Jia R, Zhang C, Zhang B. Natl Sci Rev, 2019, 6: 730–738
Wang Y, Zhou W, Jia R, Yu Y, Zhang B. Angew Chem Int Ed, 2020, 59: 5350–5354
Li XH, Antonietti M. Chem Soc Rev, 2013, 42: 6593–6604
Lin YX, Zhang SN, Xue ZH, Zhang JJ, Su H, Zhao TJ, Zhai GY, Li XH, Antonietti M, Chen JS. Nat Commun, 2019, 10: 4380
Liu J, Liu Y, Liu N, Han Y, Zhang X, Huang H, Lifshitz Y, Lee ST, Zhong J, Kang Z. Science, 2015, 347: 970–974
Zhuang Z, Li Y, Li Z, Lv F, Lang Z, Zhao K, Zhou L, Moskaleva L, Guo S, Mai L. Angew Chem Int Ed, 2018, 57: 496–500
Li D, Ding LX, Wang S, Cai D, Wang H. J Mater Chem A, 2014, 2: 5625–5630
Chen M, Zhou Q, Du X, Zhang J, Li W, Lu Y, Zhang D, Qi P, Tang Y. J Alloys Compd, 2019, 783: 363–370
Liao L, Zhang Q, Su Z, Zhao Z, Wang Y, Li Y, Lu X, Wei D, Feng G, Yu Q, Cai X, Zhao J, Ren Z, Fang H, Robles-Hernandez F, Baldelli S, Bao J. Nat Nanotech, 2014, 9: 69–73
Lu Y, Dong CL, Huang YC, Zou Y, Liu Y, Li Y, Zhang N, Chen W, Zhou L, Lin H, Wang S. Sci China Chem, 2020, 63: 980–986
Su H, Zhang KX, Zhang B, Wang HH, Yu QY, Li XH, Antonietti M, Chen JS. J Am Chem Soc, 2017, 139: 811–818
Zhang C, Shi Y, Yu Y, Du Y, Zhang B. ACS Catal, 2018, 8: 8077–8083
Gao R, Liu L, Hu Z, Zhang P, Cao X, Wang B, Liu X. J Mater Chem A, 2015, 3: 17598–17605
Biesinger MC, Payne BP, Grosvenor AP, Lau LWM, Gerson AR, Smart RSC. Appl Surf Sci, 2011, 257: 2717–2730
Zhang L, Ding L, Chen G, Yang X, Wang H. Angew Chem Int Ed, 2019, 58: 2612–2616
Zhou P, He J, Zou Y, Wang Y, Xie C, Chen R, Zang S, Wang S. Sci China Chem, 2019, 62: 1365–1370
da Cunha MCPM, De Souza JPI, Nart FC. Langmuir, 2000, 16: 771–777
Hu C, Zhang L, Li L, Zhu W, Deng W, Dong H, Zhao ZJ, Gong J. Sci China Chem, 2019, 62: 1030–1036
Figueiredo MC, Solla-Gullón J, Vidal-Iglesias FJ, Climent V, Feliu JM. Catal Today, 2013, 202: 2–11
Pérez-Gallent E, Figueiredo MC, Katsounaros I, Koper MTM. Electrochim Acta, 2017, 227: 77–84
Guo Y, Stroka JR, Kandemir B, Dickerson CE, Bren KL. J Am Chem Soc, 2018, 140: 16888–16892
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This work was supported by the National Natural Science Foundation of China (21871206, 21701122).
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Promoting Selective Electroreduction of Nitrate to Ammonia over Electron-Deficient Co Modulated by Schottky Rectifying Contact
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Yu, Y., Wang, C., Yu, Y. et al. Promoting selective electroreduction of nitrates to ammonia over electron-deficient Co modulated by rectifying Schottky contacts. Sci. China Chem. 63, 1469–1476 (2020). https://doi.org/10.1007/s11426-020-9795-x
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DOI: https://doi.org/10.1007/s11426-020-9795-x