Abstract
Electrochemical nitrogen fixation has received great attention in recent years due to its reliable and stable electrolytic efficiency. In this work, boron-doped carbon nitride with π-electron delocalization and vacancies was prepared by an in situ decomposition-thermal polymerization method. A series of characterizations were utilized to analyze the structure, morphology, and property. The results demonstrated that the secondary sintering and boron doping enhanced π-electron delocalization and induced the nitrogen vacancies of g-C3N4. The 0.24% boron-doped g-C3N4 electrocatalyst achieved the best ammonia yield (5.4 μg·h−1·mgcat−1) and the highest Faraday efficiency (14.1%) at −0.7 V vs reversible hydrogen electrode in 0.1 M Na2SO4. Furthermore, a feasible mechanism was proposed for the electrochemical nitrogen reduction process.
Graphical abstract
Similar content being viewed by others
References
Cao Y, Li Q, Wang W (2017) Construction of a crossed-layer-structure MoS2/g-C3N4 heterojunction with enhanced photocatalytic performance. RSC Adv 7:6131–6139
Chen X, Zhao X, Kong Z (2018) Unravelling the electrochemical mechanisms for nitrogen fixation on single transition metal atoms embedded in defective graphitic carbon nitride. J Mater Chem A 6:21941–21948
Chen C, Yan D, Wang Y (2019) B-N pairs enriched defective carbon nanosheets for ammonia synthesis with high efficiency. Nano Micro Lett 15:1805029
Dong G, Ho W, Wang C (2015) Selective photocatalytic N2 fixation dependent on g-C3N4 induced by nitrogen vacancies. J Mater Chem A 3:23435–23441
Guo W, Liang Z, Zhao J, Zhu B (2018) Hierarchical cobalt phosphide hollow nanocages toward electrocatalytic ammonia synthesis under ambient pressure and room temperature. Small Methods 2:1800204
Han Z, Choi G, Hong S, Wu T (2019) Activated TiO2 with tuned vacancy for efficient electrochemical nitrogen reduction. Appl Catal B 257:117896
Hu S, Lang L, Tian Y, Wei X, Ding J (2015) Simultaneous nanostructure and heterojunction engineering of graphitic carbon nitride via in situ Ag doping for enhanced photoelectrochemical activity. Appl Catal B 163:611–622
Jiang Y, Zhang X, Pei L (2018) Silver nanoparticles modified two-dimensional transition metal carbides as nanocarriers to fabricate acetycholinesterase-based electrochemical biosensor. Chem Eng J 339:547–556
Li L, Tang C, Xia B, Jin H (2019) Two-dimensional mosaic bismuth nanosheets for highly selective ambient electrocatalytic nitrogen reduction. ACS Catal 9:2902–2908
Li C, Ma D, Mou S (2020) Porous LaFeO3 nanofiber with oxygen vacancies as an efficient electrocatalyst for N2 conversion to NH3 under ambient conditions. J Energy Chem 50:402–408
Liu Y, Han M, Xiong Q, Zhao S, Zhao C (2019) Dramatically enhanced ambient ammonia electrosynthesis performance by in-operando created Li-S interactions on MoS2 electrocatalyst. Adv Energy Mater 9:1803935
Liu J, Kong W, Jin Z, Han Z, Sun J (2020a) A MoFe nitrogenase-mimicking electrocatalyst for nitrogen fixation with high faradaic efficiency. J Mater Chem A 8:19278–19282
Liu A, Yang Y, Ren X, Zhao Q (2020b) Current progress of electrocatalysts for ammonia synthesis through electrochemical nitrogen reduction under ambient conditions. ChemSusChem 11:3766–3788
Lv C, Qian Y, Yan C, Ding Y, Liu Y, Chen G (2018a) Defect engineering metal-free polymeric carbon nitride electrocatalyst for effective nitrogen fixation under ambient conditions. Angew Chem Int Ed 57:10246–10250
Lv C, Yan C, Chen G, Ding Y, Sun J (2018b) An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions. Agnew Chem Int Ed 57:6073–6076
Peng G, Wu J, Wang M, Zhou H (2020) Nitrogen-defective polymeric carbon nitride nanolayer enabled efficient electrocatalytic nitrogen reduction with high faradaic efficiency. Nano Lett 20:2879–2885
Qiu W, Xie X, Qiu J (2018) High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst. Nat Commun 9:3485
Roper W, Duckworth O, Crossman J (2020) Rhizobium leguminosarum strain combination effects on nodulation and biological nitrogen fixation with Vicia villosa. Appl Soil Ecol 156:103703
Shi M, Bao D, Wulan W, Li Y, Zhang Y (2017) Au sub-nanoclusters on TiO2 toward highly efficient and selective electrocatalyst for N2 conversion to NH3 at ambient conditions. Adv Mater 29:1606550
Sun X, Kong T (2020) Chemolithoautotropic diazotrophy dominates the nitrogen fixation process in mine tailings. Environ Sci Technol 54:6082–6093
Sun X, Huang H, Xia L, Cao R (2019) A biomass-derived carbon-based electrocatalyst for efficient N2 fixation to NH3 at ambient conditions. Chem Eur J 25:1914–1917
Tian G, Chen Y, Zhou W (2011) Facile solvothermal synthesis of hierarchical flower-like Bi2MoO6 hollow spheres as high performance visible-light driven photocatalysts. J Mater Chem C 21:887–892
Wang S, Hai X, Ding X, Chang K (2017) Light-switchable oxygen vacancies in ultrafine Bi5O7Br nanotubes for boosting solar-driven nitrogen fixation in pure water. Adv Mater 29:1701774
Wang Z, Li Y, Yu H, Xu Y, Xue H (2018) Ambient electrochemical synthesis of ammonia from nitrogen and water catalyzed by flower-like gold microstructures. ChemSusChem 11:3480–3485
Wang Z, Hu X, Liu Z, Zou G (2019a) Recent developments in polymeric carbon nitride-derived photocatalysts and electrocatalysts for nitrogen fixation. ACS Catal 9:10260–10278
Wang Z, Gong F, Zhang L (2019b) Electrocatalytic hydrogenation of N2 to NH3 by MnO: Experimental and theoretical investigations. Adv Sci 6:1801182
Wang C, Zhu X, Zuo P (2020) Novel confinement of Mn3O4 nanoparticles on two-dimensional carbide enabling high-performance electrochemical synthesis of ammonia under ambient conditions. Chem Eng J 396:125163
Xiang Z, Li H, Wang Y, Song Y (2020) Recent advances in noble-metal-free catalysts for electrocatalytic synthesis of ammonia under ambient conditions. Chem Asian J 17:1791–1807
Yan C, Chen G, Ding Y, Sun J, Zhou Y, Yu G (2018) An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions. Angew Chem Int Ed 57:6073–6076
Yu X, Han P, Wei Z (2018) Boron-doped graphene for electrocatalytic N2 reduction. Joule 2:1–13
Zhang M, Xu J, Zong R (2014) Enhancement of visible light photocatalytic activities via porous structure of g-C3N4. Appl Catal B 147:229–235
Zhao Y, Shi R, Wang B (2019) Tuning oxygen vacancies in ultrathin TiO2 nanosheets to boost photocatalytic nitrogen fixation up to 700 nm. Adv Mater 31:1806482
Zhao Z, Luo S, Ma P, Luo Y, Wu W (2020) In situ synthesis of MoS2 on C3N4 to form MoS2/C3N4 with interfacial Mo-N coordination for electrocatalytic reduction of N2 to NH3. ACS Sustain Chem Eng 8:8814–8822
Funding
Financial support for this project was provided by the National Natural Science Foundation of China (No. 51702023).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
ESM 1
(DOCX 298 kb)
Rights and permissions
About this article
Cite this article
Wang, X., Huang, J., Hu, F. et al. Synthesis of B-doped C3N4 nanosheets by secondary sintering for enhanced electrocatalytic nitrogen fixation performance. J Nanopart Res 23, 63 (2021). https://doi.org/10.1007/s11051-021-05177-6
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-021-05177-6