Abstract
At present, industrial synthetic ammonia was still obtained through the Hubble-Bosch process, with large energy consumption. It is a research hotspot to realize green synthetic ammonia by using solar energy. The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N. In this study, Ti was doped into BiOBr by one-step hydrothermal method, which was oxidized into TiO2 when the do** amount reaches the maximum, in situ forming Ti0.31B0.69OB/TiO2 composites. Benefiting from the synergistic effect of Ti do** and S-scheme heterojunction, the synthetic ammonia efficiency of Ti0.31B0.69OB/TiO2-11.96 reached 1.643 mmol·g−1cat at mild conditions and without hole scavenger for up to 7 h, the efficiency of synthetic ammonia is 115 times, 10.5 times and 3.3 times of that of BiOBr, Ti0.31B0.69OB and TiO2, respectively. Specifically, DFT calculation confirms that Ti do** accurately refine the electronic structure of BiOBr, facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier, thus accelerating the reaction kinetics of photocatalytic nitrogen reduction (NRR). Meanwhile, constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron–hole pairs, improving the reduction ability of electrons in the conduction band of TiO2 and the oxidation ability of holes in the valence band of Ti0.31B0.69OB.
Graphical abstract
摘要
工业合成氨采用Haber–Bosch工艺,需要在高温(300–500 ℃)、高压(15–25 MPa)下进行,能耗高且会产生大量的温室气体。与Haber–Bosch法相比,光催化合成氨可在常温、常压下进行,是一种能耗低、操作安全,且无CO2排放的绿色工艺。光催化固氮技术已成为当前催化领域的研究热点,是一种有望替代传统的哈伯法的新兴固氮技术。在本研究中,我们通过一步水热法将Ti掺杂取代BiOBr结构中的Bi原子,进一步增加Ti元素的掺杂量原位形成Ti0.31B0.69OB/TiO2异质结。Ti掺杂和构建异质界面的协同作用下,在不添加牺牲剂的情况下光照7小时,Ti0.31B0.69OB/TiO2的合成氨效率高达1.643 mmol·g−1cat,分别是BiOBr、Ti0.31B0.69OB和TiO2合成氨效率的115倍、10.5倍和3.3倍。DFT计算证实,Ti掺杂精准可调控BiOBr的电子结构,从而有效增**Bi位点对氮气(N2)在催化剂表面的吸附活化、降低活化氮分子(·N2)氢化反应的能垒,加速光催化氮还原(NRR)的反应动力学。同时,构建S-型异质结构可降低光生电子-空穴重组、促进电子-空穴的分离和转移,从而提高TiO2导带电子的还原能力和Ti0.31B0.69OB价带空穴的氧化能力。
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References
Yapicioglu A, Dincer I. A review on clean ammonia as a potential fuel for power generator. Renew Sust Energy Rev. 2019;103:96. https://doi.org/10.1016/j.rser.2018.12.023.
Shang SS, **ong W, Yang C, Johannessen B, Liu RG, Hsu HY, Gu QF, Leung MK, Shang J. Atomically dispersed iron metal site in a porphyrin-based metal-organic framework for photocatalytic nitrogen fixation. ACS Nano. 2021;15:9670. https://doi.org/10.1021/acsnano.0c10947.
Chen C, Zhu XR, Wen XJ, Zhou YY, Zhou L, Li H, Tao L, Li QL, Du SQ, Liu TT. Coupling N2 and CO2 in H2O to synthesize urea under ambient conditions. Nat Chem. 2020;12:717. https://doi.org/10.1021/acsnano.0c10947.
Ghavam S, Vahdati M, Wilson I, Styring P. Sustainable ammonia production processes. Front Energy Res. 2021;9:34. https://doi.org/10.3389/fenrg.2021.580808.
Han Q, Jiao HM, **ong LQ, Tang JW. Progress and challenges in photocatalytic ammonia synthesis. Mater Adv. 2021;2:564. https://doi.org/10.1039/D0MA00590H.
Bo YA, Wang HY, Lin YX, Yang T, Ye R, Li Y, Hu CY, Du PY, Hu YG, Liu Z. Altering hydrogenation pathways in photocatalytic nitrogen fixation by tuning local electronic structure of oxygen vacancy with dopant. Angew Chem Int Ed. 2021;60:16085. https://doi.org/10.1002/anie.202104001.
Li J, Li H, Zhan GM, Zhang LZ. Solar water splitting and nitrogen fixation with layered bismuth oxyhalides. Acc Chem Res. 2017;50:112. https://doi.org/10.1021/acs.accounts.6b00523.
Li JD, Zheng M, Wei F, Dong CC, **u ZY, Mu W, Zhou X, Ding YA, Han XJ. Fe doped InVO4 nanosheets with rich surface oxygen vacancies for enhanced electrochemical nitrogen fixation. Chem Eng J. 2022;431:133383. https://doi.org/10.1016/j.cej.2021.133383.
Deng Y, **ao ZY, Wang ZC, Lai JP, Liu XB, Zhang D, Han Y, Li SX, Sun W, Wang L. The rational adjusting of proton-feeding by Pt-doped FeP/C hollow nanorod for promoting nitrogen reduction kinetics. Appl Catal B: Environ. 2021;291:120047. https://doi.org/10.1016/j.apcatb.2021.120047.
Shi R, Zhao YX, Waterhouse GI, Zhang S, Zhang TR. Defect engineering in photocatalytic nitrogen fixation. ACS Catal. 2019;9:9739. https://doi.org/10.1021/acscatal.9b03246.
Wang GA, Huo TT, Deng QH, Yu F, ** enhanced generation of surface oxygen vacancies in bismuth molybdate for efficient photocatalytic nitrogen fixation. Appl Catal B: Environ. 2022;310:121319. https://doi.org/10.1016/j.apcatb.2022.121319.
Xu FY, Meng K, Cao S, Jiang CH, Chen T, Xu JS, Yu JG. Step-by-step mechanism insights into the TiO2/Ce2S3 S-scheme photocatalyst for enhanced aniline production with water as a proton source. ACS Catal. 2021;12:164. https://doi.org/10.1021/acscatal.1c04903.
Wu JH, Zhao W, Chen M, Liu CX, Chen J, Chen Z. Recent advance in visible-light-driven photocatalysis on lead-free halide perovskites. Chin J Rare Met. 2022;46:96. https://doi.org/10.13373/j.cnki.cjrm.XY21040007.
Xu QL, Zhang LY, Cheng B, Fan JJ, Yu JG. S-scheme heterojunction photocatalyst. Chem. 2020;6:1543. https://doi.org/10.1016/j.chempr.2020.06.010.
Wang TY, Feng CT, Liu JQ, Wang DJ, Hu HM, Hu J, Chen Z, Xue GL. Bi2WO6 hollow microspheres with high specific surface area and oxygen vacancies for efficient photocatalysis N2 fixation. Chem Eng J. 2021;414:128827. https://doi.org/10.1016/j.cej.2021.128827.
Zhao K, Zhang LZ, Wang JJ, Li QX, He WW, Yin JJ. Surface structure-dependent molecular oxygen activation of BiOCl single-crystalline nanosheets. J Am Chem Soc. 2013;135:15750. https://doi.org/10.1021/ja4092903.
Wang XJ, Zhao Y, Li FT, Dou LJ, Li YP, Zhao J, Hao YJ. A chelation strategy for in-situ constructing surface oxygen vacancy on {001} facets exposed BiOBr nanosheets. Sci Rep. 2016;6:1. https://doi.org/10.1038/srep24918.
Zhang G, Hu ZY, Sun M, Liu Y, Liu LM, Liu HJ, Huang CP, Qu JH, Li JH. Formation of Bi2WO6 bipyramids with vacancy pairs for enhanced solar-driven photoactivity. Adv Funct Mater. 2015;25:3726. https://doi.org/10.1002/adfm.201501009.
Ye LQ, Zan L, Tian LH, Peng TY, Zhang JJ. The {001} facets-dependent high photoactivity of BiOCl nanosheets. Chem Commun. 2011;47:6951. https://doi.org/10.1039/C1CC11015B.
Sun SM, Wang WZ. Advanced chemical compositions and nanoarchitectures of bismuth based complex oxides for solar photocatalytic application. RSC Adv. 2014;4:47136. https://doi.org/10.1039/C4RA06419D.
Li J, Yu Y, Zhang LZ. Bismuth oxyhalide nanomaterials: layered structures meet photocatalysis. Nanoscale. 2014;6:8473. https://doi.org/10.1039/C4NR02553A.
Cheng HF, Huang BB, Dai Y. Engineering BiOX (X= Cl, Br, I) nanostructures for highly efficient photocatalytic applications. Nanoscale. 2014;6:2009. https://doi.org/10.1039/C3NR05529A.
Liu Y, Hu ZF, Yu J. Fe enhanced visible-light-driven nitrogen fixation on BiOBr nanosheets. Chem Mater. 2020;32:1488. https://doi.org/10.1021/acs.chemmater.9b04448.
Cai YT, Song J, Liu XY, Yin X, Li XR, Yu JY, Ding B. Soft BiOBr@TiO2 nanofibrous membranes with hierarchical heterostructures as efficient and recyclable visible-light photocatalysts. Environ Sci: Nano. 2018;5:2631. https://doi.org/10.1039/C8EN00866C.
Meng QQ, Lv CD, Sun JX, Hong WZ, **ng WN, Qiang LS, Chen G, ** XL. High-efficiency Fe-mediated Bi2MoO6 nitrogen-fixing photocatalyst: reduced surface work function and ameliorated surface reaction. Appl Catal B: Environ. 2019;256:117781. https://doi.org/10.1016/j.apcatb.2019.117781.
Huang WM, Hua X, Zhao YP, Li K, Tang LP, Zhou M, Cai ZS. Enhancement of visible-light-driven photocatalytic performance of BiOBr nanosheets by Co2+ do**. J Mater Sci: Mater Electron. 2019;30:14967. https://doi.org/10.1007/s10854-019-01869-x.
Yang J, Liu TY, Zhou HF, Cao W, Chen C, HeX JCY, Li YF, Wang YP. In situ conversion of typical type-I MIL-125 (Ti)/BiOBr into type-II heterostructure photocatalyst via MOF self-sacrifice: photocatalytic mechanism and theoretical study. J Alloys Compd. 2022;900:163440. https://doi.org/10.1016/j.jallcom.2021.163440.
Xu C, Zhou Q, Huang WY, Yang K, Zhang YC, Liang TX, Liu ZQ. Constructing Z-scheme β-Bi2O3/ZrO2 heterojunctions with 3D mesoporous SiO2 nanospheres for efficient antibiotic remediation via synergistic adsorption and photocatalysis. Rare Met. 2022;41:2094. https://doi.org/10.1007/s12598-021-01897-9.
Yu Y, Cao CY, Liu H, Li P, Wei FF, Jiang Y, Song WG. A Bi/BiOCl heterojunction photocatalyst with enhanced electron–hole separation and excellent visible light photodegrading activity. J Mater Chem A. 2014;2:1677. https://doi.org/10.1039/C3TA14494A.
Cao F, Wang JM, Wang YA, Zhou J, LiS QGW, Fan WQ. An in situ Bi-decorated BiOBr photocatalyst for synchronously treating multiple antibiotics in water. Nanoscale Adv. 2019;1:1124. https://doi.org/10.1039/C8NA00197A.
Li K, Huang ZY, Zeng XQ, Huang BB, Gao SM, Lu J. Synergetic effect of Ti3+ and oxygen do** on enhancing photoelectrochemical and photocatalytic properties of TiO2/g-C3N4 heterojunctions. ACS Appl Mater Interfaces. 2017;9:11577. https://doi.org/10.1021/acsami.6b16191.
Li JF, Li ZY, Liu XM, Li CY, Zheng YF, Yeung KWK, Cui ZD, Liang YQ, Zhu SL, Hu WB, Qi YJ, Zhang TJ, Wang XB, Wu SL. Interfacial engineering of Bi2S3/Ti3C2Tx MXene based on work function for rapid photo-excited bacteria-killing. Nat Commun. 2021;12:1224. https://doi.org/10.1038/s41467-021-21435-6.
Parnicka P, Lisowski W, Klimczuk T, Mikolajczyk A, Zaleska-Medynska A. A novel (Ti/Ce)UiO-X MOFs@TiO2 heterojunction for enhanced photocatalytic performance: boosting via Ce4+/Ce3+ and Ti4+/Ti3+ redox mediators. Appl Catal B: Environ. 2022;310:121349. https://doi.org/10.1016/j.apcatb.2022.121349.
Guo ML, Wan SP, Li CL, Zhang K. Graphene oxide as a hole extraction layer loaded on BiVO4 photoanode for highly efficient photoelectrochemical water splitting. Rare Met. 2022;41:3795–3802. https://doi.org/10.1007/s12598-022-02014-0
Bu YY, Chen ZY. Effect of oxygen-doped C3N4 on the separation capability of the photoinduced electron-hole pairs generated by O-C3N4@TiO2 with quasi-shell-core nanostructure. Electrochim Acta. 2014;144:42. https://doi.org/10.1016/j.electacta.2014.08.095.
Li JH, Shen B, Hong ZH, Lin BZ, Gao BF, Chen YL. A facile approach to synthesize novel oxygen-doped g-C3N4 with superior visible-light photoreactivity. Chem Commun. 2012;48:12017. https://doi.org/10.1039/C2CC35862J.
Xue C, Zhang TX, Ding SJ, Wei JJ, Yang GD. Anchoring tailored low-index faceted BiOBr nanoplates onto TiO2 nanorods to enhance the stability and visible-light-driven catalytic activity. ACS Appl Mater Interfaces. 2017;9:16091. https://doi.org/10.1021/acsami.7b00433.
Huang YW, Zhu YS, Chen SJ, **e XQ, Wu ZJ, Zhang N. Schottky junctions with Bi cocatalyst for taming aqueous phase N2 reduction toward enhanced solar ammonia production. Adv Sci. 2021;8:2003626. https://doi.org/10.1002/advs.202003626.
Chen LW, Hao YC, Guo Y, Zhang QH, Li JN, Gao WY, Ren LT, Su X, Hu LY, Zhang N, Li SW, Feng X, Gu L, Zhang YW, Yin AX, Wang B. Metal-organic framework membranes encapsulating gold nanoparticles for direct plasmonic photocatalytic nitrogen fixation. J Am Chem Soc. 2021;143:5727. https://doi.org/10.1021/jacs.0c13342.
Gh E, Shaobin W, Hongqi S, Mika S. Core/shell FeVO4@BiOCl heterojunction as a durable heterogeneous Fenton catalyst for the efficient sonophotocatalytic degradation of p-nitrophenol. Sep Purif Technol. 2020;231:115915. https://doi.org/10.1016/j.seppur.2019.115915.
Zhang GA, Cheng YF. Micro-electrochemical characterization and Mott–Schottky analysis of corrosion of welded X70 pipeline steel in carbonate/bicarbonate solution. Electrochim Acta. 2009;55:316. https://doi.org/10.1016/j.electacta.2009.09.001.
Ye J, Zhang YY, Wang J, Liu S, Chang YH, Xu XP, Feng CT, Xu J, Guo L, Xu JT. Photo-Fenton and oxygen vacancies’ synergy for enhancing catalytic activity with S-scheme FeS2/Bi2WO6 heterostructure. Catal Sci Technol. 2022;12:4228. https://doi.org/10.1039/D2CY00610C.
Yan R, Zada A, Sun L, Li ZJ, Mu ZY, Chen SY, Yang F, Sun JH, Bai LL, Qu Y, **g LQ. Comparative study of metal oxides and phosphate modification with different mechanisms over g-C3N4 for visible-light photocatalytic degradation of metribuzin. Rare Met. 2022;41(1):155. https://doi.org/10.1007/s12598-021-01857-3
Chen L, He XX, Gong ZH, Li JL, Liao Y, Li XT, Ma J. Significantly improved photocatalysis-self-Fenton degradation performance over g-C3N4 via promoting Fe(III)/Fe(II) cycle. Rare Met. 2022;41(7):2429. https://doi.org/10.1007/s12598-022-01963-w.
Niu L, Wang D, Xu K, Hao W, An L, Kang Z, Sun Z. Tuning the performance of nitrogen reduction reaction by balancing the reactivity of N2 and the desorption of NH3. Nano Res. 2021;14:4093. https://doi.org/10.1007/s12274-021-3348-5.
Niu L, Liu Z, Liu G, Li M, Zong X, Wang D, An L, Qu D, Sun X, Wang XJNR. Surface hydrophobic modification enhanced catalytic performance of electrochemical nitrogen reduction reaction. Nano Res. 2022;15:3886. https://doi.org/10.1007/s12274-021-4015-6.
Qiu JY, Feng HZ, Chen ZH, Ruan SH, Chen YP, Xu TT, Su JY, Ha EN, Wang LY. Selective introduction of surface defects in anatase TiO2 nanosheets for highly efficient photocatalytic hydrogen generation. Rare Met. 2022;41(6):2074. https://doi.org/10.1007/s12598-021-01929-4.
Li Z, Wu Z, He R, Wan L, Zhang S. In2O3-x(OH)y/Bi2MoO6 S-scheme heterojunction for enhanced photocatalytic performance. J Mater Sci Technol. 2020;56:151. https://doi.org/10.1016/j.jmst.2020.02.061.
Wu Y, Mao S, Liu C, Pei F, Wang F, Hao Q, **a M, Lei W. Enhanced degradation of chloramphenicol through peroxymonosulfate and visible light over Z-scheme photocatalysts: synergetic performance and mechanism insights. J Colloid Interface Sci. 2022;608:322. https://doi.org/10.1016/j.jcis.2021.09.197.
Cheng L, Yue X, Fan J, **ang Q. Site-specific electron-driving observations of CO2-to-CH4 photoreduction on Co-doped CeO2/Crystalline carbon nitride S-scheme heterojunctions. Adv Mater. 2022;34:2200929. https://doi.org/10.1002/adma.202200929.
Zulfiqar S, Liu S, Rahman N, Tang H, Shah S, Yu X, Liu Q. Construction of S-scheme MnO2@ CdS heterojunction with core–shell structure as H2 production photocatalyst. Rare Met. 2021;40:2381. https://doi.org/10.1007/s12598-020-01616-w.
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This work was financially supported by the National Natural Science Foundation of China (Nos. 22168040 and 22162025) and the Project of Science & Technology Office of Shannxi Province (No. 2022JM-062).
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Li, RQ., Bian, YJ., Yang, CM. et al. Electronic structure regulation and built-in electric field synergistically strengthen photocatalytic nitrogen fixation performance on Ti-BiOBr/TiO2 heterostructure. Rare Met. 43, 1125–1138 (2024). https://doi.org/10.1007/s12598-023-02471-1
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DOI: https://doi.org/10.1007/s12598-023-02471-1