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Engineering >> 2023, Volume 25, Issue 6 doi: 10.1016/j.eng.2021.12.016

Persulfate-Induced Three Coordinate Nitrogen (N3C) Vacancies in Defective Carbon Nitride for Enhanced Photocatalytic H2O2 Evolution

a College of Environmental Science and Engineering, Biomedical Multidisciplinary Innovation Research Institute, Shanghai East Hospital, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092, China
b Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, China

Received: 2021-08-10 Revised: 2021-12-03 Accepted: 2021-12-16 Available online: 2022-02-25

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Abstract

In-situ photocatalytic H2O2 production has been receiving increasing attention in recent years for sustainable H2O2 synthesis. Graphitic carbon nitride (g-C3N4) is regarded as one of the most promising semiconductor photocatalysts for H2O2 evolution. Introducing N defects in g-C3N4 has been proved to be an effective strategy to enhance photocatalytic activity. However, the photocatalytic mechanism of the N vacancies is ambiguous and different types of N vacancies in g-C3N4 may exhibit different effects on photocatalytic activity. Herein, we develop a facile sodium persulfate eutectic polymerization method to prepare the g-C3N4 with abundant three coordinate nitrogen (N3C) vacancies. This type of nitrogen vacancy has not been studied in g-C3N4 for photocatalytic H2O2 production. Our results showed that the introduction of N3C vacancies in the g-C3N4 successfully broadened the light absorption range, inhibited the photoexcited charge recombination with enhanced O2 adsorption to promote oxygen activation. The photocatalytic H2O2 evolution from the N3C-rich g-C3N4 is 4.5 times higher than that of the pristine g-C3N4. This study demonstrates a novel strategy to introduce N3C vacancies in g-C3N4, which offers a new method to develop active catalysts for photocatalytic H2O2 evolution.

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References

[ 1 ] Edwards JK, Solsona B, Ntainjua EN, Carley AF, Herzing AA, Kiely CJ, et al. Switching off hydrogen peroxide hydrogenation in the direct synthesis process. Science 2009;323(5917):1037‒41. link1

[ 2 ] Lu Z, Chen G, Siahrostami S, Chen Z, Liu K, Xie J, et al. High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials. Nat Catal 2018;1:156‒62. link1

[ 3 ] Su H, Christodoulatos C, Smolinski B, Arienti P, O’Connor G, Meng X. Advanced oxidation process for DNAN using UV/H2O2. Engineering 2019;5(5):849‒54. link1

[ 4 ] Fan W, Zhang B, Wang X, Ma W, Li D, Wang Z, et al. Efficient hydrogen peroxide synthesis by metal-free polyterthiophene via photoelectrocatalytic dioxygen reduction. Energy Environ Sci 2020;13:238‒45. link1

[ 5 ] Xia C, Xia Y, Zhu P, Fan L, Wang H. Direct electrosynthesis of pure aqueous H2O2 solutions up to 20% by weight using a solid electrolyte. Science 2019;366(6462):226‒31. link1

[ 6 ] Sun Y, Han L, Strasser P. A comparative perspective of electrochemical and photochemical approaches for catalytic H2O2 production. Chem Soc Rev 2020;49(18):6605‒31. link1

[ 7 ] Wang X, Wang F, Sang Y, Liu H. Full-spectrum solar-light-activated photocatalysts for light‒chemical energy conversion. Adv Energy Mater 2017;7(23):1700473. link1

[ 8 ] Kormann C, Bahnemann DW, Hoffmann MR. Photocatalytic production of hydrogen peroxides and organic peroxides in aqueous suspensions of titanium dioxide, zinc oxide, and desert sand. Environ Sci Technol 1988;22(7):798‒806. link1

[ 9 ] Tsukamoto D, Shiro A, Shiraishi Y, Sugano Y, Ichikawa S, Tanaka S, et al. Photocatalytic H2O2 production from ethanol/O2 system using TiO2 loaded with Au‒Ag bimetallic alloy nanoparticles. ACS Catal 2012;2(4):599‒603. link1

[10] Hirakawa H, Shiota S, Shiraishi Y, Sakamoto H, Ichikawa S, Hirai T. Au nanoparticles supported on BiVO4: effective inorganic photocatalysts for H2O2 production fromwater and O2 under visible light. ACS Catal 2016;6(8):4976‒82. link1

[11] Isaka Y, Kondo Y, Kawase Y, Kuwahara Y, Mori K, Yamashita H. Photocatalytic production of hydrogen peroxide through selective two-electron reduction of dioxygen utilizing amine-functionalized MIL-125 deposited with nickel oxide nanoparticles. Chem Commun 2018;54(67):9270‒3. link1

[12] Wu Q, Cao J, Wang X, Liu Y, Zhao Y, Wang H, et al. A metal-free photocatalyst for highly efficient hydrogen peroxide photoproduction in real seawater. Nat Commun 2021;12:483. link1

[13] Hou H, Zeng X, Zhang X. Production of hydrogen peroxide by photocatalytic processes. Angew Chem Int Ed Engl 2020;59(40):17356‒76. link1

[14] Shiraishi Y, Takii T, Hagi T, Mori S, Kofuji Y, Kitagawa Y, et al. Resorcinolformaldehyde resins as metal-free semiconductor photocatalysts for solar-tohydrogen peroxide energy conversion. Nat Mater 2019;18(9):985‒93. link1

[15] Xie H, Zheng Y, Guo X, Liu Y, Zhang Z, Zhao J, et al. Rapid microwave synthesis of mesoporous oxygen-doped g-C3N4 with carbon vacancies for efficient photocatalytic H2O2 production. ACS Sustain Chem Eng 2021;9(19):6788‒98. link1

[16] Wu L, An S, Song YF. Heteropolyacids-immobilized graphitic carbon nitride: highly efficient photo-oxidation of benzyl alcohol in the aqueous phase. Engineering 2021;7(1):94‒102. link1

[17] Qian X, Wu Y, Kan M, Fang M, Yue D, Zeng J, et al. FeOOH quantum dots coupled g-C3N4 for visible light driving photo-Fenton degradation of organic pollutants. Appl Catal B 2018;237:513‒20. link1

[18] Zhang J, Jing B, Tang Z, Ao Z, Xia D, Zhu M, et al. Experimental and DFT insights into the visible-light driving metal-free C3N5 activated persulfate system for efficient water purification. Appl Catal B 2021;289:120023. link1

[19] Goclon J, Winkler K. Computational insight into the mechanism of O2 to H2O2 reduction on amino-groups-containing g-C3N4. Appl Surf Sci 2018;462:134‒41. link1

[20] Kumar A, Raizada P, Hosseini-Bandegharaei A, Thakur VK, Nguyen VH, Singh P. C-, N-vacancy defect engineered polymeric carbon nitride towards photocatalysis: viewpoints and challenges. JMater ChemAMater Energy Sustain 2021;9:111‒53. link1

[21] Yang C, Xue Z, Qin J, Sawangphruk M, Zhang X, Liu R. Heterogeneous structural defects to prompt charge shuttle in g-C3N4 plane for boosting visible-light photocatalytic activity. Appl Catal B 2019;259:118094. link1

[22] Yu H, Shi R, Zhao Y, Bian T, Zhao Y, Zhou C, et al. Alkali-assisted synthesis of nitrogen deficient graphitic carbon nitride with tunable band structures for efficient visible-light-driven hydrogen evolution. Adv Mater 2017;29(16):1605148. link1

[23] Tian J, Wang D, Li S, Pei Y, Qiao M, Li ZH, et al. KOH-assisted band engineering of polymeric carbon nitride for visible light photocatalytic oxygen reduction to hydrogen peroxide. ACS Sustain Chem Eng 2020;8(1):594‒603. link1

[24] Zhang G, Lin L, Li G, Zhang Y, Savateev A, Zafeiratos S, et al. Ionothermal synthesis of triazine-heptazine-based copolymers with apparent quantum yields of 60% at 420 nm for solar hydrogen production from “sea water.” Angew Chem Int Ed Engl 2018;57(30):9372‒6. link1

[25] Moon G, Fujitsuka M, Kim S, Majima T, Wang X, Choi W. Eco-friendly photochemical production of H2O2 through O2 reduction over carbon nitride frameworks incorporated with multiple heteroelements. ACS Catal 2017;7(4):2886‒95. link1

[26] Zhang P, Tong Y, Liu Y, Vequizo JJM, Sun H, Yang C, et al. Heteroatom dopants promote two-electron O2 reduction for photocatalytic production of H2O2 on polymeric carbon nitride. Angew Chem Int Ed 2020;59(37):16209‒17. link1

[27] Wu S, Yu H, Chen S, Quan X. Enhanced Photocatalytic H2O2 production over carbon nitride by doping and defect engineering. ACS Catal 2020;10(24):14380‒9. link1

[28] Feng C, Tang L, Deng Y, Wang J, Luo J, Liu Y, et al. Synthesis of leaf-vein-like g-C3N4 with tunable band structures and charge transfer properties for selective photocatalytic H2O2 evolution. Adv Funct Mater 2020;30(39):2001922. link1

[29] Xie Y, Li Y, Huang Z, Zhang J, Jia X, Wang XS, et al. Two types of cooperative nitrogen vacancies in polymeric carbon nitride for efficient solar-driven H2O2 evolution. Appl Catal B 2020;265:118581. link1

[30] Nguyen CC, Do TO. Engineering the high concentration of N3C nitrogen vacancies toward strong solar light-driven photocatalyst-based g-C3N4. ACS Appl Energy Mater 2018;1(9):4716‒23. link1

[31] Duan Y, Wang Y, Gan L, Meng J, Feng Y, Wang K, et al. Amorphous carbon nitride with three coordinate nitrogen (N3C) vacancies for exceptional NOx abatement in visible light. Adv Energy Mater 2021;11(19):2004001. link1

[32] Furukawa S, Shishido T, Teramura K, Tanaka T. Photocatalytic oxidation of alcohols over TiO2 covered with Nb2O5. ACS Catal 2012;2(1):175‒9. link1

[33] Miao W, Liu Y, Chen X, Zhao Y, Mao S. Tuning layered Fe-doped g-C3N4 structure through pyrolysis for enhanced fenton and photo-fenton activities. Carbon 2020;159:461‒70. link1

[34] Yuan D, Ding J, Zhou J, Wang L, Wan H, Dai WL, et al. Graphite carbon nitride nanosheets decorated with ZIF-8 nanoparticles: effects of the preparation method and their special hybrid structures on the photocatalytic performance. J Alloys Compd 2018;762:98‒108. link1

[35] Zhang H, Jia L, Wu P, Xu R, He J, Jiang W. Improved H2O2 photogeneration by KOH-doped g-C3N4 under visible light irradiation due to synergistic effect of N defects and K modification. Appl Surf Sci 2020;527:146584. link1

[36] Shen JS, Cai QG, Jiang YB, Zhang HW. Anion-triggered melamine based selfassembly and hydrogel. Chem Commun 2010;46:6786‒8. link1

[37] Huang ZF, Song J, Pan L, Wang Z, Zhang X, Zou JJ, et al. Carbon nitride with simultaneous porous network and O-doping for efficient solar-energy-driven hydrogen evolution. Nano Energy 2015;12:646‒56. link1

[38] Dong F, Ou M, Jiang Y, Guo S, Wu Z. Efficient and durable visible light photocatalytic performance of porous carbon nitride nanosheets for air purification. Ind Eng Chem Res 2014;53(6):2318‒30. link1

[39] Chen Z, Sun P, Fan B, Liu Q, Zhang Z, Fang X. Textural and electronic structure engineering of carbon nitride via doping with p-deficient aromatic pyridine ring for improving photocatalytic activity. Appl Catal B 2015;170‒171:10‒6. link1

[40] Shi L, Yang L, Zhou W, Liu Y, Yin L, Hai X, et al. Photoassisted construction of holey defective g-C3N4 photocatalysts for efficient visible-light-driven H2O2 production. Small 2018;14(9):1703142. link1

[41] Cheng J, Hu Z, Lv K, Wu X, Li Q, Li Y, et al. Drastic promoting the visible photoreactivity of layered carbon nitride by polymerization of dicyandiamide at high pressure. Appl Catal B 2018;232:330‒9. link1

[42] Miao W, Liu Y, Wang D, Du N, Ye Z, Hou Y, et al. The role of Fe‒Nx single-atom catalytic sites in peroxymonosulfate activation: formation of surface-activated complex and non-radical pathways. Chem Eng J 2021;423:130250. link1

[43] Savateev A, Pronkin S, Epping JD, Willinger MG, Wolff C, Neher D, et al. Potassium poly(heptazine imides) from aminotetrazoles: shifting band gaps of carbon nitride-like materials for more efficient solar hydrogen and oxygen evolution. Chem Cat Chem 2017;9(1):167‒74. link1

[44] Wang Y, Meng D, Zhao X. Visible-light-driven H2O2 production from O2 reduction with nitrogen vacancy-rich and porous graphitic carbon nitride. Appl Catal B 2020;273:119064. link1

[45] Deng Y, Tang L, Zeng G, Zhu Z, Yan M, Zhou Y, et al. Insight into highly efficient simultaneous photocatalytic removal of Cr(VI) and 2,4-diclorophenol under visible light irradiation by phosphorus doped porous ultrathin g-C3N4 nanosheets from aqueous media: performance and reaction mechanism. Appl Catal B 2017;203:343‒54. link1

[46] Zhu X, Yang J, Zhu X, Yuan J, Zhou M, She X, et al. Exploring deep effects of atomic vacancies on activating CO2 photoreduction via rationally designing indium oxide photocatalysts. Chem Eng J 2021;422:129888. link1

[47] Liu J, Liu Y, Liu N, Han Y, Zhang X, Huang H, et al. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway. Science 2015;347(6225):970‒4. link1

[48] Niu P, Yin LC, Yang YQ, Liu G, Cheng HM. Increasing the visible light absorption of graphitic carbon nitride (melon) photocatalysts by homogeneous selfmodification with nitrogen vacancies. Adv Mater 2014;26(47):8046‒52. link1

[49] Xiong J, Li X, Huang J, Gao X, Chen Z, Liu J, et al. CN/rGO@BPQDs high-low junctions with stretching spatial charge separation ability for photocatalytic degradation and H2O2 production. Appl Catal B 2020;266:118602. link1

[50] Liu Y, Xie C, Li H, Chen H, Zou T, Zeng D. Improvement of gaseous pollutant photocatalysis with WO3/TiO2 heterojunctional-electrical layered system. J Hazard Mater 2011;196:52‒8. link1

[51] Zhang J, Zheng L, Wang F, Chen C, Wu H, Leghari SAK, et al. The critical role of furfural alcohol in photocatalytic H2O2 production on TiO2. Appl Catal B 2020;269:118770. link1

[52] Wang R, Pan K, Han D, Jiang J, Xiang C, Huang Z, et al. Solar-driven H2O2 generation from H2O and O2 using earth-abundant mixed-metal oxide@carbon nitride photocatalysts. ChemSusChem 2016;9(17):2470‒9. link1

[53] Zheng L, Su H, Zhang J, Walekar LS, Vafaei Molamahmood H, Zhou B, et al. Highly selective photocatalytic production of H2O2 on sulfur and nitrogen codoped graphene quantum dots tuned TiO2. Appl Catal B 2018;239:475‒84. link1

[54] Wang D, Li Q, Miao W, Liu Y, Du N, Mao S. One-pot synthesis of ultrafine NiO loaded and Ti3+ in-situ doped TiO2 induced by cyclodextrin for efficient visible-light photodegradation of hydrophobic pollutants. Chem Eng J 2020;402:126211. link1

[55] Chu C, Miao W, Li Q, Wang D, Liu Y, Mao S. Highly efficient photocatalytic H2O2 production with cyano and SnO2 co-modified g-C3N4. Chem Eng J 2022;428:132531. link1

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