Preparation of Boron-Doped Graphitic Carbon Nitride and Its Photocatalytic in Photocatalytic Water Splitting for Hydrogen Production

doi:10.12422/j.issn.1006-396X.2026.01.004

Abstract

Abstract:

The dual?carbon strategy highlights the urgent need to develop efficient photocatalytic hydrogen production technologies. Graphitic carbon nitride (g?C?N?) has attracted wide attention due to its low cost and excellent stability, but it suffers from insufficient visible light absorption and rapid carrier recombination, which severely restricts its hydrogen production performance. To overcome these issues, we successfully prepared boron-doped g?C₃N₄ （BCN） using a H₃BO₃?assisted segmented temperature?controlled calcination strategy, with boric acid as the boron source precursor. The effects of boron doping on the band structure and photoelectric properties of g?C₃N₄ were systematically investigated through various photoelectric characterization techniques. The results demonstrate that an appropriate level of boron doping effectively modulates the electronic structure of g-C₃N₄, enhancing its visible light absorption and improving the separation efficiency of photogenerated carriers. Specifically, the BCN?2∶5 sample (with a mass ratio of H?BO? to g?C?N? of 2∶5) achieves a hydrogen evolution rate of up to 1 507 μmol/(g·h) under visible light irradiation. This study offers valuable insights and guidance for the design of highly efficient doped g?C₃N₄ photocatalysts.

Key words: g-C₃N₄, Boron doping, Porous structure, Band gap, Carrier separation, Photocatalytic hydrogen production

摘要：

“双碳”战略对发展高效光催化制氢技术提出了迫切需求。石墨相氮化碳（g-C₃N₄）因成本低、稳定性好而备受关注，但存在可见光吸收能力不足及载流子快速复合等问题，严重制约了其产氢性能。通过以硼酸（H₃BO₃)为硼源的“H₃BO₃协同分段控温煅烧”策略，成功制备出硼掺杂g-C₃N₄（BCN）；通过多种光电表征技术，系统探究了硼掺杂对g-C₃N₄能带结构与光电性能的影响。结果表明，适量的硼掺杂可有效调控g-C₃N₄的电子结构，提升其可见光吸收能力与光生载流子的分离效率；BCN-2∶5（H₃BO₃与CN的质量比为2∶5)样品在可见光下的析氢速率达1 507 μmol/（g·h）。这项研究对高效掺杂g-C?N?光催化剂的设计具有重要的指导意义。

关键词: g-C₃N₄, 硼掺杂, 多孔结构, 带隙, 载流子分离, 光催化产氢

CLC Number:

TQ426

Jipeng FAN, Silu HE, Jing ZOU, Haitao WANG. Preparation of Boron-Doped Graphitic Carbon Nitride and Its Photocatalytic in Photocatalytic Water Splitting for Hydrogen Production[J]. Journal of Petrochemical Universities, 2026, 39(1): 27-35.

凡纪鹏, 贺思璐, 邹菁, 王海涛. 硼掺杂石墨相氮化碳的制备及其光解水制氢性能研究[J]. 石油化工高等学校学报, 2026, 39(1): 27-35.

0
/ / Recommend

Add to citation manager EndNote|Ris|BibTeX

URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.01.004

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I1/27

Figures/Tables 12

Fig.1 Synthesis process of BCN

Fig.2 FT-IR absorption spectra, XRD patterns, and XPS spectra of CN and BCN

Fig.3 Nitrogen adsorption-desorption isotherms and pore size distributions curves of CN and BCN

Fig.4 SEM images of CN and BCN

Fig.5 UV-Vis absorption spectra and Tauc plots of CN and BCN

Fig.6 Mott-Schottky curves and band structure diagrams of CN and BCN at different frequencies

Fig.7 Electrochemical impedance spectra and linear sweep voltammetry curves of CN and BCN

Fig.8 Photocatalytic water splitting hydrogen production performance of BCN with different boron doping amounts

Fig.9 Comparison of photocatalytic water splitting hydrogen production performance between BCN-2∶5 and CN

Fig.10 The hydrogen production efficiency of BCN for 24 hours

Table 1 Comparison of photocatalytic hydrogen evolution rates between BCN-2∶5 and reported non-metal-doped g-C3N?

掺杂元素	反应条件			产氢速率/ （μmol·g⁻¹·h⁻¹）	参考文献
掺杂元素	光照条件	φ（TEOA）/%	w（Pt）/%	产氢速率/ （μmol·g⁻¹·h⁻¹）	参考文献
Br	300 W	10	1	687.0	[25]
C	300 W	10	3	1 224.0	[26]
F	300 W	10	3	1 298.0	[27]
O	300 W	10	3	1 492.0	[28]
P	300 W	10	3	1 093.0	[29]
P	300 W	10	3	256.4	[30]
P	300 W	10	3	50.6	[31]
P	300 W	10	3	1 146.8	[32]
S	300 W	10	3	572.0	[33]
P	300 W	10	3	1 507.0	本文

Fig.11 Mechanism diagram of the photocatalytic H2 production of CN and BCN

References 38

[1]	XIA K Q， WU D， FU J M， et al. Tunable output performance of triboelectric nanogenerator based on alginate metal complex for sustainable operation of intelligent keyboard sensing system［J］. Nano Energy， 2020， 78： 105263.
[2]	邵志刚，衣宝廉. 氢能与燃料电池发展现状及展望［J］. 中国科学院院刊， 2019， 34（4）： 469-477.
	SHAO Z G， YI B L. Developing trend and present status of hydrogen energy and fuel cell development［J］. Bulletin of the Chinese Academy of Sciences， 2019， 34（4）： 469-477.
[3]	MALLICK P， SAHOO S K， SATPATHY S K. Different strategies to improve photocatalytic activity of graphitic carbon nitride（g-C₃N₄） semiconductor nanomaterials for hydrogen generation［J］. Journal of Molecular Liquids， 2024， 406： 125071.
[4]	谢磊，刘帅，孙有为，等. 石墨相氮化碳光催化剂的研究进展［J］. 石油化工高等学校学报， 2021， 34（6）： 27-34.
	XIE L， LIU S， SUN Y W， et al. Research progress of graphite carbon nitride photocatalyst［J］. Journal of Petrochemical Universities， 2021， 34（6）： 27-34.
[5]	NAGELLA S R， VIJITHA R， RAMESH NAIDU B， et al. Benchmarking recent advances in hydrogen production using
	g-C₃N₄-based photocatalysts［J］. Nano Energy， 2023， 111： 108402.
[6]	陆亚男，邹晓莉，王磊，等. ZnIn₂S₄/g-C₃N₄/MoS₂三元异质结的制备及其光催化产氢性能［J］. 聊城大学学报（自然科学版）， 2023， 36（6）： 57-64.
	LU Y N， ZOU X L， WANG L， et al. Preparation and hydrogen evolution properties of ZnIn₂S₄/g-C₃N₄/MoS₂ ternary heterojunctions［J］. Journal of Liaocheng University （Natural Science Edition）， 2023， 36（6）： 57-64.
[7]	LI D D， DONG Y M， WANG G L， et al. Controllable photochemical synthesis of amorphous Ni（OH）₂ as hydrogen production cocatalyst using inorganic phosphorous acid as sacrificial agent［J］. Chinese Journal of Catalysis， 2020， 41（5）： 889-897.
[8]	张彭义，余刚，蒋展鹏. 半导体光催化剂及其改性技术进展［J］. 环境科学进展， 1997， 5（3）： 1-10.
	ZHANG P Y， YU G， JIANG Z P. Review of semiconductor photocatalyst and its modification［J］. Advances in Environmental Science， 1997， 5（3）： 1-10.
[9]	JIANG Z， LIU D S， LI C H， et al. Signature of p-type semiconductor features in paper-based back gate metal-organic framework thin-film transistors［J］. Applied Physics Letters， 2020， 117（9）： 093303.
[10]	WANG X N， WU L， WANG Z W， et al. C/N vacancy co-enhanced visible-light-driven hydrogen evolution of g-C₃N₄ nanosheets through controlled He⁺ion irradiation［J］. Solar RRL， 2019， 3（4）： 1800298.
[11]	FAN J P， WANG H T， SUN W， et al. Recent developments and perspectives of Ti-based transition metal carbides/nitrides for photocatalytic applications： A critical review［J］. Materials Today， 2024， 76： 110-135.
[12]	WANG H T， FAN J P， ZOU J， et al. Sulfur-doped g-C₃N₄/V₂C MXene schottky junctions for superior photocatalytic H₂ evolution［J］. Journal of Materials Chemistry A， 2024， 12（44）： 30429-30441.
[13]	REHMAN Z U， BILAL M， REHMAN S U， et al. Boron doped g-C₃N₄ porous nanosheets to increase electron-hole pair generation for excellent photocatalytic H₂ production and CO₂ reduction［J］. Separation and Purification Technology， 2025， 354（Part 8）： 129535.
[14]	KHANBEIKI O， GHASEMI S， EMADI H. Preparation of NiFe layered double hydroxide/graphitic carbon nitride nanocomposite for enhanced sonocatalytic deterioration of tetracycline hydrochloride［J］. Diamond and Related Materials， 2024， 143： 110852.
[15]	荆慧娟，栾梦格，叶灏霖，等. 超分子自组装法制备钒掺杂的g-C₃N₄纳米管及其光催化制氢性能［J］. 聊城大学学报（自然科学版）， 2025， 38（6）： 927-934.
	JING H J， LUAN M G， YE H L， et al. Preparation of vanadium-doped g-C₃N₄ nanotubes via supramolecular self-assembly method and its photocatalytic hydrogen production performance［J］. Journal of Liaocheng University （Natural Science Edition）， 2025， 38（6）： 927-934.
[16]	XIAO Y T， GUO S E， TIAN G H， et al. Synergetic enhancement of surface reactions and charge separation over holey C₃N₄/TiO₂ 2D heterojunctions［J］. Science Bulletin， 2021， 66（3）： 275-283.
[17]	GUO R F， LIU Z H， GU Q， et al. BCN/Bi₂O₂［BO₂（OH） hollow hemisphere nanocomposite with 2D-2D Z-scheme heterostructure for excellent photocatalytic water purification［J］. Applied Surface Science， 2025， 701： 163288.
[18]	ZHANG M L， YANG L， WANG Y J， et al. High yield synthesis of homogeneous boron doping C₃N₄ nanocrystals with enhanced photocatalytic property［J］. Applied Surface Science， 2019， 489： 631-638.
[19]	CHEN X X， CHEN C Z， ZANG J Y. Construction of B-doped g-C₃N₄/MoO₃ photocatalyst to promote light absorption and Z-scheme charge transfer［J］. Diamond and Related Materials， 2023， 132： 109606.
[20]	杜恭贺. 石墨烯及其掺杂体系电子结构性质的理论研究［D］. 西安：西北大学， 2010.
[21]	LIU K N， WANG X， LI C， et al. Facile fabrication metal Cu-decorated g-C₃N₄ photocatalyst with schottky barrier for efficient pollutant elimination［J］. Diamond and Related Materials， 2022， 126： 109116.
[22]	DHANARAMAN E， VERMA A， ANAND P， et al. Influence of B-atom in g-C₃N₄ matrix to enhance the photocatalytic dinitrogen to ammonia conversion［J］. Journal of Environmental Chemical Engineering， 2023， 11（6）： 111323.
[23]	陈金宝，李开宁，黎小芳，等. 结晶氮化碳的制备与改性策略［J］. 无机化学学报， 2021， 37（10）： 1713-1726.
	CHEN J B， LI K N， LI X F， et al. Preparation and modification of crystalline carbon nitride［J］. Chinese Journal of Inorganic Chemistry， 2021， 37（10）： 1713-1726.
[24]	FAN J P， WANG H T， LIAO G D， et al. Potassium-doped g-C₃N₄/nitrogen-doped g-C₃N₄ step-scheme homojunction for enhanced H₂ evolution photocatalysis［J］. Science China Technological Sciences， 2025， 68（6）： 1620206.
[25]	YU G Y， ZHAO H T， XING C W， et al. Creation of carbon defects and in-plane holes with the assistance of NH₄Br to enhance the photocatalytic activity of g-C₃N₄［J］. Catalysis Science & Technology， 2021， 11（15）： 5349-5359.
[26]	LIU E L， LIN X， HONG Y Z， et al. Rational copolymerization strategy engineered C self-doped g-C₃N₄ for efficient and robust solar photocatalytic H₂ evolution［J］. Renewable Energy， 2021， 178： 757-765.
[27]	SUN L D， LI Y， FENG W. Gas-phase fluorination of g-C₃N₄ for enhanced photocatalytic hydrogen evolution［J］. Nanomaterials， 2021， 12（1）： 37.
[28]	ZHANG J Y， HU Y F， LI H， et al. Molecular self-assembly of oxygen deep-doped ultrathin C₃N₄ with a built-in electric field for efficient photocatalytic H₂ evolution［J］. Inorganic Chemistry， 2021， 60（20）： 15782-15796.
[29]	LIU Y F， MA Z. g-C₃N₄ modified by pyropheophorbide-a for photocatalytic H₂ evolution［J］. Colloids and Surfaces A-Physicochemical and Engineering Aspects， 2021， 615： 126128.
[30]	YANG H Y， ZHOU Y M， WANG Y Y， et al. Three-dimensional flower-like phosphorus-doped g-C₃N₄ with a high surface area for visible-light photocatalytic hydrogen evolution［J］. Journal of Materials Chemistry A， 2018， 6（34）： 16485-16494.
[31]	ZHOU Y J， ZHANG L X， LIU J J， et al. Brand new P-doped g-C₃N₄： Enhanced photocatalytic activity for H₂ evolution and Rhodamine B degradation under visible light［J］. Journal of Materials Chemistry A， 2015， 3（7）： 3862-3867.
[32]	LIU X L， GUO Y H， WANG P， et al. The synergy of thermal exfoliation and Phosphorus doping in g-C₃N₄ for improved photocatalytic H₂ generation［J］. International Journal of Hydrogen Energy， 2021， 46（5）： 3595-3604.
[33]	GUO H， SHU Z， CHEN D H， et al. One-step synthesis of S-doped g-C₃N₄ nanosheets for improved visible-light photocatalytic hydrogen evolution［J］. Chemical Physics， 2020， 533： 110714.
[34]	张金水，王博，王心晨. 石墨相氮化碳的化学合成及应用［J］. 物理化学学报， 2013， 29（9）： 1865-1876.
	ZHANG J S， WANG B， WANG X C. Chemical synthesis and applications of graphitic carbon nitride［J］. Acta Physico-Chimica Sinica， 2013， 29（9）： 1865-1876.
[35]	张力嫱，高陆玺，吕雪川，等. 铁改性石墨相氮化碳催化苯酚羟基化反应合成二酚［J］.石油学报（石油加工），2020，36（2）： 403-409.
	ZHANG L Q， GAO L X， LÜ X C. Hydroxylation of phenol to produce dihydroxybenzene catalyzed by iron modified graphitic carbon nitride ［J］. Acta Petrolei Sinica （Petroleum Processing Section）， 2020， 36（2）： 403-409.
[36]	DUAN H Q， FAN J P， LIU C， et al. Green synthesis of phosphorus-doped g-C₃N₄ as an advanced photocatalyst for H₂ evolution［J］. Nano Energy， 2025， 20（9）： 2550032.
[37]	杨文科，卢连雪，李鹏，等. 光催化材料石墨相氮化碳的合成、改性及应用［J］. 石油化工高等学校学报， 2024， 37（1）： 43-51.
	YANG W K， LU L X， LI P， et al. Synthesis， modification and application of photocatalytic material graphite phase carbon nitride［J］. Journal of Petrochemical Universities， 2024， 37（1）： 43-51.
[38]	袁瀚钦，董雯，吴兴良，等. 改性石墨相氮化碳活化过硫酸盐降解水中有机污染物的研究进展［J］. 化工环保， 2022， 42（6）： 645-653.
	YUAN H Q， DONG W， WU X L， et al. Research progress of modified graphitic carbon nitride activating persulfate for degradation of organic pollutants in water［J］. Environmental Protection of Chemical Industry， 2022， 42（6）： 645-653.