The development of metal-free photocatalysts with tunable electrochemical properties has attracted widespread attention for next-generation materials innovation. Boron-doped graphitic carbon nitride (B-g-C₃N₄) stands out due to its unique electronic structure and photophysical characteristics; however, its limited processability and difficulty in thin-film fabrication hinder practical implementation. In this work, we report a facile “grafting-to” strategy, where visible-light irradiation is employed to covalently immobilize poly(methyl methacrylate) (PMMA) onto B-g-C₃N₄. The resulting PMMA/B-g-C₃N₄ composite films exhibit enhanced stability, processability, and photo-functionalization, enabling their direct integration into electrochemical impedance spectroscopy (EIS) platforms. The synergistic interaction between PMMA and B-g-C₃N₄ not only improves charge transfer dynamics but also amplifies optical response, representing a significant step toward functional thin-film architectures. This study provides a promising route for advancing boron-doped carbon nitride in electrochemical and optoelectronic applications, paving the way for sustainable, high-performance materials development.
AmorinLHSuzukiVYde PaulaNH, et al.Electronic, structural, optical, and photocatalytic properties of graphitic carbon nitride. New J Chem2019; 43: 13647–13653.
2.
MelissenSLe BahersTSteinmannSN, et al.“Relationship between carbon nitride structure and exciton binding energies: a DFT perspective”. J Phys Chem C2015; 119: 25188–25196.
3.
LinWHongWSunL, et al.“Bioinspired mesoporous chiral nematic graphitic carbon nitride photocatalysts modulated by polarized light”. ChemSusChem2018; 11: 114–119.
4.
La PortaFAAndresJVismaraMVG, et al.“Correlation between structural and electronic order-disorder effects and optical properties in ZnO nanocrystals”. J Mater Chem C2014; 2: 10164–10174.
5.
OstaciR-VDamironDGrohensY, et al.Brushes grafted to passivated silicon substrates using click chemistry. Polym Chem2007; 2: 348–354.
6.
OstaciR-VDamironDCapponiS, et al.“Polymer brushes grafted to ⃞passivated⃞ Silicon substrates using click chemistry”. Langmuir24: 2732–2739. (2008).
7.
SenaratneWAndruzziLOberCK. “Self-assembled monolayers and polymer brushes in biotechnology: current applications and future perspectives”. Biomacromolecules6: 2427–2448. (2005).
8.
GoujonFMalfreytPTildesleyDJ. The compression of polymer brushes under shear: the friction coefficient as a function of compression, shear rate and the properties of the solvent. Mol Phys2005; 103: 2285–2675.
9.
LiaoW-PElliottIGFallerR, et al.Normal and shear interactions between high grafting density polymer brushes grown by atom transfer radical polymerization. Soft Matter2013; 9: 5753–5761.
10.
LiXBuJYangS, et al.Surface modification of C3N4 through oxygen-plasma treatment: a simple way toward excellent hydrophilicity. ACS Appl Mater Interfaces2016; 8: 31419–31425.
11.
OliveiraLHDe MouraAPLa PortaFA, et al. “Influence of Cu-doping on the structural and optical properties of CaTiO3 powders”. Mater Res Bull2016; 81: 1–9.
12.
PottkerWEOnoRCobosMA, et al.Influence of order-disorder effects on the magnetic and optical properties of NiFe2O4 nanoparticles. Ceram Int2018; 44: 17290–17297.
13.
ZhangYMoriTNiuL, et al.Non-covalent doping of graphitic carbon nitride polymer with graphene: controlled electronic structure and enhanced optoelectronic conversion. Energy & Environ Sci2011; 4: 4517–4521.
14.
ZhangJZhangGChenX, et al.Co-monomer control of carbon nitride semiconductors to optimize hydrogen evolution with visible light. Angew Chemie Int Ed2012; 51: 3183–3187.
15.
ZhangJChenXTakanabeK, et al.Synthesis of a carbon nitride structure for visible-light catalysis by copolymerization. Angew Chemie-International Ed2010; 49: 441–444.
16.
DongGZhangYPanQ, et al.Fantastic graphitic carbon nitride (g-C3N4) material: electronic structure, photocatalytic and photoelectronic properties. J Photochem Photobiol C Photochem Rev20: 33–50. (2014).
17.
LiuNLiTZhaoZ, et al. “From triazine to heptazine: origin of graphitic carbon nitride as a photocatalyst”. ACS omega5: 12557–12567. (2020).
18.
WangYZhangMWangL, et al.Graphitic carbon nitride emitter: From structural modification to optoelectronics applications. Adv Opt Mater2023; 11: 2301547.
19.
ZhangYPanQChaiG, et al.Synthesis and luminescence mechanism of multicolor-emitting g-C3N4 nanopowders by low temperature thermal condensation of melamine. Sci Rep2013; 3: 1943.
20.
WangBBZhuMKOstrikovK, et al.Conversion of vertically-aligned boron nitride nanowalls to photoluminescent CN compound nanorods: efficient composition and morphology control via plasma technique. Carbon N Y2016; 109: 352–362.
21.
TahirMSherrynaAKhanAA, et al.Defect engineering in graphitic carbon nitride nanotextures for energy efficient solar fuels production: a review. Energy \& Fuels2022; 36: 8948–8977.
22.
NabeelMIHussainDAhmadN, et al.Recent advancements in the fabrication and photocatalytic applications of graphitic carbon nitride-tungsten oxide nanocomposites. Nanoscale Adv2023; 5: 5214–5255.
23.
ReddyKRReddyCHVNadagoudaMN, et al.Polymeric graphitic carbon nitride (g-C3N4)-based semiconducting nanostructured materials: synthesis methods, properties and photocatalytic applications. J Environ Manage2019; 238: 25–40.
24.
PatnaikSMarthaSParidaKM. An overview of the structural, textural and morphological modulations of gC 3 N 4 towards photocatalytic hydrogen production. Rsc Adv2016; 6: 46929–46951.
25.
VelusamyDBHaqueMAParidaMR, et al.2D organic–inorganic hybrid thin films for flexible UV–visible photodetectors. Adv Funct Mater2017; 27: 1605554.
26.
Li andYDuH. Engineering graphitic carbon nitride for next-generation photodetectors: a mini review. RSC Adv2023; 13: 25968–25977.
27.
HohHYZhangYZhongYL, et al.Harnessing the potential of graphitic carbon nitride for optoelectronic applications. Adv Opt Mater2021; 9: 2100146.
28.
LiuPSunYWangS, et al.Two dimensional graphitic carbon nitride quantum dots modified perovskite solar cells and photodetectors with high performances. J Power Sources 2020; 451, 227825.
29.
ChaubeySYadavRKKimTW, et al.Fabrication of graphitic carbon nitride-based film: an emerged highly efficient catalyst for direct C-H arylation under solar light. Chinese J Chem2021; 39: 633–639.
30.
Babu GanganboinaADung NguyenMHien Luong NguyenT, et al.Boron and phosphorus co-doped one-dimensional graphitic carbon nitride for enhanced visible-light-driven photodegradation of diclofenac. Chem Eng J2021; 425: 131520.
31.
GautamHYadavRKMishraS, et al.Crafting in situ boron and selenium-doped carbon nitride nanosheets for turbocharged benzaldehyde to benzyl alcohol under solar spectrum. Diam Relat Mater2024; 146: 111140.
32.
InuiTSatoEMatsumotoA. Pressure-Sensitive adhesion system using acrylate block copolymers in response to photoirradiation and postbaking as the dual external stimuli for on-demand dismantling. ACS Appl Mater Interfaces2012; 4: 2124–2132.
33.
CaoQKumruBAntoniettiM, et al.“Grafting polymers onto carbon nitride via visible-light-induced photofunctionalization”. Macromolecules52: 4989–4996. (2019).
34.
de Castro MonsoresKGda SilvaAOSant’d, et al.Influence of ultraviolet radiation on polymethylmethacrylate (PMMA). J Mater Res Technol2019; 8: 3713–3718.
35.
PatnaikSSahooDPParidaK. Nanocomposites for visible light-induced photocatalysis” cham. In: KhanMMPradhanDSohnY (eds) Nanocomposites of g-C3N4 with carbonaceous $π$-conjugated/polymeric materials towards visible light-induced photocatalysts. Heidelberg: Springer International Publishing, 2017, pp.251–294.
36.
LiangCCuiXDongW, et al.Enhanced non-linear optical properties of porphyrin-based polymers covalently functionalized with graphite phase carbon nitride. Front Chem2022; 10: 1–12.
37.
YeomD-YJeonWTuNDK, et al.High-concentration boron doping of graphene nanoplatelets by simple thermal annealing and their supercapacitive properties. Sci Rep2015; 5: 9817.
38.
GeniselMFUddinMNSayZ, et al.Bias in bonding behavior among boron, carbon, and nitrogen atoms in ion implanted a-BN, a-BC, and diamond like carbon films. J Appl Phys2011; 110: 074906.
39.
VidyasagarDGhugalSGUmareSS, et al.Extended π-conjugative n-p type homostructural graphitic carbon nitride for photodegradation and charge-storage applications. Sci Rep2019; 9: 1–10.
40.
LiuSZhouSHuC, et al.Coupling graphitic carbon nitrides with tetracarboxyphenyl porphyrin molecules through π–π stacking for efficient photocatalysis. J Mater Sci Mater Electron2020; 31: 10677–10688.
41.
Newbury andDERitchieNWM. Elemental mapping of microstructures by scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDS): extraordinary advances with the silicon drift detector (SDD). J Anal At Spectrom2013; 28: 973–988.
42.
Monga andDBasuS. Tuning the photocatalytic/electrocatalytic properties of MoS2/MoSe2heterostructures by varying the weight ratios for enhanced wastewater treatment and hydrogen production. RSC Adv2021; 11: 22585–22597.
43.
SwarnkarNYadavRKSinghS, et al.Highly selective in-situ prepared g-C3N4/P-B composite photocatalyst for direct C-H bond arylation and NADH regeneration cofactor under solar light. J Chem Sci2023; 135: 29.
44.
JaysivaGManavalanSChenSM, et al.Mon nanorod/Sulfur-doped graphitic carbon nitride for electrochemical determination of chloramphenicol. ACS Sustain Chem Eng2020; 8: 11088–11098.
45.
ShinagawaTGarcia-EsparzaATTakanabeK. Insight on Tafel slopes from a microkinetic analysis of aqueous electrocatalysis for energy conversion. Sci Rep2015; 5: 13801.
46.
van der HeijdenOParkSVosRE, et al.Tafel slope plot as a tool to analyze electrocatalytic reactions. ACS Energy Lett2024; 9: 1871–1879.
47.
ShahinRYadavRKVermaRK, et al.Sein-EY marvels: effortless elegance in crafting flexible film photocatalysts for formic acid production from CO2 and cyclization of thioamides in the air’s embrace. New J Chem2024; 48: 12102–12111.
48.
ThaweesakSWangSLyuM, et al.Boron-doped graphitic carbon nitride nanosheets for enhanced visible light photocatalytic water splitting. Dalt Trans2017; 46: 10714–10720.
49.
ÂngeloJMagalhãesPAndradeL, et al.Characterization of TiO2-based semiconductors for photocatalysis by electrochemical impedance spectroscopy. Appl Surf Sci2016; 387: 183–189.
