Photocatalytic H2 Generation Research Articles

Insulated π-Conjugated Azido Scaffolds for Stepwise Functionalization via Huisgen Cycloaddition on Metal Oxide Surfaces.

In organic-inorganic hybrid devices, fine interfacial controls by organic components directly affect the device performance. However, fabrication of uniformed interfaces using π-conjugated molecules remains challenging due to facile aggregation by their strong π-π interaction. In this report, a π-conjugated scaffold insulated by covalently linked permethylated α-cyclodextrin moiety with an azido group is synthesized for surface Huisgen cycloaddition on metal oxides. Fourier-transformed infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy confirm the successful immobilization of the insulated azido scaffold on ZnO nanowire array surfaces. Owing to the highly independent immobilization, the scaffold allows rapid and complete conversion of the surface azido group in Huisgen cycloaddition reactions with ethynyl-terminated molecules, as confirmed by FT-IR spectroscopy monitoring. Cyclic voltammetry analysis of modified indium tin oxide substrates shows the positive effects of cyclic insulation toward suppression of intermolecular interaction between molecules introduced by the surface Huisgen cycloaddition reactions. The utility of the scaffold for heterogeneous catalysis is demonstrated in electrocatalytic selective O2 reduction to H2O2 with cobalt(II) chlorin modified fluorine doped tin oxide electrode and photocatalytic H2 generation with iridium(III) dye-sensitized Pt-loadedTiO2 nanoparticle. These results highlight the potential of the insulated azido scaffold for a stepwise functionalization process, enabling precise and well-defined hybrid interfaces.

Improving the Photoactivity of Porphyrin-Based Metal-Organic Frameworks via Constructing [Ce-O] Active Site and Vacancy.

Defect engineering of metal-organic frameworks (MOFs) is a versatile approach to tailoring their electronic structures and photocatalytic performance. Herein, Ce-based porphyrin MOFs (CMFs) featuring controlled structural defects were successfully prepared using a simple acid modulation strategy to drive the photocatalytic H2 generation. The [Ce-O] unit serves as the active site via a ligand-to-metal charge transfer process, which has been confirmed by in situ XPS analysis. Abundant exposed coordinatively unsaturated Ce-O centers are beneficial for the adsorption and activation of water molecules, which is an important factor for improving the photocatalytic performance of the synthesized defective MOFs. In addition, optical and electrochemical experiments indicate that CMFs with more oxygen vacancies possess higher charge separation efficiency. As a result, the optimized CMF(Zn)-200 sample afforded high stability and activity in the H2 generation (up to 1603.3 μmol·g-1·h-1 under cocatalyst-free conditions) and tetracycline hydrochloride removal efficiency (97%), which was 8.45 and 97 times higher than that of pure meso-tetra(4-carboxyphenyl)porphine. This study demonstrates that effective structural modulation and defect introduction can improve the activity and stability of PMOF-based photocatalysts.

Accelerated Charge Transfer through Interface Chemical Bonds in MoS2/TiO2 for Photocatalytic Conversion of Lignocellulosic Biomass to H2.

Solar photocatalytic H2 production from lignocellulosic biomass has attracted great interest, but it suffers from low photocatalytic efficiency owing to the absence of highly efficient photocatalysts. Herein, we designed and constructed ultrathin MoS2-modified porous TiO2 microspheres (MT) with abundant interface Ti-S bonds as photocatalysts for photocatalytic H2 generation from lignocellulosic biomass. Owing to the accelerated charge transfer related to Ti-S bonds, as well as the abundant active sites for both H2 and ●OH generation, respectively, related to the high exposed edge of MoS2 and the large specific surface area of TiO2, MT photocatalysts demonstrate good performance in the photocatalytic conversion of α-cellulose and lignocellulosic biomass to H2. The highest H2 generation rate of 849 μmol·g-1·h-1 and apparent quantum yield of 4.45% at 380 nm was achieved in α-cellulose aqueous solution for the optimized MT photocatalyst. More importantly, lignocellulosic biomass of corncob, rice hull, bamboo, polar wood chip, and wheat straw were successfully converted to H2 over MT photocatalysts with H2 generation rate of 10, 19, 36, 29, and 8 μmol·g-1·h-1, respectively. This work provides a guiding design approach to develop highly active photocatalysts via interface engineering for solar H2 production from lignocellulosic biomass.

A S-scheme 0D/2D heterojunction formed by decorating Cd0.5Zn0.5S nanoparticles on Cu2MoS4 plates for efficient photocatalytic hydrogen generation

Rationally designing a Step-scheme (S-scheme) hetero-structured photocatalyst with high redox capability and separation efficiency of photoinduced carriers is considered as an attractive approach to address the shortcomings of single component and traditional hetero-structured photocatalyst. Herein, enlightened by the predictions of density functional theory (DFT), a unique S-scheme heterojunction photocatalyst was successfully fabricated by incorporating zero-dimensional (0D) Cd0.5Zn0.5S (CZS) on two-dimensional (2D) lamellar Cu2MoS4 (CMS) plates via a facile coprecipitation method, which substantially enhances the photocatalytic activity for hydrogen (H2) generation. CZS nanoparticles deposited on the surface of CMS nanoplates play a crucial role in creating highly intimate heterojunction interfaces and abundant exposed reaction sites, laying the foundation for improved photocatalytic performance. Furthermore, the significant difference in Fermi levels and band structures between CZS and CMS result in the formation of the internal electric field (IEF) and energy band bending at the interface of the heterojunction. This S-scheme charge transfer path enables 0D/2D CZS/CMS heterojunction possesses an exceptional capacity to maintain the robust redox potential and boosts the separation efficiency of light-induced carriers, as verified by DFT calculations and energy band structure analyses. As expected, the optimal heterojunction exhibits a satisfactory H2 generation rate of 13.1 mmol·g-1·h−1, which is nearly 7.7-fold higher than that of individual CZS. This study is expected to inspire the design of morphology-controlled hetero-structured photocatalyst with S-scheme charge transfer route for photocatalytic H2 generation.

CuGaS2@NH2-MIL-125(Ti) nanocomposite: Unveiling a promising catalyst for photocatalytic hydrogen generation

The development of efficient nanocomposites represents a promising strategy for enhancing the transfer and separation of photogenerated carriers within metal-organic frameworks (MOFs) for photocatalytic H2 generation. In this study, we report, for the first time, the successful fabrication of a novel CuGaS2@NH2-MIL-125(Ti) nanocomposite in a two-step synthesis, consisting of octahedral NH2-MIL-125(Ti) metal-organic frameworks interspersed with flat hexagonal plates of CuGaS2. The CuGaS2@NH2-MIL-125(Ti) nanocomposite effectively mitigates the recombination rate of photogenerated electron-hole pairs. Notably, the most active CuGaS2@NH2-MIL-125(Ti) composite (containing 30 wt% CuGaS2) achieves a remarkable hydrogen generation rate of 965.07 μmol/gcat, surpassing the performance of NH2-MIL-125(Ti) and CuGaS2 by approximately 83 and 144 times, respectively. Additionally, the apparent quantum efficiency for the most active material at a wavelength of 380 nm is 9.07%. This study provides valuable insights into the design of efficient I-III-VI2 compound-MOF nanocomposites for H2 generation applications.

Constructing multifunctional novel noble-metal free NiS/ZnS/g-C3N4 ternary nanocomposites for highly active superior photocatalytic water splitting

Ultrasound-assisted wet-impregnation approach and cation-exchange hydrothermal method are employed effectively to develop the ternary nanocomposites NiS/ZnS/g-C3N4 (NZ-CN) with promising photocatalytic hydrogen (H2) generation activity. Several analytical techniques are utilized to characterize the as-synthesized NiS/ZnS/g-C3N4 nanocomposites to study their physical and chemical characteristics. The H2 production activity of the synthesized photocatalysts was tested using a 250 W halogen lamp with Na2S (0.25 M) and Na2SO3 (0.35 M) as sacrificial reagents. The optimized NZ-CN7.5% (3% NiS/ZnS/7.5% g-C3N4) catalyst displayed an exceptional H₂ generation rate of 8624 μmol h⁻1 g⁻1, exceeding both, pristine g-C3N4 (by 22.1 times) and 3% NiS/ZnS (by 3 times). This represents the highest reported rate of H₂ evolution for a graphitic carbon nitride (g-C3N4) based ternary nanocomposite under simulated solar radiation. By reusing the used NZ-CN7.5% (3% NiS/ZnS/7.5% g-C3N4) photocatalyst in four consecutive runs, the stability of the catalyst was investigated, and their individual activity in the H2 production activity was assessed. This study provides valuable insights for designing efficient noble metal-free g–C3N4–based photocatalysts, which can significantly contribute to the transition to solar-driven hydrogen generation. Further, we proposed a plausible mechanism for the photocatalytic H2 generation process over the NiS/ZnS/g-C3N4 photocatalyst.

Directionally charging d-orbital electron of Mo2C MXene via in-situ coupled MoSe2 nanosheets for exceptional photocatalytic H2 generation

Mo2C MXene as a promising noble-metal-free cocatalyst has attracted considerable attention in the domain of photocatalytic H2 evolution due to its unique 2D layered structure, outstanding metallic conductivity, and Pt-like d-band electronic structure. However, the plentiful −F terminal groups with high electronegativity of Mo2C MXene (referred as Mo2CFx) owing to the residue of F-containing etchants lead to strong interaction between active Mo sites and adsorbed atomic H (Mo-Had bond), thereby decreasing the H2-evolution activity of Mo2CFx. In this work, a directionally charging d-orbital electron strategy of Mo2CFx-MoSe2 heterojunction via increasing the antibonding-orbital occupancy state of Mo to weaken Mo-Had bond in Mo2CFx is presented for the enhanced H2-generation performance. Herein, the ultrathin MoSe2 nanosheets are first vertically grown on the Mo2CFx surface via an in-situ selenization route to form Mo2CFx-MoSe2 heterojunction, and subsequently combined with the TiO2 to prepare the TiO2/Mo2CFx-MoSe2 through an ultrasonic-assisted method. The H2-evolution activity test indicates that the optimal TiO2/Mo2CFx-MoSe2 photocatalyst possesses an exceptional H2-evolution rate (427.66 μmol h−1 g−1), which is 38.98 and 1.94 folds higher than that of the TiO2 and TiO2/Mo2CFx, respectively. The experimental data and density functional theory (DFT) calculations substantiate that the generation of Mo2CFx-MoSe2 heterojunction can weaken the Mo-Had bond by electron transfer from MoSe2 to Mo2CFx for charging d-orbital electrons, accordingly promoting the photocatalytic H2-evolution efficiency of TiO2. This study highlights the optimization of Mo-Had bond by constructing Mo2CFx-based heterojunction to realize high-efficient photocatalytic H2 evolution.

Enhanced photoelectrochemical water splitting and photocatalytic decomposition performance of visible light active MgMnO3 perovskite nanostructure

Clean energy production and environmental remediation are imperative for sustainable future. Specially, exploration of multifunctional catalyst, for production of low-cost and eco-friendly hydrogen (H2) fuel as well as efficient decomposition of emerging pollutants are certainly needed. This study investigates magnesium manganese oxide (MgMnO3), a perovskite oxide, synthesized by simple citrate sol–gel technique, and its structural, morphological, optical, and photoelectrochemical properties were analyzed for the photodegradation of ciprofloxacin (CIP) antibiotic, methylene blue (MB) dye, and photoelectrochemical (PEC) water splitting. The cubic spinel crystal structure of MgMnO3 was confirmed through powder X-ray diffraction (XRD) analysis. FE-SEM images of the MgMnO3 material revealed a cauliflower-like morphology, consisting of an assembly of microspherical grains of varying sizes. UV–Vis spectroscopy exhibited broad absorption in the UV–Visible region, and the Tauc plot estimated a band gap of 1.54 eV. The MgMnO3 catalyst showed 88% and 96% for photodecomposition of CIP (10 mg/L) and MB (10 mg/L), respectively, using 35 mg and 30 mg of catalyst quantity over 90 min. In addition, MgMnO3 photoelectrode showcases superior photoelectrochemical behavior, exhibiting maximal photocurrent density of 13.21 mA cm−2 measured at 1.2 V vs. RHE and achieving a solar-to-hydrogen conversion efficiency of 2.45% compared to MgO and MnO2 photoelectrode. EIS measurements of MgMnO3 show enhanced charge transfer and recombination kinetics. Notably, the MgMnO3 electrode reveals outstanding photoelectrochemical durability, maintaining its stability even after continuous illumination for 9 h. Improved PEC properties could be attributed to wider light absorption, enhanced photo-induced charge-separations, and electron mobility. Thus, present study established an efficient and enduring multifunctional catalyst, catering photocatalytic degradation and PEC H2 generation.

Molecular Doping on Carbon Nitride for Efficient Photocatalytic Hydrogen Production.

Molecular doping is an innovative approach to modify the electronic configuration of carbon nitride (CN) photocatalysts, enhancing visible light absorption and optimizing the recombination of electron-hole pairs in photocatalytic H2 generation. Unlike the conventional heteroatom incorporation strategy, molecular doping offers a more effective means of structure optimization and conjugated framework. This Perspective studies recent advancements in benzene-ring doping for CN, emphasizing the correlation between structure and photocatalytic activity. The advantages and disadvantages of molecular doping in CN are thoroughly demonstrated, underscoring the importance of utilizing molecular doping to fine-tune both electronic and physical structures for enhanced photocatalytic efficacy. Insights are provided on strategies to address limitations and explore new prospects in the field of molecular doping methodologies.

Synergy of oxygen doping and nitrogen vacancy for promoting photocatalytic hydrogen generation of g-C3N4

Photocatalytic hydrogen (H2) generation is a promising and renewable solution to address the energy crisis, but is currently hindered by the limited carrier separation and deficient active sites of photocatalysts. In this study, oxygen (O) doping and nitrogen (N) vacancy co-modified hollow tubular g-C3N4 (O-CN-NV) is successfully prepared to enhance the photocatalytic H2 production. The incorporation of O doping facilitates the separation of photogenerated carriers within the tubular CN, while the N vacancy acts as the surface active site for capturing the photoinduced electrons. As a result, the photocatalytic H2 generation over O–CN–NV reaches 339.4 μmol g−1 h−1 under visible light irradiation, which is 6.1 times higher than that of bulk g-C3N4 (CN). This unique design holds great promise for the development of high-performance photocatalysts to produce renewable fuels.

Pd(II) coordination molecule modified g-C3N4 for boosting photocatalytic hydrogen production

The photocatalytic H2 production activity of polymer carbon nitride (g-C3N4) is limited by the rapid recombination of photoelectron-hole pairs and slow surface reduction dynamic process. Here, a supramolecular complex (named R-TAP-Pd(II)) was fabricated via self-assembly of (R)-N-(1-phenylethyl)-4-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)benzamide (R-TAP) with Pd(II) and used to modify g-C3N4. In the R-TAP-Pd(II)@g-C3N4 composite photocatalyst, the spin polarization of R-TAP-Pd(II) can promote charge transfer and inhibit photogenerated carrier recombination, as confirmed by spectral tests and photoelectrochemical performance tests. Electrochemical tests and in situ X-ray photoelectron spectroscopy (XPS) tests proved that the Pd(II) ion in the R-TAP-Pd(II) molecule can serve as active sites to accelerate H2 production. The R-TAP-Pd(II)@g-C3N4 presented a photocatalytic H2 generation rate of 1085 μmol g−1 h−1 when exposed to visible light, which was a about 278-fold increase compared with g-C3N4. This work finds a new approach to boost the photocatalytic efficiency of g-C3N4 via supramolecular self-assembly.

Surface plasmon resonance-mediated photocatalytic H2 generation.

The limited yield of H2 production has posed a significant challenge in contemporary research. To address this issue, researchers have turned to the application of surface plasmon resonance (SPR) materials in photocatalytic H2 generation SPR, arising from collective electron oscillations, enhances light absorption and facilitates efficient separation and transfer of electron-hole pairs in semiconductor systems, thereby boosting photocatalytic H2 production efficiency. However, existing reviews predominantly focus on SPR noble metals, neglecting non-noble metals and SPR semiconductors. In this review, we begin by elucidating five different SPR mechanisms, covering hot electron injection, electric field enhancement, light scattering, plasmon-induced resonant energy transfer, and photo-thermionic effect, by which SPR enhances photocatalytic activity. Subsequently, a comprehensive overview follows, detailing the application of SPR materials-metals, non-noble metals, and SPR semiconductors-in photocatalytic H2 production. Additionally, a personal perspective is offered on developing highly efficient SPR-based photocatalysis systems for solar-to-H2 conversion in the future. This review aims to guide the development of next-gen SPR-based materials for advancing solar-to-fuel conversion.

Fabricating of multi-interfacial charge transfer paths in the novel noble-metal-free Ni2P/ZnS/g-C3N4 ternary nanocomposite for enhanced charge separation and transfer for photocatalytic H2 generation

This work reports the development of a novel Ni₂P/ZnS/C₃N₄ ternary nanocomposite photocatalyst for efficient hydrogen (H₂) production. The nanocomposite was synthesized using a facile approach combining hydrothermal synthesis, ball milling, and wet impregnation methods then characterized using various techniques. Photocatalytic H₂ generation was evaluated under simulated solar irradiation with sodium sulfite (Na₂SO₃)/sodium sulfide (Na₂S) as sacrificial reagents. The optimized 3NP/ZnS-8CN (3% Ni2P/ZnS/8% C3N4) catalyst displayed an exceptional H₂ generation rate of 3991 µmol h⁻¹ g⁻¹, exceeding both pristine g-C3N4 (by 10.2 times) and 3% Ni2P/ZnS (by 1.2 times). This represents the highest reported rate of H₂ evolution for a graphitic carbon nitride (g-C3N4) based ternary nanocomposite under simulated solar radiation. Furthermore, the 3NP/ZnS-8CN photocatalyst exhibited good stability over four reaction cycles. This study provides valuable insights for designing efficient noble metal-free g-C3N4-based photocatalysts, which can significantly contribute to the transition to solar-driven hydrogen generation. The results of this study suggest that the synthesized composite materials hold significant promise for the advancement of new energy technologies.

Deposition state of CoS significantly affects the photocatalytic H2 generation performance of CdS–CoS heterostructure

Activity and stability are two scientific issues of concern in catalyst design and synthesis. In this study, supported (CoS/CdS) and encapsulated (CdS@CoS) catalysts were synthesized with controlled variations in solvent. Remarkably, the CoS/CdS exhibited higher activity, achieving an impressive average H2 generation rate of 29.26 mmol g−1 h−1 for the optimized sample. Conversely, the CdS@CoS demonstrated superior stability, showing no significant activity decline over a 20-h period. These findings highlight the importance of the cocatalyst deposition state in affecting the photocatalytic performance of catalysts. This research provides valuable insights for the synthesis of photocatalysts.

Effect of precursors on Cu particle distribution in g-C3N4 nanosheets towards efficient photocatalytic degradation and H2 generation

N-rich precursors govern the thermal polymerization formation of graphitic carbon nitride (g-C3N4) based catalysts towards enhanced photocatalytic performance. In this paper, Cu components were introduced in superior thin g-C3N4 nanosheets using the thermal polymerization copper acetate and bulk g-C3N4 created by different precursors including melamine, dicyandiamide, and thiourea, such as melamine-g-C3N4 (MCN), dicyandiamide-g-C3N4 (DCN), and thiourea-g-C3N4 (TCN). The performance of Cu-g-C3N4 nanosheets depended strongly on the precursors of bulk g-C3N4 samples. The well-developed Cu nanoparticles with clear lattice fringes were observed in the sample prepared using MCN (sample Cu-MCN) while the crystallinity of Cu nanoparticles became worse in the sample prepared using DCN (sample Cu-DCN). Interestingly, Cu clusters were homogeneously distributed in superior thin g-C3N4 nanosheets in the case of using TCN (sample Cu-TCN) because of S components in thiourea affected the thermal polymerization. The photocatalytic activity of Cu-TCN was drastically improved compared with other Cu-g-C3N4 samples. The photocatalytic hydrogen production rate of Cu-TCN with 1% of Cu components was 4035.6 μmol g-1 h-1. Cycle stability test indicated that sample Cu-TCN revealed high stability, in which the H2 generation rate was retained 95% of their initial value after 5 cycles. These results supply efficient approaches for the study and application of g-C3N4 based photocatalysts.

Bismuth nanocluster loaded on N-doped porous carbon with “memory catalysis” effect for efficient photocatalytic H2 generation and uranium(VI) reduction

Photocatalytic hydrogen production and uranium reduction can solve the problems of energy crisis and environmental pollution. Here, bismuth nanocluster loaded on N-doped porous carbon (Bi0/NC) with “memory catalysis” effect was prepared through a Bi-MOF precursor pyrolysis strategy for H2 generation and UO22+ reduction. The photocatalyst achieved an enhanced H2 production rate of 12.8 mmol g−1 h−1 and an improved UO22+ removal ratio of 95.9 %, which was 3.2 and 1.8 times as pristine carbon material, respectively. Moreover, both the H2 generation and UO22+ reduction showed a sustained activity under dark condition. Improved activity is ascribed to the optimized electronic property and the enhanced charge separation in Bi0/NC, which can be proved by the DFT calculation of projected density of state, Fermi level and charge density difference. This work provides a new strategy to realize the continuous H2 generation and U(VI) reduction in day and night.

(Sr0.6Bi0.305)2Bi2O7/KNbO3 nanocomposites with significantly enhanced photocatalytic H2 generation driven by simulated sunlight

A novel (Sr0.6Bi0.305)2Bi2O7/KNbO3 Z-scheme heterojunction was synthesized by two-step hydrothermal method and its photocatalytic activity for splitting water was studied under simulated sunlight. Compared with KNbO3 and (Sr0.6Bi0.305)2Bi2O7, the as-prepared (Sr0.6Bi0.305)2Bi2O7/KNbO3 samples exhibited remarkably enhanced photocatalytic activity for H2 production. It was found that the H2 production efficiency of (Sr0.6Bi0.305)2Bi2O7/KNbO3 (1:800) composite was nearly 39.5 times as large as that of pure KNbO3. The potential fields at interfaces between KNbO3 and (Sr0.6Bi0.305)2Bi2O7 with different energy band potential can drive the secondary distribution of photogenerated carriers, thereby improving photocatalytic activity. The composite demonstrates good stability for photocatalytic activities and still has excellent H2 production performance after four cycle experiments. This work verifies that the addition of a small amount of (Sr0.6Bi0.305)2Bi2O7 into the photocatalytically H2-generating semiconducting materials is an efficient strategy for significantly boosting photocatalytic H2 evolution.

Photocatalytic H2 generation and CO2 reduction by WB5-x cocatalyst of TiO2 catalyst

Catalytic reactions play an important role in modern industry as almost 90 % of the chemical industry is based on catalytic reactions. The development of new, more efficient catalysts will allow significant advances in chemical production, but still remains a rather challenging problem for materials scientists. Here, we have proposed and investigated a new composite photocatalyst based on WB5-x-WB2 and TiO2 for H2 evolution from aqueous ethanol solution and CO2 reduction under visible light irradiation (410 nm). New composite photocatalysts WB5-x-WB2/TiO2 were synthesized and characterized by X-ray diffraction, UV–vis spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Photocatalytic measurements show that the maximum activity of the composite photocatalyst 4 and 23 times higher than the activity of unmodified TiO2 in CO2 reduction and H2 evolution, respectively. Density functional calculations of the proposed reaction are in agreement with the provided experiments confirming the higher efficiency of the modified catalyst compared to TiO2.

Stable and Highly Active Single Atom Configurations for Photocatalytic H2 Generation.

The employment of single atoms (SAs), especially Pt SAs, as co-catalysts in photocatalytic H2 generation has gained significant attention due to their exceptional efficiency. However, a major challenge in their application is the light-induced agglomeration of these SAs into less active nanosized particles under photocatalytic conditions. This study addresses the stability and reactivity of Pt SAs on TiO2 surfaces by investigating various post-deposition annealing treatments in air, Ar, and Ar-H2 environments at different temperatures. It is described that annealing in an Ar-H2 atmosphere optimally stabilizes SA configurations, forming stable 2D rafts of assembled SAs ≈0.5-1nm in diameter. These rafts not only resist light-induced agglomeration but also exhibit significantly enhanced H2 production efficiency. The findings reveal a promising approach to maintaining the high reactivity of Pt SAs while overcoming the critical challenge of their stability under photocatalytic conditions.

Adjustable n→π* electronic transition by sulfonated benzene functionalized g-C3N4 for enhanced photocatalytic H2 generation

The photocatalytic efficiency of graphitic carbon nitride (g-C3N4) in hydrogen production is primarily hindered by its poor absorption of visible light, rapid recombination of electron-hole pairs, and the absence of hydroxyl radical formation. Herein, a novel g-C3N4 nanosheets functionalized with sulfonic acid groups were effectively produced through thermal polymerization of melamine and 2, 4-diamino-6-phenyl-1, 3, 5-triazine (DPT), followed by sulfonation treatment. The introduction of the phenyl group brings about alterations to the initial symmetrical arrangement of g-C3N4, leading to the disruption of certain hydrogen bonds. This, in turn, facilitates the movement of electrons from the n to π* orbitals, resulting in enhanced light absorption and improved efficiency in charge separation. Moreover, it induces modifications to the band structure and amplifies the production of hydroxyl radicals. Additionally, the introduction of sulfonic acid enhances the water affinity and the ability of dispersing graphitic carbon nitride in water. The optimized sulfonated benzene-substituted g-C3N4 (1000-BCN-SO3H) with a melamine to DPT ratio of 4:1 exhibits a maximum hydrogen production rate of 6.52 mmol·h−1·g−1 under simulated sunlight irradiation with good cycling stability, which is 3.93 times higher than that of g-C3N4 nanosheets. This research offers a promising opportunity for a novel approach in advancing carbon nitride materials for effective photocatalytic processes.