Hydrogen Photoproduction Research Articles

Oriented Crystal Polarization Tuning Bulk Charge and Single-Site Chemical State for Exceptional Hydrogen Photo-Production.

Rapid bulk charge recombination and mediocre surface catalytic sites harshly restrict the photocatalytic activities. Herein, the aforementioned concerns are well addressed by coupling macroscopic spontaneous polarization and atomic-site engineering of CdS single-crystal nanorods for superb H2 photo-production. The oriented growth of CdS nanorods along the polar axis, vectorially superimposing substantial polar units with orderly arrangement, renders a strong polarization electric field (20.1 times enhancement), which boosts bulk charge separation with an efficiency up to 72.4% (80.4-fold). Remarkably, polarization electric field alters the chemical state of Pt single sites by orderly reducing the binding energy of Pt atom with stepwise polarization enhancement of CdS substrate, which increases the onsite electron density of Pt from 10.232 to 10.261e- and *H key intermediates, providing preponderant Volmer-Tafel/Volmer-Heyrovsky reaction pathways with significantly decreased energy barriers for H2 production. Thus, highly polarized CdS nanorods with atomically dispersed Pt sites perform an outstanding H2 space-time yield of 118.5mmol g-1 h-1 and apparent quantum efficiency of 57.7% at λ = 420nm, and a record-high H2 turnover frequency of 57798.4 h-1, being one of the best catalysts for photocatalytic H2 evolution. This work highlights the function of polarization in manipulating charge separation and catalytic reaction.

Ternary ZnS/ZnO/Graphitic Carbon Nitride Heterojunction for Photocatalytic Hydrogen Production.

Ternary ZnS/ZnO/graphitic carbon nitride (gCN) photocatalysts were prepared by coupling gCN sheets with ZnO nanorods under solvothermal conditions followed by sulfurization using Na2S. SEM and TEM analyses show that small-sized ZnS particles (ca. 7.2 nm) deposit homogeneously on the surface of ZnO/gCN nanohybrids. Photoluminescence and electrochemical impedance spectroscopy show that ZnS allows for an enhanced charge separation efficiency as well as prolonged lifetime of photogenerated charge carriers, leading to improved hydrogen photoproduction under UV light irradiation compared to ZnO/gCN. Moreover, the deposition of ZnS nanoparticles improves the photostability of the ZnS/ZnO/gCN catalyst for hydrogen production. A double Z-scheme mechanism is proposed for hydrogen photoproduction using the ZnS/ZnO/gCN heterojunction.

In-situ construction of In2O3/In2S3-CdIn2S4 Z-scheme heterojunction nanotubes for enhanced photocatalytic hydrogen production

Semiconductor photocatalysis was considered as an ideal solution to energy shortages. Herein, a novel ternary In2O3/In2S3-CdIn2S4 (IOSC) nanotube (NTs) photocatalyst was successfully constructed via in situ growth of In2S3 and CdIn2S4 nanosheets onto In2O3 skeleton. It was used for the efficient and stable photo-production of hydrogen from water splitting. The rationally designed IOSC NTs displayed significantly enhanced photocatalytic H2 production under visible light irradiation (≥420 nm), with the highest H2 yield determined to be 2892 μmol·g−1, which is much higher than that of pristine In2S3 and In2O3/In2S3 (IOS) NTs. Cyclic testing has shown that the IOSC2 product remains stable after four cycles of repeated use. The enhanced photocatalytic activity was contributed by its tightly bound tube-nanosheets heterogeneous structure and superior light absorption. Photoelectrons transfer in IOSC2 follows a Z-scheme mechanism, which greatly facilitates its utilization of photogenerated electrons and prevents CdIn2S4 from undergoing photo-corrosion affecting material stability. This work demonstrates the key role of in situ growth in the interface design of ternary heterostructures.

Glycerol photoreforming for photocatalytic hydrogen production on binary and ternary Pt-g-C3N4-TiO2 systems: A comparative study

Photocatalytic hydrogen production using two sacrificial agents (triethanolamine and glycerol) was conducted on several binary (Pt/TiO2 and Pt/g-C3N4) and ternary systems (Pt on a heterojunction between TiO2 and g-C3N4 (Pt/(g-C3N4-TiO2) and on a physical mixture of semiconductors (Pt/(TiO2 +g-C3N4)). Reactions were carried out under visible light (450 nm) and UV (365 nm) radiation, from 10% (v/v) and 0.5% (v/v) sacrificial agent aqueous solutions, hydrogen production values being ca- 2–3 times greater in the former case. For visible light, the heterojunction was the most active system using triethanolamine whereas Pt/TiO2 system and glycerol was the best option under UV radiation. All in all, the highest hydrogen production value from a 10% (v/v) glycerol in water solution was on Pt/TiO2 (named Ptuv/Ti), under UV light, yielding around 165 mmol H2·gcat−1·after 6 h (that is, ca. 27.5 mmol·gcat−1·h−1). Hydrogen photoproduction studies from glyceraldehyde, dihydroxyacetone, and glycerol either alone or in binary mixtures (i.e., competitive reactions) cast further light on the glycerol reaction mechanism. Results evidenced that the adsorption strength on the catalysts follows the sequence glyceraldehyde > dihydroxyacetone > glycerol, adsorption of the former being particularly high on the heterojunction. Reactions were ca. twice as fast on Pt/TiO2 as on the Pt/(g-C3N4-TiO2) heterojunction and even though initial stages of the mechanism seems to differ a bit for the semiconductors, there is a hydrogen production value from which mechanism is apparently the same on both solids.

Synthesis and characterization of Mo-doped PbS thin films for enhancing the photocatalytic hydrogen production

Photocatalytic hydrogen production has gained considerable attention as a sustainable method for renewable energy production. Lead sulfide (PbS) compound has significant reserves and a suitable bandgap for the production of hydrogen gas via the water photo-splitting process. However, the charge recombination effect of the charge carriers severely limits their potential use in solar water splitting. Herein, the photoelectrodes of PbS were fabricated through the chemical bath deposition method and then doped with different Mo concentrations to optimize the hydrogen photo-production activity. Both structural and performance characterizations of the photoelectrodes have been carried out using various characterization techniques. The photoelectrochemical (PEC) performance of molybdenum (Mo)-doped PbS photoelectrodes exhibits a significant increase in the photocurrent density with the optimum photocurrent density of 1.2 mA/cm2 obtained at 0.8 % Mo doping atomic ratio which was twelve times higher than that of a pure PbS photoelectrode. The doping of Mo induces the electron-hole separation yield which results in improved electron transport characteristics. The Mo doping was as act as a donor site that increased the PbS film conductivity. The newly optimized Mo–PbS was used as a promising photoelectrode supported on commercial glass using the optimum Mo-doped PbS photoelectrode, the photoelectrochemical (PEC) hydrogen production rate was reached 122 μmol/h cm2 during the solar water splitting process and the conversion efficiency of the incident photon-to-current (IPCE) value was 7.0 % at 390 nm monochromatic exposure. Moreover, the stability of the optimum electrode was evaluated as a function of the number of runs and exposure time in addition to the electrochemical impedance study.

Chlamydomonas reinhardtii and Microbacterium forte sp. nov., a mutualistic association that favors sustainable hydrogen production

A naturally occurring multispecies bacterial community composed of Bacillus cereus and two novel bacteria (Microbacterium forte sp. nov. and Stenotrophomonas goyi sp. nov.) has been identified from a contaminated culture of the microalga Chlamydomonas reinhardtii. When incubated in mannitol- and yeast extract-containing medium, this bacterial community can promote and sustain algal hydrogen production up to 313 mL H2·L−1 for 17 days and 163.5 mL H2·L−1 for 25 days in high-cell (76.7 μg·mL−1 of initial chlorophyll) and low-cell density (10 μg·mL−1 of initial chlorophyll) algal cultures, respectively. In low-cell density algal cultures, hydrogen production was compatible with algal growth (reaching up to 60 μg·mL−1 of chlorophyll). Among the bacterial community, M. forte sp. nov. was the sole responsible for the improvement in hydrogen production. However, algal growth was not observed in the Chlamydomonas-M. forte sp. nov. consortium during hydrogen-producing conditions (hypoxia), suggesting that the presence of B. cereus and S. goyi sp. nov. could be crucial to support the algal growth during hypoxia. Still, under non‑hydrogen producing conditions (aerobiosis) the Chlamydomonas-M. forte sp. nov. consortium allowed algal growth (up to 40 μg·mL−1 of chlorophyll) and long-term algal viability (>45 days). The genome sequence and growth tests of M. forte sp. nov. have revealed that this bacterium is auxotroph for biotin and thiamine and unable to use sulfate as sulfur source; it requires S-reduced forms such as cysteine and methionine. Cocultures of Chlamydomonas reinhardtii and M. forte sp. nov. established a mutualistic association: the alga complemented the nutrient deficiencies of the bacterium, while the bacterium released ammonium (0.19 mM·day−1) and acetic acid (0.15 mM·day−1) for the alga. This work offers a promising avenue for photohydrogen production concomitant with algal biomass generation using nutrients not suitable for mixotrophic algal growth.

3DOM BiOI/TiO2 composites modified by metal Ag with broad spectrum response for photocatalytic degradation and water splitting

In order to improve the photocatalytic performance of TiO2 and expand its absorption range in the visible light region, depositing noble metals, constructing the p-n heterojunction and controlling the morphology were used to modify TiO2. First, the TiO2 photocatalyst with a three-dimensional ordered macroporous structure was prepared by vacuum impregnation combined with calcination, and then the 3DOM Ag/BiOI/TiO2 composites were successfully prepared by the in-situ deposition and photoreduction. The characterization results show that the composites present a large number of open and transparent pore structures. The pore wall is formed by stacking TiO2 nanoparticles, with BiOI and Ag nanoparticles evenly distributed on the surface of the pore wall and in the macroporous framework, which expands the specific surface area of 3DOM TiO2 and provides more active sites for the reaction. The introduction of BiOI and Ag expands the visible light response range and improves the light utilization efficiency. Furthermore, the formation of the Schottky barrier and the internal electric field formed by the p–n heterojunction effectively promotes the interfacial electron transfer and suppress the electron–hole recombination, thereby generating more active species during the photocatalytic process. The experimental results of multi-mode photocatalytic degradation of methyl orange (MO) also show that 3DOM Ag/BiOI/TiO2 photocatalyst has the best photocatalytic degradation activity. In addition, different samples were tested for hydrogen production by photolysis of water under simulated sunlight conditions, and the results show that 3DOM Ag/BiOI/TiO2 has the best hydrogen production ability of photolysis of water. The excellent performance of multi-modal photocatalytic degradation of organic pollution and high photohydrogen production activity in 3DOM Ag/BiOI/TiO2 composites is attributed to the synergistic effect between the introduction of metallic Ag, the unique 3DOM structure, and the p–n heterojunction.

Enhancing the hydrogen photo-production using zinc oxide films doped with iron, tin, and aluminum

Hydrogen is recognized as the most promising renewable energy source and can be efficiently produced through water photo-electrolysis green process. This study investigates the performance of ZnO nanorods doped with Fe, Al, and Sn at a 2 % molar ratio for hydrogen photo-production. The films were prepared using a combination of successive ionic layer adsorption and reaction (SILAR) and chemical bath deposition (CBD) methods. X-ray diffraction (XRD) analysis confirmed the hexagonal structure of the doped ZnO films with preferential growth along the (002) orientation, while energy-dispersive X-ray spectroscopy (EDX) confirmed their high purity. The doping with Al maintains the ZnO nanorods morphology while Fe, and Sn doping induced changes to overlapped nanoflakes/nanoflowers morphology. Optical analysis revealed a clear trend in the energy band gap, with Fe-ZnO film exhibiting the lowest value (2.95 eV), followed by Al-ZnO (3.03 eV), Sn-ZnO (3.07 eV), and ZnO (3.11 eV). The Fe-ZnO film also demonstrated the best performance as a photoelectrode for hydrogen generation, achieving optimized incident photon-to-current efficiency (IPCE) and applied bias photon-to-current efficiency (ABPE) values of 1.45 % and 0.20 % respectively, under 500 nm monochromatic illumination, with high reproducibility, and durability. These findings represent one step forward to developing ZnO-doped photoanodes for efficient and sustainable hydrogen green production.

Lattice-matched controllable construction of nanometer scale CdS/TiO2 hollow nanoboxes Z-scheme heterojunctions based on micrometer and sub-nanometer CdS for comparison of visible photocatalytic activity

Size effect exerts a significant influence on the photocatalytic properties of materials. Nanometer CdS/TiO2 hollow nanoboxes (TiO2-HNBs) (tetragonal phase) Z-scheme heterojunctions were lattice-matched controllably fabricated by using cubic TiOF2 as a template and loading with micrometer CdS micron rods (hexagonal phase) or sub-nanometer CdS quantum dots (cubic phase) through one-pot template ultrasonic hydrothermal method. The morphology, constitution, physical property, as well as photocatalytic properties of as-prepared samples were investigated comprehensively. Under visible light irradiation (λ ≥ 420 nm), the hydrogen production rates of CdS micron rods, CdS nanorods/TiO2-HNBs (CT-7), CdS quantum dots/TiO2-HNBs (CTQ-7) and CdS quantum dots was 1642.61, 455.35, 148.92 and 1025.53 μmol/g/h, which was 26.39, 7.32, 2.39 and 16.48 times that of TiO2-HNBs, respectively. Meanwhile, the photodegradation rate of Rhodamine B by CdS micron rods, CT-7, CTQ-7 and CdS quantum dots within 60 min was 69.59%, 99.90%, 89.96% and 40.70%, which were 4.77, 6.85, 6.17 and 2.79 times that of P25, respectively. CdS micron rods had the largest size but the strongest photo-hydrogen production properties. Due to its Z-scheme heterojunction structure and Ti-S bond, CT-7 exhibited enhanced electron-hole separation rate and electron transfer rate, resulting in superior RhB degradation performance. Although CdS quantum dots had the smallest size, it did not boast the best performance, indicating that smaller size does not necessarily correlate with better photocatalytic performance. This study provides a reference for comparing the performance of photocatalytic materials with different sizes.

Pt-Ni contact engineering in carbon nitride based photocatalysts for hydrogen production

The effect of a binary PtNi co-catalyst supported on graphitic carbon nitride nanosheets is studied in the photo-production of hydrogen from methanol:water mixtures. The physicochemical analysis provides evidence that the carbon nitride support allows the formation of highly dispersed PtNi nanoparticles with an average composition of Pt 85 % Ni 15 %. The binary system outperforms the monometallic Pt and Ni counterparts and renders an extraordinary quantum efficiency of 8.8 % for hydrogen photo-production. The formation of a PtNi alloy, with a Pt-enriched surface and electronic properties influenced by the heterometallic contact, provides high and stable activity, mostly as a consequence of the effects that the co-catalyst exerts on the charge carrier handling capability of the solid.

PdCu deposited alloys on TiO2 for hydrogen photo-production

The role of a Pd-based co-catalyst supported on a high surface area anatase powder is analyzed for the photo-production of hydrogen from methanol:water mixtures. The co-catalyst chemical composition was modified by replacing palladium atoms with copper. The preparation method renders alloyed particles with a primary particle size in the 5–6 nm interval. A Pd:Cu 3:1 ratio promotes strongly the activity of the noble metal. According to the quantum efficiency parameter, the Pd:Cu 3:1 alloy increases by ca. 2 the activity of the monometallic Pd counterpart. The analysis of the photoactivity points out that alloying does not affect positively charge recombination and handling

Hydrogen photoproduction using Au promoted ZrOx-TiO2 composite catalysts

In this research study, the impact of adding zirconium oxide to titanium oxide-supported gold systems on photocatalytic hydrogen production was analyzed. The activity was evaluated as a function of the zirconium content, with up to 5 mol.% tested under UV, visible light, and sunlight illumination. It was found that the highest activity was achieved with a 1.75 mol.% zirconium oxide, as measured using reaction rate and quantum efficiency parameters under various illumination conditions. The results showed a quantum efficiency close to 1.9% under sunlight, which represents a substantial improvement of over two orders of magnitude compared to the original titanium system. The addition of zirconium influenced the recombination of charge carriers and boosted photoactivity through the interaction between gold and zirconium.

Dual Defective K-Doping and Cyano Group Sites on Carbon Nitride Nanotubes for Improved Hydrogen Photo-Production

In this work, dual defective potassium (K) doping and cyano group sites have been introduced into carbon nitride (CN) with various morphologies by a co-condensation method for highly efficient photocatalytic hydrogen production. The photocatalysts with potassium doping and inserted cyano groups display higher photocatalytic activity of hydrogen evolution under visible light irradiation in contrast to undoped bulk CN, CN nanosheets, and CN nanotubes. Potassium-doped CN nanotubes present the greatest hydrogen generation yield of 2.11 mmol g–1 h–1 with an apparent quantum efficiency of 5.28% at 420 nm, which is about 2.0 and 40 times that of K-incorporated bulk CN and the bare CN nanotubes, respectively. Benefiting from uniformly distributed potassium ions, the introduction of cyano groups, and the one-dimensional tubular structure of CN nanotubes, the resultant K-doped CN nanotubes have new charge transfer paths between potassium ions and adjacent heptazine units, accelerating photogenerated carrier transfer and enhanced photoreduction ability, thereby improving the photocatalytic performance. This study presents a reliable method for element doping of CN with various morphologies to photocatalytic hydrogen evolution through water splitting.

Synthesis of Fe-TiO2 and Cu-TiO2 Based Materials by Olive Leaves Biotemplating—Application to Hydrogen Production from Glycerol Photoreforming

Hydrogen production is mainly based on the use of fossil fuels, but currently, many alternative routes are being developed, among which the photo-reforming of oxygenated organic compounds stands out. Recently, several studies have been carried out in order to develop new techniques to create bio-inspired TiO2 structures. One of these is 'biotemplating', a process that replicates a biological system in an inorganic TiO2-based structure. In this study, olive by-products-olive leaves-are valorized as a biotemplate for the synthesis of new Fe-TiO2- and Cu-TiO2-based photocatalysts with the aim of improving the replication of the leaf structure and enhancing hydrogen photoproduction. In conclusion, the incorporation of iron and copper decreases the band gap and increases the energetic disorder at the band edges. Moreover, it is verified by SEM and TEM that the metals are not found forming particles but are introduced into the formed TiO2 structure. The accuracy of the internal and external structure replication is improved with the incorporation of Fe in the synthesis, while the incorporation of Cu substantially improves the production of hydrogen, which is multiplied 14 times under UV light and 6 times under sunlight, as compared to a pure TiO2 structure.

Elucidation of the electron transfer mechanisms of hydrogen production from light by Shewanella oneidensis - cadmium sulfide biohybrid system

The biological hydrogen production from sunlight using biohybrid systems is an emergent attractive technology developed to help decarbonize manufacturing, transportation, and energy production. The electroactive organism Shewanella oneidensis MR-1 has been successfully used as a biocatalyst in whole-cell biohybrid systems for hydrogen production. In this work, knock-out mutants of the key proteins involved in the extracellular electron transfer pathway of S. oneidensis MR-1 were used to unravel the electron transfer pathway of the biohybrid S. oneidensis-CdS system for the photoproduction of hydrogen. While the cytochromes OmcA, MtrC, MtrA and CymA were shown to be crucial for electron uptake and hydrogen production, the periplasmic proteins STC and FccA do not participate in this process. This information was used to improve hydrogen production, demonstrating that the photoproduction of hydrogen by a biohybrid system can be improved and can be a promising approach to address global energy and environmental problems.

A compact photoreactor for automated H2 photoproduction: Revisiting the (Pd, Pt, Au)/TiO2 (P25) Schottky junctions

The configuration and geometry of chemical reactors underpins the accuracy of performance evaluation for photocatalytic materials and, accordingly, the development and validation of thermodynamic and kinetic model reactions. The lack of accurate photonic, mass, and heat transport profiles for photochemical reactors hinder standardization, scale-up, and ultimately comparison between different experiments. This work proposes two contributions at the interface between engineering of chemical process and materials science: (A) an automated compact stainless-steel photoreactor with 40 cm3 and 65 cm2 of volume and area, respectively, for hydrogen photoproduction as a model reaction and (B) the synthesis, characterization, and performance of TiO2 Schottky junctions, using Pd, Pt, or Au nanoparticles (ca. 0.5, 1, 2 wt% loadings each) to validate the operation of the reactor. A photonic profile methodology is implemented to the studied reactor to obtain the local light absorption profile, opening up for evaluation of the local quantum yield calculation for the selected materials. A combination of transmission electron microscopy, (X-ray/ultraviolet) photoelectron/electron, energy loss/infrared spectroscopies, X-ray scattering, inductively coupled plasma atomic emission spectroscopy, and ultraviolet–visible spectrophotometry is employed to determine the distinctive surface and bulk properties to build structure–function correlations. The (Pd, Pt, Au)/TiO2 Schottky junction exhibits H2 production rates slightly higher than previous studies, with quantum yields almost 2-fold higher than reported values. These results, demonstrate that the proposed novel geometry of the photoreactor improves the photonic, heat, and mass profiles. An in-depth analysis of the Au plasmon was investigated coupling electron energy loss spectroscopy, UV–vis, and transmission electron microscope, resulting in insightful information about the Au NP mode at the TiO2 interface.

Pd-Sn promoted NbOx/TiO2 catalysts for hydrogen photoproduction: Effect of Pd-Sn interaction on charge handling and reaction mechanism

Enhanced performance of Pd in the photocatalytic production of green hydrogen from methanol:water mixtures is achieved through the use of a sn-containing binary co-catalyst. For a Pd:Sn molar ratio of 1:1, the binary co-catalyst leads to an outstanding enhancement of activity under UV, visible and sunlight illumination, rendering a quantum efficiency value of 4 % in the latter case. A core–shell type interaction occurs between Pd metal nanoparticles and Sn oxo-hydroxyde nanoentities, resulting in an electronic modification of both components. The chemical effects of the binary co-catalyst were explored under reaction conditions using infrared spectroscopy. Overall, this study provides evidence that the electronic interaction between Pd and Sn promotes the adsorption and attack of the charge carrier species on the methanol molecule and controls the reaction mechanism, favoring the generation of hydrogen. This new system appears to be a strong candidate in the contribution to the new hydrogen economy through a green and eco-efficient process using renewable energy and reagents.

Controlled photodeposition of Pt onto TiO2-g-C3N4 systems for photocatalytic hydrogen production

Platinum (0.5 wt. %) was photodeposited on g-C3N4-TiO2 systems using UV or Vis light. Different absorption by semiconductors seemed to somehow influence resulting platinum particle size and distribution. Thus, lower platinum particle sizes were obtained on g-C3N4 utilizing visible light and on TiO2 using UV radiation. Furthermore, there was a preferential platinum photodeposition on g-C3N4 or TiO2, more evident in physical mixtures of both semiconductors, depending on radiation source being visible or UV light, respectively. The solids were tested for hydrogen photoproduction using triethanolamine as the sacrificial agent. g-C3N4 synthesis on P25 TiO2 allowed the effective formation of a heterojunction (as determined by UV–vis and EPR). Subsequent platinum photodeposition resulted in solids yielding ca. 5100 μmol·g−1·h−1 H2 under visible light. This represents a ca. 7-fold increase in activity as compared to the physical mixture of platinum-containing semiconductors and a 2-fold increase as compared to simultaneous incorporation of platinum to the reaction medium.

Promising photocatalysts based on nanoshaped TiO2 - rGO composite doped with metals (Pt and Cu) for hydrogen photoproduction

Photocatalysts based on TiO2 and its modification have become popular as promising materials for the sustainable photoproduction of hydrogen. In this work, novel Pt - Cu - TiO2 composites with different TiO2 nanoshapes and modified with biomass-derived reduced graphene oxide (rGO) are reported as promising photocatalysts for the generation of hydrogen from water-alcohol mixtures. The developed photocatalyst has been characterized by X-ray diffraction, X-ray fluorescence spectroscopy, Raman and Fourier-transform infrared spectroscopies, scanning electron microscopy and Brunauer-Emmett-Teller surface area analysis. The partial replacement of platinum with copper definitely lowered the cost of hydrogen photoproduction still keeping its high efficiency. Furthermore, the additional modification of the composite with rGO successfully boosted the amount of generated H2, which was ca. 27 mmol h−1 g−1.

Efficient photohydrogen production by edge-modified carbon nitride with nonmetallic group

As an efficient photocatalyst, graphitic carbon nitride (g-C3N4) has been widely used in the field of photocatalytic hydrogen production. However, how to prepare hydrogen efficiently and stably has become a challenge. Herein, we successfully realize metal-free edge modification with phenyl groups by one-step thermal polymerization of urea with 4-phenyl-3-thiosemicarbazide. Consequently, the optimal photocatalytic hydrogen production rate for the modified graphitic carbon nitride is increased by three times to a value of 2390.6 μmol h−1 g−1, while the apparent quantum efficiency (AQE) reaches 8.3 % at a wavelength of 420 nm. We also provide a theoretical explanation for the experiments using density functional theory (DFT) calculations, which suggest that energy level changes and electron redistribution for the modified carbon nitride materials contribute to the observed changes in catalytic performance. This work provides an effective solution for improving the photocatalytic activity of carbon nitride materials and provides theoretical support for the edge modification of carbon nitride materials to promote their photocatalytic hydrogen production efficiency.