Efficient Charge Separation Research Articles

Novel Inorganic-Organic Dual-Photosensitizing Dinuclear-Metal Self-Assembly System for Efficient Artificial Photosynthesis without Sacrificial Electron Donors.

Owing to the unique synergistic effect, dinuclear-metal-molecule-catalysts (DMCs) show excellent performance in catalytic fields. However, for overall photocatalytic CO2 reaction (CO2RR), it is still a challenge to construct well-matched photosensitizer (PS) components for DMCs-based photocatalysts. Inorganic-quantum-dot PS possesses capacities of multiple exciton generation and catalyzing water oxidation but is incompatible with DMCs. In contrast, organic PS can be covalently linked with DMCs but inescapable of using sacrificial electron donors. For overall photocatalytic CO2RR, organic-inorganic dual-photosensitizing system might be a promising candidate. Herein, we employed covalent-linking and electrostatic-driven approaches to construct the self-assembly of pyrene-sensitized Co2L DMCs (Py-Co2L) and perovskite (PVK) quantum dots, i.e., PVK@[Py-Co2L]. Using H2O as an electron donor, PVK@[Py-Co2L] realized 105.24 μmol·g-1·h-1 CO yield in photocatalytic CO2RR, much higher than PVK (15.44 μmol·g-1·h-1) and PVK@Co2L (32.30 μmol·g-1·h-1), ascribing to the efficient photogenerated charge separation and transfer. The experimental results and theoretical investigations demonstrated that the pyrene linked on Co2L boosted the electron delivery from PVK to DMCs. Besides, this strategy could also be extended to the photocatalytic H2 evolution coupled with alcohol oxidation. As a proof-of-concept, our work lightens the integration of DMCs, organic and inorganic PS components, promoting the development of photocatalysis without sacrificial electron donors.

Regulation of the Built‐In Electric Fields of MIL‐125(Ti)@Ti‐Ce‐MOF Yolk‐Shell Z‐Scheme Heterojunctions via Ligand Defects Toward Optimized Photocatalytic Performances

AbstractThe controllable formation of a built‐in electric field (IEF) can effectively separate photogenerated electrons and holes and optimize the band structure of a material, thus improving its photocatalytic performance. Here, a novel type of defective metal‐organic framework (MOF), i.e., an MIL‐125(Ti)@Ti‐Ce‐MOF yolk‐shell Z‐scheme heterojunction, is synthesized using a simple ion‐etching‐coupled reconstruction method. By controlling the concentration of ligand defects within the MOF heterojunction, the strength of the IEF within the heterojunction can be effectively regulated. Moreover, the experimental and theoretical results demonstrated that ligand defects within the Z‐scheme heterojunction structure can enhance the efficiency of photogenerated carrier separation and improve the transport capacity by regulating the IEF. The photocatalytic tetracycline (TC) degradation performance of the resultant MIL‐125(Ti)@Ti‐Ce‐MOF yolk‐shell heterojunction is ≈52.5‐ and 5.5‐fold higher than those of Ti‐Ce‐MOF and MIL‐125(Ti), respectively, indicating the efficient spatial charge separation due to the enhanced IEF. This study reveals the precise control of the IEF over the MIL‐125(Ti)@Ti‐Ce‐MOF yolk‐shell Z‐scheme heterojunction, elucidating the relationship between the IEF and ligand defect concentration and promoting the photocatalytic performances of MOF@MOF‐based catalysts via density functional theory and related experiments.

Oxygen vacancy induced defect dipoles in BiVO4 for photoelectrocatalytic partial oxidation of methane

A strong driving force for charge separation and transfer in semiconductors is essential for designing effective photoelectrodes for solar energy conversion. While defect engineering and polarization alignment can enhance this process, their potential interference within a photoelectrode remains unclear. Here we show that oxygen vacancies in bismuth vanadate (BiVO4) can create defect dipoles due to a disruption of symmetry. The modified photoelectrodes exhibit a strong correlation between charge separation and transfer capability and external electrical poling, which is not seen in unmodified samples. Applying poling at −150 Volt boosts charge separation and transfer efficiency to over 90%. A photocurrent density of 6.3 mA cm−2 is achieved on the photoelectrode after loading with a nickel-iron oxide-based cocatalyst. Furthermore, using generated holes for methane partial oxidation can produce methanol with a Faradaic efficiency of approximately 6%. These findings provide valuable insights into the photoelectrocatalytic conversion of greenhouse gases into valuable chemical products.

Elucidating the Advancement in the Optoelectronics Characteristics of Benzoselenadiazole-Based A2-D-A1-D-A2-Type Nonfullerene Acceptors for Efficient Organic Solar Cells.

The potential applications of nonfullerene acceptors (NFAs) such as tunable band gaps, improved charge separation, wide-range absorption, enhanced power conversion efficiency, and operational stability make them highly favorable for organic photovoltaic applications. Herein, we designed eight novel structurally modified nonfused benzoselenadiazole (BSe)-based A2-D-A1-D-A2-type NFAs for efficient organic solar cells (OSCs). These newly modeled BSe-based NFA series contain BSe as the central core. We employed strong electron-withdrawing moieties at terminal acceptor A2 to further enhance the optical, optoelectronics, and photovoltaic characteristics of OSCs. These designed molecules (HNM1-HNM8) along with the synthetic reference molecule (HNM) were thoroughly characterized by using efficient and advanced quantum chemical simulation approaches. Thus, to ascertain the enhancement of both optical and photochemical response, a thorough density functional theory (DFT) study was carried out using the M062X level in association with the 6-31G(d,p) basis set. All of the investigated molecules (HNM1-HNM8) had their excited states calculated using the time-dependent density functional theory method. The newly designed molecules (HNM1-HNM8) presented narrower band gaps, improved absorption and optoelectronics properties, and reduced excitation and binding energies. The electrostatic potential, density of states, transition density matrix, ionization potential, and electron affinity analysis of this newly designed (HNM1-HNM8) series revealed a strong coherence with those of the reference HNM molecule. Electron density difference mapping allowed us to visualize the spatial movement of electrons between the donor and acceptor molecules during excitation. This insight helps us to understand the efficiency of charge separation and recombination processes that are critical for the performance of organic photovoltaics. The reorganization energy and charge transfer analysis suggests that HNM1-HNM8 molecules could act as NFAs for organic photovoltaic applications to enhance their efficiency further. The donor: acceptor charge transfer analysis was also carried out, which revealed that the PTB7-Th:HNM2 donor:acceptor complex shows a great charge transportation process at the donor-acceptor interface. Moreover, the photovoltaic analysis shows that the designed (HNM1-HNM8) NFA series has a great potential to produce improved open-circuit voltage and fill factor values, which may be helpful in enhancing the overall PCEs of the OSCs.

Facile one-step synthesis of a WO3/ZnWO4 heterojunction modified using ZnFe LDH enhances the PEC water splitting efficiency.

Photoelectrochemical water splitting represents a promising approach for directly converting solar energy into green hydrogen, offering a potential solution to the challenges of energy shortages and environmental pollution. In this work, a WO3/ZnWO4 binary heterojunction was synthesised by a simple and effective one-step drop casting method to enhance the charge separation efficiency; ZnFe LDH was deposited on the surface of the heterojunction with the aim of accelerating water oxidation and synergising with the heterojunction to enhance the photoelectrochemical performance of the photoanode. The photocurrent density of the WO3/ZnWO4/ZnFe LDH electrode can reach 2.1 mA cm-2 at 1.23 V (vs. RHE). This value is approximately 4 times greater than that observed for pure WO3 (0.53 mA cm-2). The IPCE and ABPE were able to improve by 3.1 times and 6 times, respectively.

Surface Epitaxial Growth of 2D/2D Bi2O2S/CdS Heterojunction Photoanodes and Their Photoelectrochemical Properties.

Constructing high catalytic activity heterojunctions to compensate for the shortcomings of single catalysts has promoted the development of semiconductor catalysts in photoelectrochemical (PEC) water splitting. In this case, the 2D/2D Bi2O2S/CdS composite was successfully constructed by an in situ surface epitaxial growth method. At 1.23 V vs RHE, the catalytic activity of Bi2O2S/CdS with a 2D/2D heterojunction is the highest, and the current density of the Bi2O2S/CdS photoanode is 3.46 mA/cm2. Compared with the Bi2O2S photoanode (0.59 mA/cm2), the performance has been improved by 5.86 times. In electrochemical impedance spectroscopy testing, the arc radius of 2D/2D Bi2O2S/CdS is smaller than that of Bi2O2S, indicating faster charge-transfer kinetics. The data show that the 2D/2D heterojunction with surface-surface contact successfully enhances the catalytic activity of Bi2O2S, greatly elevating the efficiency of charge separation and migration. This study provides a method to enhance the PEC activity in type-I heterojunction photoelectrodes, promoting the application of Bi2O2S-based materials in photoelectrochemistry.

Efficient and selective photocatalytic oxidation of benzylic alcohols with built-in electric field CsPbBr3/SiO2 nanocomposites through Fe3+ gradient doping

Lead halide perovskite nanocrystals (PNCs) have emerged as promising materials for photocatalysis due to their exceptional optoelectronic properties, yet achieving efficient charge separation and selective oxidation reactions remains a significant challenge. In this study, we report the synthesis of Fe3+-doped CsPbBr3/SiO2 nanocomposites (Fe-PNCs/SNPs) with gradient energy levels, designed to enhance photocatalytic performance. Our results demonstrate that Fe3+ doping introduces mid-gap states, promotes photoinduced charge separation, and generates reactive oxygen species (ROS) such as O2− and OH radicals under sunlight-simulating light irradiation from a 300 W Xe arc lamp. The Fe20-PNCs/SNPs catalyst achieved over 99 % conversion of benzyl alcohol to benzaldehyde with high selectivity and stability in the ethanol under ambient conditions. Additionally, the catalyst exhibited excellent recyclability and broad substrate tolerance. These findings highlight the innovative design of gradient energy levels in perovskite nanocomposites, offering a new strategy for enhancing photocatalytic efficiency in selective organic transformations.

MIL-125-PDI/ZnIn2S4 Inorganic-Organic S-Scheme Heterojunction With Hierarchical Hollow Nanodisc Structure for Efficient Hydrogen Evolution from Antibiotic Wastewater Remediation.

Efficient photocatalytic production of H2 from wastewater is expected to address environmental pollution and energy crises effectively. However, the rapid recombination of photoinduced carriers results in low photoconversion efficiency. At present, inorganic-organic S-scheme heterojunction have become a prominent and promising technology. In this study, an organic ligand modified MIL-125-PDI/ZnIn2S4 (ZIS) inorganic-organic S-scheme heterojunction catalyst is designed. ZIS nanosheets are grown on the disc-shaped MIL-125-PDI surface to form a distinctive hollow nanodiscs with hierarchical structure, giving the material an abundance of surface active sites, an optimized electronic structure, and a spatially separated redox surface. Consequently, the optimal 100MIL-125-PDI250/ZIS exhibited high photocatalytic HER of 508.99 µmol g-1 h-1 in Tetracycline hydrochloride (TC-HCl) solution. Meanwhile, the catalyst achieved complete TC-HCl removal and mineralization rate of 66.62% in 4h. Experimental and theoretical calculations corroborate that the staggered band alignment and work function difference between MIL-125-PDI and ZIS induce the formation of a built-in electric field, thus regulating the charge transfer routes and consequently enhancing charge separation efficiency. The possible photocatalytic mechanism is analyzed using liquid chromatography-mass spectrometry (LC-MS), and the toxicities of the degradation products are also evaluated. This work presents a green dual-function strategy for H2 production and antibiotic wastewater recycling.

Fabrication of pyridine incorporated and O-doped g-C3N4/COF: A type-II heterojunction for enhanced hydrogen production under visible light irradiation

The fabrication of heterojunction photocatalysts is important for achieving highly efficient electron transfer, charge separation, and catalytic activity. In this study, we report the successful creation of a type II heterojunction between pyridine incorporated and O-doped g-C3N4 (POCN) and a covalent organic framework (COF). The heterojunction formation significantly reduced the fluorescence intensity of the POCN/COF, indicating effective separation of electron-hole pairs. Additionally, POCN/COF demonstrated excellent interface charge transfer resistance and photocurrent response. Its hydrogen production rate was remarkably high at 3500 μmol g⁻1 h⁻1, about 1.6 times that of pure COF (2200 μmol g⁻1 h⁻1) and 3.5 times that of the physical mixture (1000 μmol g⁻1 h⁻1), and it also exhibited enhanced stability. This indicates that it can be effectively fabricated into a heterojunction of POCN and COF. The optimal value for adding POCN was approximately 5 wt% of COF. This demonstrates greater activity compared to other composite catalysts made from graphitic carbon nitride and COF. This study presents a valuable approach for fabricating reusable heterojunction photocatalytic systems and efficiently generating hydrogen from natural energy sources.

Hollow Nanobox‐Shaped Cu2‐xS@ZnxCd1‐xS Heterojunction by Light Multireflection with Z‐Scheme Mechanism for Enhanced Photocatalytic Hydrogen Production

AbstractAchieving efficient spatial photoinduced charge separation and light utilization for improving the high photocatalytic activity is still a major obstacle. Here, a Cu2‐xS@ZnxCd1‐xS (Cu2‐xS@ZnCdS) heterojunction is reported featuring a distinctive core–shell hollow nanobox structure. The Cu2‐xS@ZnxCd1‐xS exhibits high photocatalytic activity in hydrogen evolution reaction (HER) at the rate of 8175 µmol∙g−1∙h−1 under visible light irradiation, outperforming pristine ZnCdS nanoparticles and Cu2‐xS hollow nanoboxes. The remarkable activity and outstanding stability of Cu2‐x@ZnCdS are attributed to the development of robust interfacial electric fields, and improved light multireflection absorption efficiency as well as the Z‐scheme mechanism. The electron paramagnetic resonance (EPR) and in situ X‐ray photoelectron spectroscopy (XPS) measurements gave the direct evidence of the formation of the Z‐scheme, which maintained the high redox potentials of each ZnCdS and Cu2‐xS. This study gives the guideline for the design of heterojunction with the Z‐scheme mechanism, leading to the high photocatalytic performance and remarkable stability.

Hydrogen- assisted synthesis of defective triazine/heptazine homostructured nanosheets for efficient CO2photoreduction.

Homostructure construction has been demonstrated to be an effective way for boosting the photocatalytic activity of polymeric carbon nitride. However, the contribution of the intrinsic activity of molecular fragments in the catalytic performance of homostructured carbon nitride is yet to be explored. In this paper, a facile hydrogen-assisted strategy was used to synthesize triazine/heptazine intermolecular homojunctions (g-C3N4(MU-H)) with an ultrathin and defective structure, via the co-pyrolysis of melamine and urea precursors. Experimental characterizations and theoretical calculations revealed the copolymerization of triazine- and heptazine-based carbon nitride generated a homostructured interface with a large build-in electric field for efficient separation of photogenerated carriers. Due to the synergestic effect between the homostructured interface and nitrogen vacancies, as-synethesized g-C3N4(MU-H) exhibited an outstanding activity for photocatalytic CO2 reduction, with a CO yield rate of 14.45 μmol h-1, which was 23.5 and 3.64 times higher than those of bulk g-C3N4 and g-C3N4(M-H) synthesized from a single precursor, respectively. This study provides a new avenue for optimizing the charge separation efficiency of CO2 photoreduction catalysts by constructing intramolecular homojunction.

Donor-Acceptor Type Supra-Carbon-Dots with Long Lifetime Photogenerated Radicals Boosting Tumor Photodynamic Therapy.

Carbon dots (CDs) have gained significant interest because of their potential in biomedical applications. Nevertheless, developing CDs with efficient photoinduced charge separation for tumor photodynamic therapy (PDT) remains a challenge. This study presents a novel class of supra-carbon-dots (supra-CDs) developed by fusing red emissive CDs with 2,3-dicyanohydroquinone (DCHQ) via post-solvothermal treatment. In supra-CDs, the core, acting as electron donors, is formed by assembled CDs with substantial sp2 domains, the fused interface originating from DCHQ with electron-withdrawing groups functions as the electron acceptor. This configuration creates the unique donor-acceptor nanostructure. Upon white light irradiation, the excited electrons from the assembled CDs were transferred to the electron-withdrawing interface, whereas the photogenerated holes were retained within the assembled CDs as radicals, leading to effective photoinduced charge separation. The separated photogenerated electrons then react with oxygen to generate superoxide radicals. Simultaneously, the photogenerated holes undergo oxidation of crucial cellular substrates. This dual action underscores the exceptional cell-killing efficacy of supra-CDs. Moreover, the increased particle sizes (~20 nm) ensure supra-CDs to exhibit a notable capacity for tumor accumulation via the improved permeability and retention effect, thereby achieving satisfactory anti-tumor PDT efficacy in a mouse subcutaneous tumor model.

Prussian Blue Analogues-Derived ZnFe2O4 in CuO/ZnFe2O4 p-n Junction for H2 Production.

ZnFe2O4 is an n-type semiconductor spinel oxide with promising applications in various fields, including photocatalysis. This study reports the successful synthesis of a novel ZnFe2O4 derivative based on Prussian Blue Analogues (PBAs) through an electrosynthesis method. To enhance photocatalytic performance, the synthesized ZnFe2O4 was employed as a cocatalyst in p-n junction materials, specifically CuO/ZnFe2O4. Our findings reveal that introducing ZnFe2O4 could significantly improve the photocatalytic activity and hydrogen (H2) production rate of the CuO/ZnFe2O4 system compared to bare CuO. This enhancement was sustained over an extended operational period, indicating the material's potential for long-term use in photocatalytic applications. The superior performance of the ZnFe2O4 cocatalyst is attributed to its efficient charge separation and improved light absorption properties, which collectively contribute to higher photocatalytic efficiency. This study highlights the potential of PBA-based derivative ZnFe2O4 as an effective cocatalyst in developing advanced photocatalytic systems for sustainable hydrogen production.

Functionalized Modification of Conjugated Porous Polymers for Full Reaction Photosynthesis of H2O2

AbstractModulating the molecular structure to achieve the full reaction including oxygen reduction reaction and water oxidation reaction is a promising strategy for efficient photosynthesis of hydrogen peroxide (H2O2) but remains a challenge. Herein, a triphenylamine and naphthalimide‐based conjugated porous polymers are synthesized with photo oxidation‐reduction structures, then sulfonate (─SO3H) and quaternary ammonium groups are introduced via a post‐modification strategy to produce two photocatalysts named NI‐TPA‐NI‐SO3H and NI‐TPA‐NI‐N, respectively. Introducing charged functional groups has improved the hydrophilicity and oxygen (O2) adsorption, beyond that, the ─SO3H further stabilizes the adsorbed O2 via hydrogen bonding as well as accelerates the photogenerated carrier separation and electron/proton transport that enables full reaction photosynthesis of H2O2. Therefore, motivated by efficient charge separation, stabilized O2 adsorption, and boosted proton‐coupled electron transfer, NI‐TPA‐NI‐SO3H exhibits the highest light‐driven H2O2 production rate among the three photocatalysts, reaching 3.40 mmol g−1 h−1, which is 4.9‐fold of NI‐TPA‐NI. Remarkably, in the presence of ethylenediaminetetraacetic acid disodium salt, its rate significantly enhances to 14.5 mmol g−1 h−1, superior to most reported organic photocatalysts to the best of the knowledge.

Adjusting the Covalency of Metal-Oxygen Bonds in CuBi2O4 by Zn Cation Doping to Achieve Highly Efficient Photocathodes.

Zn doped CuBi2O4 photocathodes are prepared by using a low-cost solution-based spray pyrolysis method. The doping of Zn in CuBi2O4 promotes the separation and migration of carriers and effectively increases the carrier density. Compared with CuBi2O4 alone, the photoelectrochemical activity of the Zn doped CuBi2O4 photoelectrode is improved with the photocurrent density of -0.56 mA/cm2 at 0.4 V vs. RHE. This improvement is due to the lower electronegativity of Zn, which leads to the covalent increase of Cu-O and Bi-O bonds in CuBi2O4, which limits the recombination of photogenerated electrons and holes and improves charge separation and transport. This study presents an innovative approach to enhance the charge separation efficiencies of photocathodes by implementing element doping strategies, which may contribute to further research on photocatalytic water splitting.

Heterojunction Organic Solar Cells with Efficient Charge Mobility and Separation Capabilities Studied by DFT.

The properties of the active layer materials play a decisive role in determining the power conversion efficiency of organic solar cells (OSCs). Chlorophyll and its derivatives are abundant and environmentally friendly functional organic molecular materials. Using density functional theory (DFT) and time-dependent density functional theory (TD-DFT), we have calculated the absorption spectra and their excited state properties based on optimized ground state structures. It was found that bacteriochlorin exhibits superior structural properties, a smaller energy gap and hole reorganization energy, redshifted absorption spectra, and higher hole mobility compared to the donor D18. This suggests that bacteriochlorin exhibits superior donor properties. Comparative studies between o-AT-2Cl and m-AT-2Cl showed that o-AT-2Cl had superior acceptor properties, implying that differences in substitution positions can influence the physicochemical properties of non-fullerene acceptors (NFAs). Subsequently, six bulk heterojunctions (BHJs) were constructed by combining three donors with nonfused ring electron acceptors, o-AT-2Cl and m-AT-2Cl. The bacteriochlorin-based BHJs performed well among them, with BChl3/o-AT-2Cl and BChl4/o-AT-2Cl having the largest interfacial charge separation rate. The results suggested that BHJs composed of bacteriochlorin and NFAs can improve OSCs' photovoltaic performance, providing a feasible scheme for designing efficient OSCs.

Photoelectroreduction CO2 to Ethanol Over BiFeO3 with Synergistic Effect of Self‐Polarization and External Electric Field

The exploitation of semiconductor self‐polarization is an effective mean of improving the efficiency of electron utilization. In this work, the synthesis of BiFeO3 (BFO) samples with varying photoelectric properties is achieved by modulating the concentration of KOH. The experimental results reveal that BFO‐4 (4 m KOH) has excellent carrier efficiency. Interestingly enough, the ethanol yield of up to 7.05 μmol cm−2 h−1 in the photoelectrocatalytic process, which is 1.4 times than that of single electrocatalysis. Based on the characterization data, the external electric field forms a multi‐electric field coupling in the BFO (external electric field can enhance the self‐polarization electric field), which enhances charge separation efficiency and facilitates surface reactions, and the CO2 reduction performance is improved. Finally, the free energy in the key step of CC coupling on the surface of BiFeO3 is calculated by DFT. This study offers a valuable reference for the application of ferroelectric materials in the photoelectrocatalytic reduction of CO2 and the design of catalysts for C2+ products.

Suppressing Nonradiative Recombination through Dielectric Screening of Defects in Crystalline Carbon Nitride for Enhanced Photocatalytic Activity.

Abundant defect-induced nonradiative recombination greatly reduces the charge separation efficiency in photocatalysts. Dielectric screening of defects has been proven to be an effective strategy to improve the charge separation efficiency; however, it has been rarely reported in photocatalysis. Here, a developed calcium poly(heptazine imide) (CaPHI) is utilized as a model photocatalyst to explore the dielectric screening of defects. Through embedding potassium ions in CaPHI, the dipole moment and polarity of the PHI structure are increased, thus enhancing the dielectric constant and enabling the dielectric screening of defects. In addition, compared to the original CaPHI, the optimized Ca/KPHI exhibits a 79.3% reduction in defect capture cross-section, and a decrease in the nonradiative recombination rate from 0.6224 to 0.1452 ns-1, thus achieving an apparent quantum efficiency of 51.4% for H2 production at 420 nm. This proposed dielectric screening strategy effectively addresses the issue of slow carrier transport and separation caused by defect-induced nonradiative recombination in photocatalysts.

Integration of Plasmonic Ag(I) Clusters and Fe(II) Porphyrinates into Metal–Organic Frameworks for Efficient Photocatalytic CO2 Reduction Coupling with Photosynthesis of Pure H2O2

AbstractEfficient photocatalytic CO2 reduction coupled with the photosynthesis of pure H2O2 is a challenging and significant task. Herein, using classical CO2 photoreduction site iron porphyrinate as the linker, Ag(I) clusters were spatially separated and evenly distributed within a new metal–organic framework (MOF), namely Ag27TPyP‐Fe. With water as electron donors, Ag27TPyP‐Fe exhibited remarkable performances in artificial photosynthetic overall reaction with CO yield of 36.5 μmol g−1 h−1 and ca. 100 % selectivity, as well as H2O2 evolution rate of 35.9 μmol g−1 h−1. Since H2O2 in the liquid phase can be more readily separated from the gaseous products of CO2 photoreduction, high‐purity H2O2 with a concentration up to 0.1 mM was obtained. Confirmed by theoretical calculations and the established energy level diagram, the reductive iron(II) porphyrinates and oxidative Ag(I) clusters within an integrated framework functioned synergistically to achieve artificial photosynthesis. Furthermore, photoluminescence spectroscopy and photoelectrochemical measurements revealed that the robust connection of Ag(I) clusters and iron porphyrinate ligands facilitated efficient charge separation and rapid electron transfer, thereby enhancing the photocatalytic activity.

In-Situ Construction of Atomic-Level Fe-O Bond Bridges within Fe2N/g-C3N4 Heterojunction for Efficient Visible-Light-Driven Photocatalytic H2 Production.

The limited active sites and faster photogenerated electron-hole pair recombination rate of g-C3N4 restrict its application in photocatalytic H2 production. Constructing heterojunctions has been shown to improve the spatial (directional) separation of photogenerated electrons and holes. However, due to interface mismatch in traditional heterojunction structures and a lack of precise electron transport channels, the photocatalytic efficiency is limited. Here, we developed a two-step calcination approach to create an Fe2N/g-C3N4 heterojunction linked by Fe-O bonds (named as Fe-OCN). The newly formed Fe-O bonds within the heterojunction can act as atomic-level interface electron transfer channels, directly transferring the photogenerated electrons of g-C3N4 to the reactive center Fe2N, significantly improving the charge transfer rate and utilization, thus promoting visible-light-driven photocatalytic H2 production. The optimal Fe-OCN achieved a H2 production rate of 5986.29 μmol g-1 h-1 under visible light, 13.44 times higher than that of the OCN due to efficient charge separation and transfer capabilities. This work provides a constructive reference for the design and synthesis of organic-inorganic heterojunction with chemically bonded interfaces, establishing quick electron transfer channels, and achieving targeted electron transfer.