Promote Charge Separation Research Articles

Efficient photocatalytic remediation of persistent organic pollutants using magnetically recoverable spinel manganese ferrite nanoparticles supported on activated carbon

Magnetically recoverable spinel manganese ferrite (MFO) nanoparticles (NPs) supported on activated carbon (AC) (MFC), a promising photocatalyst, were prepared by simple and cost-effective gel combustion. AC supports prevented particle agglomeration and functioned as electron acceptors to promote charge separation on MFO. MFC samples demonstrated significant surface area, paramagnetic characteristics, and visible-light absorption bandgap of 2.02 eV. Pentachlorophenol (PCP) photodegradation using MFC showed degradation efficiency of at least 90 % after 150 min at pH 6.0 with the catalyst dose and PCP concentration of no more than 10 mg.L−1 and 9.0 ppm, respectively. MFC exhibited durability and recyclability with approximately 4 % decrease in degradation efficiency after five reuses while maintaining its material structure. The crucial roles of photo-generated electrons and hydroxyl radicals related to dechlorination and hydroxylation during PCP photodegradation were also highlighted in active species investigations with appropriate scavengers. Subsequently, a plausible PCP photodegradation mechanism with intermediates was proposed.

Bifunctional Co3O4/g-C3N4 Hetrostructures for Photoelectrochemical Water Splitting.

This study explored the synergistic potential of photoelectrochemical water splitting through bifunctional Co3O4/g-C3N4 heterostructures. This novel approach merged solar panel technology with electrochemical cell technology, obviating the need for external voltage from batteries. Scanning electron microscopy and X-ray diffraction were utilized to confirm the surface morphology and crystal structure of fabricated nanocomposites; Co3O4, Co3O4/g-C3N4, and Co3O4/Cg-C3N4. The incorporation of carbon into g-C3N4 resulted in improved catalytic activity and charge transport properties during the visible light-driven hydrogen evolution reaction and oxygen evolution reaction. Optical properties were examined using UV-visible spectroscopy, revealing a maximum absorption edge at 650 nm corresponding to a band gap of 1.31 eV for Co3O4/Cg-C3N4 resulting in enhanced light absorption. Among the three fabricated electrodes, Co3O4/Cg-C3N4 exhibited a significantly lower overpotential of 30 mV and a minimum Tafel slope of 112 mV/dec This enhanced photoelectrochemical efficiency was found due to the established Z scheme heterojunction between Co3O4 and gC3N4. This heterojunction reduced the recombination of photogenerated electron-hole pairs and thus promoted charge separation by extending visible light absorption range chronoamperometric measurements confirmed the steady current flow over time under constant potential from the solar cell, and thus it provided the effective utilization of bifunctional Co3O4/g-C3N4 heterostructures for efficient solar-driven water splitting.

Strong Interactions between Au Nanoparticles and BiVO4 Photoanode Boosts Hole Extraction for Photoelectrochemical Water Splitting.

Strong metal-support interaction (SMSI) is widely proposed as a key factor in tuning catalytic performances. Herein, the classical SMSI between Au nanoparticles (NPs) and BiVO4 (BVO) supports (Au/BVO-SMSI) is discovered and used innovatively for photoelectrochemical (PEC) water splitting. Owing to the SMSI, the electrons transfer from V4+ to Au NPs, leading to the formation of electron-rich Au species (Auδ-) and strong electronic interaction (i.e., Auδ--Ov-V4+), which readily contributes to extract photogenerated holes and promote charge separation. Benefitted from the SMSI effect, the as-prepared Au/BVO-SMSI photoanode exhibits a superior photocurrent density of 6.25 mA cm-2 at 1.23 V versus the reversible hydrogen electrode after the deposition of FeOOH/NiOOH cocatalysts. This work provides a pioneering view for extending SMSI effect to bimetal oxide supports for PEC water splitting, and guides the interfacial electronic and geometric structure modulation of photoanodes consisting of metal NPs and reducible oxides for improved solar energy conversion efficiency.

Strong Interactions between Au Nanoparticles and BiVO4 Photoanode Boosts Hole Extraction for Photoelectrochemical Water Splitting

AbstractStrong metal‐support interaction (SMSI) is widely proposed as a key factor in tuning catalytic performances. Herein, the classical SMSI between Au nanoparticles (NPs) and BiVO4 (BVO) supports (Au/BVO‐SMSI) is discovered and used innovatively for photoelectrochemical (PEC) water splitting. Owing to the SMSI, the electrons transfer from V4+ to Au NPs, leading to the formation of electron‐rich Au species (Auδ−) and strong electronic interaction (i.e., Auδ−‐Ov‐V4+), which readily contributes to extract photogenerated holes and promote charge separation. Benefitted from the SMSI effect, the as‐prepared Au/BVO‐SMSI photoanode exhibits a superior photocurrent density of 6.25 mA cm−2 at 1.23 V versus the reversible hydrogen electrode after the deposition of FeOOH/NiOOH cocatalysts. This work provides a pioneering view for extending SMSI effect to bimetal oxide supports for PEC water splitting, and guides the interfacial electronic and geometric structure modulation of photoanodes consisting of metal NPs and reducible oxides for improved solar energy conversion efficiency.

An All-In-One Integrating Strategy for Designing Platinum(II)-Based Supramolecular Polymers for Photocatalytic Hydrogen Evolution.

Organic polymer photocatalysts have achieved significant progress in photocatalytic hydrogen evolution, while developing the integrated organic polymers possessing the functions of photosensitizer, electron transfer mediator, and catalyst simultaneously is urgently needed and presents a great challenge. Considering that chalcogenoviologens are able to act as photosensitizers and electron-transfer mediators, a series of chalcogenoviologen-containing platinum(II)-based supramolecular polymers is designed, which exhibited strong visible light-absorbing ability and suitable bandgap for highly efficient photocatalytic hydrogen evolution without the use of a cocatalyst. The hydrogen evolution rate (HER) increases steadily with the decrease in an optical gap of the polymer. Among these "all-in-one" polymers, Se-containing 2D porous polymer exhibited the best photocatalytic performance with a HER of 3.09mmolg-1h-1 under visible light (>420nm) irradiation. Experimental and theoretical calculations reveal that the distinct intramolecular charge transfer characteristics and heteroatom N in terpyridine unit promote charge separation and transfer within the molecules. This work could provide new insights into the design of metallo-supramolecular polymers with finely tuned components for photocatalytic hydrogen evolution from water.

Heteroatom‐Doped Ag25 Nanoclusters Encapsulated in Metal–Organic Frameworks for Photocatalytic Hydrogen Production

AbstractAtomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light‐induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg24 (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal–organic framework (MOF), UiO‐66‐NH2, affording MAg24@UiO‐66‐NH2. Strikingly, compared with Ag25@UiO‐66‐NH2, the MAg24@UiO‐66‐NH2 doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg24@UiO‐66‐NH2 presents the best activity up to 3.6 mmol g−1 h−1, far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X‐ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg24 NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z‐scheme heterojunction, when exposed to visible light. This promotes charge separation, along with optimized Ag electronic state, which are responsible for the superior activity in photocatalytic hydrogen production.

Boosted Sacrificial-Agent-Free Selective Photoreduction of CO2 to CH3OH by Rhenium Atomically Dispersed on Indium Oxide.

Solar-energy-driven photoreduction of CO2 is promising in alleviating environment burden, but suffers from low efficiency and over-reliance on sacrificial agents. Herein, rhenium (Re) is atomically dispersed in In2O3 to fabricate a 2Re-In2O3 photocatalyst. In sacrificial-agent-free photoreduction of CO2 with H2O, 2Re-In2O3 shows a long-term stable efficiency which is enhanced by 3.5 times than that of pure In2O3 and is also higher than those on Au-In2O3, Ag-In2O3, Cu-In2O3, Ir-In2O3, Ru-In2O3, Rh-In2O3 and Pt-In2O3 photocatalysts. Moreover, carbon-based product of the photoreduction overturns from CO on pure In2O3 to CH3OH on 2Re-In2O3. Re promotes charge separation, H2O dissociation and CO2 activation, thus enhancing photoreduction efficiency of CO2 on 2Re-In2O3. During the photoreduction, CO is a key intermediate. CO prefers to desorption rather than hydrogenation on pure In2O3, as CO binds to pure In2O3 very weakly. Re strengthens the interaction of CO with 2Re-In2O3 by 5.0 times, thus limiting CO desorption but enhancing CO hydrogenation to CH3OH. This could be the origin for photoreduction product overturn from CO on pure In2O3 to CH3OH on 2Re-In2O3. The present work opens a new way to boost sacrificial-agent-free photoreduction of CO2.

Boosted Sacrificial‐Agent‐Free Selective Photoreduction of CO2 to CH3OH by Rhenium Atomically Dispersed on Indium Oxide

AbstractSolar‐energy‐driven photoreduction of CO2 is promising in alleviating environment burden, but suffers from low efficiency and over‐reliance on sacrificial agents. Herein, rhenium (Re) is atomically dispersed in In2O3 to fabricate a 2Re‐In2O3 photocatalyst. In sacrificial‐agent‐free photoreduction of CO2 with H2O, 2Re‐In2O3 shows a long‐term stable efficiency which is enhanced by 3.5 times than that of pure In2O3 and is also higher than those on Au‐In2O3, Ag‐In2O3, Cu‐In2O3, Ir‐In2O3, Ru‐In2O3, Rh‐In2O3 and Pt‐In2O3 photocatalysts. Moreover, carbon‐based product of the photoreduction overturns from CO on pure In2O3 to CH3OH on 2Re‐In2O3. Re promotes charge separation, H2O dissociation and CO2 activation, thus enhancing photoreduction efficiency of CO2 on 2Re‐In2O3. During the photoreduction, CO is a key intermediate. CO prefers to desorption rather than hydrogenation on pure In2O3, as CO binds to pure In2O3 very weakly. Re strengthens the interaction of CO with 2Re‐In2O3 by 5.0 times, thus limiting CO desorption but enhancing CO hydrogenation to CH3OH. This could be the origin for photoreduction product overturn from CO on pure In2O3 to CH3OH on 2Re‐In2O3. The present work opens a new way to boost sacrificial‐agent‐free photoreduction of CO2.

Enhancing Iron(III) Oxide Photoelectrochemical Water Splitting Performance Using Defect Engineering and Heterostructure Construction.

Fe2O3 is a promising semiconductor for photoelectrochemical (PEC) water decomposition. However, severe charge recombination problems limit its applications. In this study, a F-Fe2O3-x/MoS2 nanorod array photoanode was designed and prepared to facilitate charge separation. Detailed characterization and experimental results showed that F doping in Fe2O3 regulated the electronic structure to improve the conductivity of Fe2O3 and induced abundant oxygen vacancies to increase the carrier concentration and promote charge separation in bulk. In addition, the internal electric field between F-Fe2O3-x and MoS2 facilitated the qualitative transfer of the photogenerated charge, thus inhibiting their recombination. The synergistic effect between the oxygen vacancy and F-Fe2O3-x/MoS2 heterojunction significantly enhanced the PEC performance of Fe2O3. This study provides a universal strategy for designing other photoanode materials with high-efficiency charge separation.

Enhanced hydrogen evolution and tetracycline degradation by a Z-scheme g-C3N4 nanosheets loaded CeO2 photocatalyst under visible light irradiation

In the quest to enhance photocatalytic performance, structural regulation and interface engineering stand out as effective strategies for amplifying active sites and fostering the separation of photogenerated electron-hole pairs. In this study, a pioneering approach was employed, utilizing a straightforward two-step calcination method to prepare a novel photocatalyst: porous graphite carbon nitride (g-C3N4, CN) nanosheets (NS) loaded with mesoporous cerium oxide (CeO2/CNNS). The distinctive architecture of CeO2/CNNS not only elevates the specific surface area and catalytic active sites but also facilitates efficient mass transfer. Experimental results and density functional theory (DFT) calculations corroborate the existence of an internal electric field (IEF) within the Z-scheme heterojunction formed by uniformly dispersed CeO2 and CNNS. This IEF proves pivotal in promoting charge separation and migration, thereby maintaining robust redox capabilities. Under visible light irradiation, CeO2/CNNS demonstrates an impressive 4.2-fold increase in the hydrogen production rate compared to bulk g-C3N4 (BCN), coupled with a 48.5% boost in the photocatalytic degradation rate constant (k) of tetracycline (TC). This study not only unveils the innovative design of CeO2/CNNS but also paves the way for a fresh perspective on the design and preparation of multifunctional photocatalysts.

Conjugated Polythiophene Frameworks as a Hole‐Selective Layer on Ta3N5 Photoanode for High‐Performance Solar Water Oxidation

AbstractDiscovering a competent charge transport layer promoting charge separation in photoelectrodes is a perpetual pursuit in photoelectrochemical (PEC) water splitting to achieve high solar‐to‐hydrogen (STH) conversion efficiency. Here, a conjugated polythiophene framework (CPF‐TTB) on Ta3N5 is elaborately electropolymerized, substantiating the hole transport behavior in their heterojunction. Tailored band structures of the CPF‐TTB/Ta3N5 reinforce the separation of photogenerated carriers, elevating a fill factor of the photoanode modified with a cocatalyst. The enhanced hole extraction enables the NiFeOx/CPF‐TTB/Ta3N5/TiN photoanode to generate a remarkable water oxidation photocurrent density of 9.12 mA cm−2 at 1.23 V versus the reversible hydrogen electrode. A tandem device combining the photoanode with a perovskite/Si solar cell implements an unbiased solar water splitting with a STH conversion efficiency of 6.26% under parallel illumination mode. This study provides novel strategies in interface engineering for metal nitride‐based photoelectrodes, suggesting a promise of the organic–inorganic hybrid photoelectrode for high‐efficiency PEC water splitting.

Heteroatom-Doped Ag25 Nanoclusters Encapsulated in Metal-Organic Frameworks for Photocatalytic Hydrogen Production.

Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light-induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg24 (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal-organic framework (MOF), UiO-66-NH2, affording MAg24@UiO-66-NH2. Strikingly, compared with Ag25@UiO-66-NH2, the MAg24@UiO-66-NH2 doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg24@UiO-66-NH2 presents the best activity up to 3.6 mmol g-1 h-1, far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X-ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg24 NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z-scheme heterojunction, when exposed to visible light. This promotes charge separation, along with optimized Ag electronic state, which are responsible for the superior activity in photocatalytic hydrogen production.

A novel ZnCo2O4/BiOBr p-n/Z-scheme heterojunction photocatalyst for enhancing photocatalytic activity.

In this study, we developed a novel p-n/Z-scheme heterojunction photocatalyst, ZnCo2O4/BiOBr (ZCo/BB), through a straightforward and safe hydrothermal-calcination-solvent thermal method. The composite photocatalyst demonstrated exceptional photocatalytic efficacy, particularly when the mass ratio of ZnCo2O4 was 25% (referred to as 25% ZCo/BB). Structural characterization and electrochemical analysis revealed that 25% ZCo/BB exhibited a larger specific surface area and a faster electron transfer rate. Under visible light exposure for 30min, methylene blue (MB) degradation reached 92%, and the reaction rate constants were 8.2 and 3.7 times higher than those observed for individual ZnCo2O4 and BiOBr, respectively. Furthermore, the 25% ZCo/BB demonstrated exceptional photocatalytic stability over four cycles, maintaining over 80% MB degradation after each cycle. The outstanding photocatalytic activity was attributed to the p-n/Z-scheme heterojunction construction, which promoted charge separation and inhibited carrier recombination. In addition, ·OH and h+ were the major active species in photocatalysis, and · was identified as a secondary active species. This work presents an efficient heterojunction photocatalyst for the degradation of organic wastewater.

Photocatalytic enhancement of n-p-n ternary heterostructure of BiVO4/rGO/BiOBr for RhB degradation under visible light irradiation

Herein, the ternary phase of n-type BiVO4/p-rGO/n- BiOBr (3%rGO/1V2Br) was synthesized by one-pot hydrothermal method and firstly evaluated for its potential application in photocatalysis. The 3 %rGO/1V2Br shows the highest photocatalytic efficiency of 100 % compared to that of the binary BiVO4/BiOBr (1V2Br), single BiVO4, and BiOBr phases of 87 %, 25 %, and 55 % respectively. Scanning electron microscope and X-ray diffraction results suggest successful preparation of the ternary BiVO4/rGO/BiOBr phase and close contacts among the three components. Chemical interactions at heterointerface, supported by new V-C bond formation and binding energy shift from X-ray photoelectron spectroscopy study, could facilitate charge transfer and promote charge separation as evidenced by photoluminescence and photoelectrochemical studies. Photocatalytic mechanism and energy band alignment are proposed based on Mott-Schottky, UV–vis diffuse reflectance, and scavenger trapping experiments.

Modulating the electron interaction of Cu-Ni hybrid sites for boosting photocatalytic hydrogen evolution over Al-doped SrTiO3

Cocatalysts play a pivotal role in enhancing the efficiency of photocatalytic water splitting. In this study, we introduced a novel and straightforward pre-impregnation strategy to anchor a CuNi dual cocatalyst onto the surface of Al-doped SrTiO3 (Al-STO), coupled with photodeposition. This approach led to a remarkable 11.07-fold (77.5 µmol/h) increase in hydrogen evolution performance compared to the conventional photodeposition method for decorating with CuNi dual cocatalysts. Not only that, after the 18 h cycle experiment, the catalyst still maintains high activity and high stability similar to that of precious metals, which overcomes the defects of poor stability and short life of non-precious metals. This strategy capitalizes on the pre-adsorption of cocatalyst precursor ions on the Al-STO support via impregnation, enhancing both the adsorption energy and capacity between the precursor ions and the active sites. Detailed characterizations have revealed a strong electronic interaction within the Cu-Ni structure and improved interfacial coupling between CuNi and Al-STO. This not only significantly promotes charge separation and transfer but also provides a plethora of active sites for the photocatalytic generation of H2. Moreover, extensive theoretical calculations have provided deep insights into the reaction mechanism of the CuNi system and elucidated the reasons behind the varying degrees of activity enhancement across different cocatalyst architectural systems.

Quantum Dots Mediated Heterojunction Coupling MoSe2 Photoanode for Photoelectrochemical Water Splitting.

Graphene quantum dots (GQDs) possess the photosensitive absorption for photoelectrochemical hydrogen evolution owing to special band structures, whereas they usually confront with photo-corrosion or undesired charge recombination during photoelectrochemical reactions. Hence, we establish the heterojunction between GQDs and MoSe2 sheets via a hydrothermal process for improved stability and performance. Photoanodic water splitting with hydrogen evolution boosted by the heteroatom doped N,S-GQDs/MoSe2 heterojunction has been attained due to the abundant active sites, promoted charge separation and transfer kinetics with reduced energy barriers. Diphasic 1T and 2H MoSe2 sheet-hybridized quantum dots contribute to the Schottky heterojunction, which can play a key role in expedited carrier transport to inhibit accumulative photo-corrosion and increase photocurrent. Heteroatom dopants lead to favored energy band matching, bandgap narrowing, stronger light absorption and high photocurrent density. The external quantum efficiency of the doped heterojunction has been elevated twofold over that of the non-doped pristine heterojunction. Modification of the graphene quantum dots and MoSe2 heterojunction demonstrate a viable and adaptable platform toward photoelectrochemical hydrogen evolution processes.

Comprehensive investigations into the synergy of S-scheme heterojunction between nitrogen-doped ZnO nano-rods and g-C3N4 nanosheets for improved photocatalytic degradation

In this work, N-ZnO nanorods decorated with 2D g-C3N4 prepared by hydrothermal synthesis are studied for their synergistic effect in regard to enhanced photocatalytic activity. The synthesized material is characterized with XRD, FESEM, EDX, TEM and HR-TEM to perform the structural, morphological and elemental analysis along with XPS and FTIR for tracking sample purity and to study the elemental composition on the surface of the material; UV–Visible spectroscopy and PL spectroscopy for investigating the optical properties, bandgap calculation and to inquire about the defects in the structure. N-ZnO/g-C3N4 shows remarkable photocatalytic MB degradation ability upon solar irradiation which is 2.8 and 1.2 times exceeds than pristine ZnO and g-C3N4, attributed to the s-scheme mechanism for charge migration. The construction of s-scheme heterojunction among N-ZnO and g-C3N4 generates an internal electric field that saliently promotes charge separation at the interface. Furthermore, post-stability test for 8 cycles with XRD and FTIR analysis to verify the material integrity is presented. The scavenger experiments revealed the involved active species. This research does seem to pique interest in the creation of cutting-edge photocatalysts that utilize the solar spectrum to remove harmful organic dyes from water.

Regulation of phase composition and oxygen vacancy in hydrothermally synthesized NaNbO3 nanowire and its enhanced piezocatalytic activity for antibiotic elimination

Piezocatalysis based on piezoelectricity has shown potential for environmental remediation and production of clean energy, which, however, cannot meet the standard of practical application due to its insufficiency. Herein, we successfully regulated phase composition (monoclinic, orthogonal and amorphous) in NaNbO3 nanowire through controlling the annealing temperature and time, where the decreased structural symmetry at the two-phase interface improved the piezoelectricity and meanwhile the increased oxygen vacancies in amorphous structure acted as active sites to promote charge separation and oxygen adsorption. As a result, the optimized NaNbO3 sample annealed under 350 °C for 2 h presented much higher piezocatalytic activity for antibiotic degradation than the pristine NaNbO3. In detail, the effects of pH, antibiotic concentration, antibiotic type and reusability on the piezocatalytic performance were systematically studied. The enhanced piezocatalytic activity of the annealed NaNbO3 was revealed through testing piezoelectric coefficient, surface potential, piezoelectric current response and generation rate of active oxygen species, and therefore a possible piezocatalytic mechanism was proposed. Based on the determined intermediate products in the antibiotic degradation process, the reasonable degradation pathway was suggested.

IGZO Phototransistor with Ultrahigh Sensitivity at Broad Spectrum Range (450–950 nm) Realized by Incorporating PM6:Y6 Bulk Heterojunction

AbstractAmong various photoresponsive materials, organic materials have gained interest due to their low cost, large‐scale yields, and compatibility with flexible substrates. However, their low photoresponsivity compared to inorganic counterparts has been consistently pointed out as a limitation. To address this issue, a highly photoresponsive PM6:Y6/IGZO hybrid phototransistor is presented with a broad spectral range of 450–950 nm. The photoresponse of the device is enhanced by controlling the PM6:Y6 blending ratio, active layer thickness, and solvent additive treatment. The PM6:Y6 blending ratio and thickness are optimized to promote charge separation and efficient charge transport, leading to a significant increase in photoresponsivity. Moreover, solvent additives are employed to improve the crystallinity of the PM6:Y6 film, which further enhanced the charge transport. As a result, the PM6:Y6/IGZO hybrid phototransistor exhibited exceptional performance, with an ultrahigh photoresponsivity of 2.2 × 108 A W−1 and specific detectivity of 9.8 × 1016 Jones under 750 nm light with an intensity of only 1.03 nW cm−2. These results highlight the potential of organic materials in developing high‐performance phototransistors.

P-N Bonds-Mediated Atomic-Level Charge-Transfer Channel Fabricated between Violet Phosphorus and Carbon Nitride Favors Charge Separation and Water Splitting.

Heterostructures are widely employed in photocatalysis to promote charge separation and photocatalytic activity. However, their benefits are limited by the linkages and contact environment at the interface. Herein, violet phosphorus quantum dots (VPQDs) and graphitic carbon nitride (g-C3N4) are employed as model materials to form VPQDs/g-C3N4 heterostructures by a simple ultrasonic pulse excitation method. The heterostructure contains strong interfacial P-N bonds that mitigate interfacial charge-separation issues. P-P bond breakage occurs in the distinctive cage-like [P9] VPQD units during longitudinal disruption, thereby exposing numerous active P sites that bond with N atoms in g-C3N4 under ultrasonic pulse excitation. The atomic-level interfacial P-N bonds of the Z-scheme VPQDs/g-C3N4 heterostructure serve as photogenerated charge-transfer channels for improved electron-hole separation efficiency. This results in excellent photocatalytic performance with a hydrogen evolution rate of 7.70mmolg-1h-1 (over 9.2 and 8.5 times greater than those of pure g-C3N4 and VPQDs, respectively) and apparent quantum yield of 11.68% at 400nm. Using atomic-level chemical bonds to promote interfacial charge separation in phosphorene heterostructures is a feasible and effective design strategy for photocatalytic water-splitting materials.