Charge Transfer Pathway Research Articles

Construction of direct Z-scheme Co9S8/CdS with tubular heterostructure through the simultaneous immobilization and in-situ reduction strategy for enhanced photocatalytic Cr(VI) reduction under visible light

Tubular Co9S8/CdS heterostructures have been successfully synthesized by in-situ growing CdS onto Co9S8 nanotubes through a simultaneous immobilization and in-situ reduction strategy. It turned out that the so-obtained heterostructure with Co9S8/CdS molar ratio of 1/10 can display a broad light absorption edge and especially much enhanced capacity for photocatalytic reduction of Cr(VI) under visible light. The characterization analysis and experimental results suggested that an interfacial electrostatic field between Co9S8 and CdS elements in the heterostructure could be constructed due to their different Fermi levels, allowing for more quantities of highly reductive electrons to participate in the photocatalytic reaction. Therefore, the so-obtained Co9S8/CdS (1/10) heterostructures could achieve the photocatalytic reduction efficiency of 100% within 20 min, which was more than two and four times larger than that of pristine CdS and Co9S8, respectively. Moreover, the possible photocatalytic reaction mechanism for reducing Cr(VI) was investigated and found to follow the direct Z-scheme charge transfer pathway. This novel fabrication route for composite photocatalysts with tubular heterostructures could lead to the widespread implementations for the elimination of various harmful pollutants in the process of environmental governance.

The role of the plasmon in interfacial charge transfer.

The lack of a detailed mechanistic understanding for plasmon-mediated charge transfer at metal-semiconductor interfaces severely limits the design of efficient photovoltaic and photocatalytic devices. A major remaining question is the relative contribution from indirect transfer of hot electrons generated by plasmon decay in the metal to the semiconductor compared to direct metal-to-semiconductor interfacial charge transfer. Here, we demonstrate an overall electron transfer efficiency of 44 ± 3% from gold nanorods to titanium oxide shells when excited on resonance. We prove that half of it originates from direct interfacial charge transfer mediated specifically by exciting the plasmon. We are able to distinguish between direct and indirect pathways through multimodal frequency-resolved approach measuring the homogeneous plasmon linewidth by single-particle scattering spectroscopy and time-resolved transient absorption spectroscopy with variable pump wavelengths. Our results signify that the direct plasmon-induced charge transfer pathway is a promising way to improve hot carrier extraction efficiency by circumventing metal intrinsic decay that results mainly in nonspecific heating.

Construction of metal-free dual S-scheme heterojunction photocatalysts by rational band alignment for efficient hydrogen evolution

Designing ternary heterojunction photocatalysts is regarded as a compelling approach to attain exceptional photocatalytic activity. However, they always suffer from poor interfacial contact and unclear charge transfer pathways. Herein, a metal-free dual S-scheme heterojunction photocatalyst comprised of black phosphorus (BP), carbon nitride (CN), violet phosphorus (VP) was designed by electrostatic self-assembly. The non-metallic feature of the BPCNVP heterostructure facilitates to form strong interfacial contact by coordinating active P sites in VP and BP with N atoms in CN. Notably, a definite dual S-scheme heterojunction configuration is achieved by rational band alignment of VP and BP, respectively, which significantly boosts the driving force for charge separation. The BPCNVP heterostructure exhibited a hydrogen evolution rate of 1669μmol h-1g−1 with excellent stability, surpassing most reported metal-free photocatalysts. This work demonstrates that the design of dual S-scheme heterojunction by metal-free materials provides valuable insights into the intricate reaction mechanism of ternary heterojunction photocatalysts.

Steric hindrance induced low exciton binding energy enables low‐driving‐force organic solar cells

AbstractExciton binding energy (Eb) has been regarded as a critical parameter in charge separation during photovoltaic conversion. Minimizing the Eb of the photovoltaic materials can facilitate the exciton dissociation in low‐driving force organic solar cells (OSCs) and thus improve the power conversion efficiency (PCE); nevertheless, diminishing the Eb with deliberate design principles remains a significant challenge. Herein, bulky side chain as steric hindrance structure was inserted into Y‐series acceptors to minimize the Eb by modulating the intra‐ and intermolecular interaction. Theoretical and experimental results indicate that steric hindrance‐induced optimal intra‐ and intermolecular interaction can enhance molecular polarizability, promote electronic orbital overlap between molecules, and facilitate delocalized charge transfer pathways, thereby resulting in a low Eb. The conspicuously reduced Eb obtained in Y‐ChC5 with pinpoint steric hindrance modulation can minimize the detrimental effects on exciton dissociation in low‐driving‐force OSCs, achieving a remarkable PCE of 19.1% with over 95% internal quantum efficiency. Our study provides a new molecular design rationale to reduce the Eb.

Bidentate mode coordinated Ti3CNTx MXene-controlled interfacial engineering enables high-performance indoor organic photovoltaic devices

Two-dimensional MXenes demonstrate exceptional optoelectronic properties and tunable surface terminations, making them highly desirable materials for advanced organic photovoltaic (OPV) devices in indoor settings. This study introduced a solution-processed hybrid hole-transport layer (HTL) composed of a blend of 2-(9H-carbazol-9-yl)ethyl]phosphonic acid and titanium carbonitride (2PACz–Ti3CNTx). Introducing Ti3CNTx into 2PACz enhanced the work function for improved hole transport and also induced molecular alignment and interface dipole changes via formation of Ti–O–P covalent bond. This synergistic interaction led to atomic charge polarization, improving the hole-transport kinetics at the heterointerface of 2PACz and Ti3CNTx. Furthermore, the large surface area of conductive MXene and its chemical interaction with π-conjugated 2PACz promote the conductivity and charge-transfer pathways, improving the device’s performance. Consequently, OPV devices employing 2PACz–Ti3CNTx HTLs achieved the maximum power conversion efficiency of 30.3 % under a light-emitting diode lamp (1000 lx) and an output power density of 413 µW·cm−2 under a halogen lamp (1000 lx), corresponding to enhancements of approximately 16 % and 12 %, respectively, compared to OPV devices based on undoped HTLs. These results highlight new opportunities for further exploration of MXene compositions in high-performance indoor OPV devices.

Mott–Schottky heterostructural TiO2@Ag@AgBr nanohybrids for efficient photocatalytic degradation of Cr (VI) and enhanced on-site SERS detection

In the study, a novel ternary composite TiO2@Ag@AgBr was successfully prepared by surface modification of complete Ag layer and AgBr particles for photocatalytic degradation of representative heavy metal ions Cr (VI) and on-site Surface-enhanced Raman spectroscopy (SERS) detection of the Cr (VI) reduction process. The Mott–Schottky heterojunction contained structure exhibited remarkable photocatalytic ability for heavy metal ions Cr (VI) by tuning the ratio of Ag and AgBr, which could reduce Cr (VI) ions within 30 min and the reaction rate constant is 0.12 min−1. The remarkable photo-reduction performance is attributed to synergistic effect among the various components: the AgBr decorated on the surface of TiO2@Ag could significantly enhance the absorption of visible light and generate numerous photoexcited electrons and holes. Furthermore, the complete Ag layer was constructed on the TiO2 microspheres surface to form heterojunctions in the photocatalytic system by in-situ deposition of AgNO3. Mott–Schottky junctions formed between AgBr/Ag and Ag/TiO2 interface which could extend the charge transfer pathway and facilitate separation of photoexcited electrons and holes. The plasmonic metal layer of nano Ag could generate significant surface plasmon resonance (SPR) effect which not only enhanced the absorption of visible light but also exhibited remarkable SERS effect for probe molecules. And an amazing detection limit of 1 × 10–10 M could be obtained when using crystal violet (CV) as probe molecules. In addition, the SERS substrates exhibited significant linear relationship between concentration and SERS signal intensity which ensures the accuracy of quantitative analysis and monitoring photoreduction process. The substrates have good cycling stability, enabling it to be reused for SERS detection many times. Thus, the excellent photocatalytic and SERS performance of Mott–Schottky hetero-structural TiO2@Ag@AgBr substrates shows great potential toward rapidly photocatalytic removal Cr (VI) ions and SERS on-site detection reduction process of Cr (VI) in waste water, which is of great significance to environmental protection and ecological restoration.

Interlayer Delocalized Electrons Activate Basal Plane for Ultrahigh-Current-Density Hydrogen Evolution.

The basal plane of transition metal dichalcogenides (TMDCs) is inert for the hydrogen evolution reaction (HER) due to its low-efficiency charge transfer kinetics. We propose a strategy of filling the van der Waals (vdW) layer with delocalized electrons to enable vertical penetration of electrons from the collector to the adsorption intermediate vertically. Guided by density functional theory, we achieve this concept by incorporating Cu atoms into the interlayers of tantalum disulfide (TaS2). The delocalized electrons of d-orbitals of the interlayered Cu can constitute the charge transfer pathways in the vertical direction, thus overcoming the hopping migration through vdW gaps. The vertical conductivity of TaS2 increased by 2 orders of magnitude. The TaS2 basal plane HER activity was extracted with an on-chip microcell. Modified by the delocalized electrons, the current density increased by 20 times, reaching an ultrahigh value of 800 mA cm-2 at -0.4 V without iR compensation.

The Ferroelectric Effects of Rhombohedral and Tetragonal BiFeO3 in Photoelectrochemical Water Splitting.

The phase of BiFeO3 (BFO) as well as its domain configuration can be tuned by strain engineering. Phase change may greatly influence the properties of the polarization field and hence charge separation. However, the photoelectrochemical properties of different BFO phases have rarely been addressed. Here, the photoelectrochemical study of tetragonal (T-) and rhombohedral (R-) phase BFO films was conducted under visible light illumination. The photocurrent density of R-BFO is 5 times that of T-BFO. A ferroelectric domain study shows that T-BFO features single domain structure in contrast to the polydomain structure of R-BFO. Higher charge separation efficiency is achieved in R-BFO, dominated by the domain walls as conducting pathways for efficient charge separation and transfer. This work provides a fundamental understanding of the photoelectrochemical properties of T- and R-BFO, offering valuable insights for the development of BFO-based materials for solar energy conversion.

Partially amorphization induced S-scheme charge migration in g-C3N4/Mn1.1Fe1.9O4 defective heterojunction for boosting fenton-like degradation of tetracycline under visible light

S-scheme photo-Fenton catalyst is promising in water purification, whereas its rational design and carrier transfer mechanism remain a challenge. Here, a novel defective heterojunction via combining g-C3N4 with amorphous/crystalline Mn1.1Fe1.9O4 (Mn1.1Fe1.9O4-a/c) is fabricated for the degradation of tetracycline. The rich oxygen defects introduced by partially amorphization strategy can regulate the work function of Mn1.1Fe1.9O4-a/c, and switch the charge transfer path of g-C3N4/Mn1.1Fe1.9O4 from type-II to S-scheme, which demonstrates by ultraviolet photoelectron spectroscopy, in-situ kelvin probe force microscopy and density functional theory calculations. Driven by internal electron field, photogenerated electrons can transfer from Mn1.1Fe1.9O4-a/c to g-C3N4, which accelerated the separation of photoexcited carriers and H2O2 activation. Benefiting from the accelerated redox conversion with the action of bimetallic sites, oxygen defects and electrons, the g-C3N4/Mn1.1Fe1.9O4-a/c photocatalyst achieves 94.7 % tetracycline removal within 60 min, and the normalized kinetic rate exceeds reported works by 1–2 orders of magnitude. Multiple synergistic pathways lead to more reactive oxygen species generation, which achieves efficient mineralization of tetracycline (79.9 %). This work provides a simple partially amorphization strategy to switch charge transfer pathway from type-II to S-scheme for efficient water purification.

Anchoring ZnIn2S4 nanosheets on cross-like FeSe2 to construct photothermal-enhanced S-scheme heterojunction for photocatalytic H2 evolution

Rational design of the morphology and heterojunction to accelerate the separation of electron-hole pairs has played an indispensable role in improving the photocatalytic hydrogen evolution. ZnIn2S4 (ZIS) has aroused considerable attention in solar-to-chemical energy conversion due to its remarkable photoelectrical properties and relatively negative energy band, whereas it still suffers from the severe photogenerated carrier recombination and catalyst aggregation. Herein, guided by density functional theory calculations, the constructed FeSe2@ZnIn2S4 (FS@ZIS) heterojunction model has a hydrogen Gibbs free energy closer to zero compared with pure ZIS and FS, which is beneficial for hydrogen adsorption and desorption on the photocatalyst surface. Therefore, a novel cross-like core–shell FS@ZIS Step-scheme (S-scheme) heterojunction was synthesized successfully by in-situ growing ZIS nanosheets on the surface of cross-like FS. The structure with cross-like core–shell morphology not only inhibits the agglomeration of ZIS to increase specific surface area, but also provides a tight interface with S-scheme heterojunction. Moreover, the S-scheme heterojunction with a tight interface can effectively separate electron-hole pairs, leaving photoinduced charges with higher potentials. Furthermore, FS@ZIS-20 possesses exceptional photothermal capabilities, enabling the conversion of optical energy from visible and near infrared light to heat, thereby further enhancing the photocatalysis reaction. As a result, the cross-like core–shell FS@ZIS S-scheme heterojunction exhibits an excellent photocatalytic hydrogen evolution rate (7.640 mmol g−1 h−1), which is 24 times higher than that of pure ZIS (0.319 mmol g−1 h−1) under visible and near infrared light. Furthermore, employing more in-depth density functional theory calculations further investigates the charge transfer pathway of the FS@ZIS S-scheme heterojunction. This work provides insights into the construction of S-scheme heterojunctions with core–shell structure and photothermal effect for photocatalytic evolution hydrogen.

CdS-based Schottky junctions for efficient visible light photocatalytic hydrogen evolution

Heterojunctions photocatalysts play a crucial role in achieving high solar-hydrogen conversion efficiency. In this work, we mainly focus on the charge transfer dynamics and pathways for sulfides-based Schottky junctions in the photocatalytic water splitting process to clarify the mechanism of heterostructures photocatalysis. Sulfides-based Schottky junctions (CdS/CoP and CdS/1T-MoS2) were successfully constructed for photocatalytic water splitting. Because of the higher work function of CdS than that of CoP and 1T-MoS2, the direction of the built-in electric field is from CoP or 1T-MoS2 to semiconductor. Therefore, CoP and 1T-MoS2 can act as electrons acceptors to accelerate the transfer of photo-generated electron on the surface of CdS, thus improving the charge utilization efficiency. Meanwhile, CoP and 1T-MoS2 as active sites can also promote the water dissociation and lower the H+ reduction overpotential, thus contributing to the excellent photocatalytic hydrogen production activity (23.59 mmol·h−1·g−1 and 1195.8 mol·h−1·g−1 for CdS/CoP and CdS/1T-MoS2).

Construction of novel BiOI/CuInS2/ZnO dual S-scheme charge transfer pathway for efficient antibiotic degradation

The present work explored the photocatalytic activity of BiOI–CuInS2–ZnO ternary heterojunction for the photodegradation of the tetracycline (TCl). The bare photocatalysts were prepared via hydrothermal method while the ternary heterojunction was synthesized using simple physical mixing route. The ternary heterojunction of BiOI, CuInS2 and ZnO followed the S-scheme charge transfer pathway exhibiting superior photodegradation ability compared to other synthesized photocatalysts. The attained degradation efficiency of BiOI–CuInS2–ZnO S-scheme ternary heterojunction was 96.75 % within 90 min of light illumination which was much higher than other photocatalysts. Electron spin resonance (ESR) investigations and scavenging experiment indicated that •O2−, and •OH radicals plays an important role in photodegradation of TCl. Furthermore, the structural analysis of synthesized bare photocatalysts was also done via density functional theory (DFT) calculations. The results showed that after the formation of S-scheme heterojunction, the ternary heterojunction showed lower recombination rate (validated via PL analysis) with boosted charge carriers separation rate (confirmed through EIS and TPR analysis) and light absorption ability. This had led to upgradation in photodegradation efficiency of ternary BiOI–CuInS2–ZnO photocatalyst. The reusability test of the photocatalysts confirmed excellent stability of ternary photocatalysts with 90.25 % degradation rate up to five catalytic cycles.

Charge Transport Approaches in Photocatalytic Supramolecular Systems Composing of Semiconductor and Molecular Metal Complex for CO2 Reduction.

The design of photocatalytic supramolecular systems composing of semiconductors and molecular metal complexes for CO2 reduction has attracted increasing attention. The supramolecular system combines the structural merits of semiconductors and metal complexes, where the semiconductor harvests light and undertakes the oxidative site, while the metal complex provides activity for CO2 reduction. The intermolecular charge transfer plays crucial role in ensuring photocatalytic performance. Here, we review the progress of photocatalytic supramolecular systems in reduction of CO2 and highlight the interfacial charge transfer pathways, as well as their state-of-the-art characterization methods. The remaining challenges and prospects for further design of supramolecular photocatalysts are also presented.

A novel multifunctional photocatalytic membrane based on ternary heterojunction TiO2@PDA@BiOBr for biochemical oily wastewater purification

Membrane separation technology is a promising alternative for oily wastewater purification. However, developing membrane for the purification of biochemical oily wastewater is still challengeable. To this aim, a novel multifunctional photocatalytic membrane of PTPB-8 is fabricated by sequentially loading of TiO2, polydopamine (PDA), and BiOBr onto polyacrylonitrile (PAN) nanofibers in situ. PTPB-8 is of water contact angle (WCA) ∼ 0° and underwater oil contact angle (UOCA) 154.7 ± 2.5°, allowing it with outstanding separation and anti-fouling capability, and good reusability for emulsion separation under gravity (i.e., separation efficiency >90 %, permeation flux >300 L m-2h−1, and flux recovery rate >82 % for n-hexane-in-water emulsion after 15 cycles). Under simulated solar light, the ternary heterojunction TiO2@PDA@BiOBr is catalytically active with generating active species and the charge transfer pathway follows the mechanism of Z-type heterojunction. Consequently, PTPB-8 can kill E. coli and S. aureus by ∼ 100 % and degrade tetracycline by >90 %. The application trial results have demonstrated the great potential of PTPB-8 in the purification of biochemical oily wastewater containing bacteria and antibiotics. This study will also give a new idea for enhancing the photocatalytic activity of heterojunctions by PDA decoration.

A hybrid MOFs/Ti-Fe2O3 Z-scheme photoanode with enhanced charge separation and transfer for efficient photoelectrochemical water oxidation

The construction of Z-scheme charge transfer pathways simulating natural photosynthesis is considered a promising method for improving reaction driving forces. Here, we modified the surface of titanium doped Fe2O3 (Ti-Fe2O3) nanorods with NH2-MIL-125(Ti) (Ti-MOFs) and a promising organic-inorganic hybrid Z-scheme NH2-MIL-125(Ti)/Ti-Fe2O3 was successfully prepared. At 1.23 V vs. RHE, the photocurrent density of the composite photoanode reaches 2.67 mA/cm2, which is 5 times higher than that of Ti-Fe2O3. The results of surface photovoltage, ESR and fs-TAS indicate that this improvement is mainly due to the effective Z-scheme charge transfer mechanism providing a strong driving force for charge separation and transport, greatly suppressing carrier recombination and allowing carriers with strong oxidation ability to participate in water oxidation. Meanwhile, NH2-MIL-125(Ti) can enhance light absorption and reduce the surface defect state of Ti-Fe2O3. This study not only provides a feasible approach for the photoanode water splitting of traditional inorganic semiconductor/MOF based heterostructures, but also provides rich and effective means for revealing Z-scheme charge transfer mechanism in depth.

Promoting charge separation in CuInS2/CeO2 photocatalysts by an S-scheme heterojunction for enhanced photocatalytic H2 production

Low charge separation efficiency significantly hampers the performance of photocatalytic hydrogen production. Constructing heterojunctions emerges as a crucial strategy to enhance photocatalytic activity by improving charge separation. An S-scheme heterojunction not only effectively separates the photogenerated charge in composite photocatalysts but also preserves optimal redox capabilities. This study presents the first report of CuInS2/CeO2 (CIS/CeO2) and demonstrates how charge separation within CIS/CeO2 to enhance photocatalytic hydrogen production through the construction of an S-scheme heterojunction. The UV–visible-driven hydrogen production rate of CIS/CeO2 is 4.6 and 9.4 times higher than that of CIS and CeO2 alone, respectively. The improved photocatalytic performance primarily stems from enhanced charge separation promoted by the S-scheme heterojunction. The charge transfer pathway was confirmed as an S-scheme mechanism through a combination of band structure experiments, density functional theory (DFT) calculations on work function, internal electric field, and charge differential density distribution, alongside electron paramagnetic resonance (EPR) experiments. Multiple perspectives were employed to elucidate the reasons behind facilitating efficient charge separation. This research provides valuable insights for advancing photocatalytic performance.

Integrated Photoelectrochemical-SERS Platform Based on Plasmonic Metal-Semiconductor Heterostructures for Multidimensional Charge Transfer Analysis and Enhanced Patulin Detection.

Comprehending the charge transfer mechanism at the semiconductor interfaces is crucial for enhancing the electronic and optical performance of sensing devices. Yet, relying solely on single signal acquisition methods at the interface hinders a comprehensive understanding of the charge transfer under optical excitation. Herein, we present an integrated photoelectrochemical surface-enhanced Raman spectroscopy (PEC-SERS) platform based on quantum dots/metal-organic framework (CdTe/Yb-TCPP) nanocomposites for investigating the charge transfer mechanism under photoexcitation in multiple dimensions. This integrated platform allows simultaneous PEC and SERS measurements with a 532 nm laser. The obtained photocurrent and Raman spectra of the CdTe/Yb-TCPP nanocomposites are simultaneously influenced by variable bias voltages, and the correlation between them enables us to predict the charge transfer pathway. Moreover, we integrate gold nanorods (Au NRs) into the PEC-SERS system by using magnetic separation and DNA biometrics to construct a biosensor for patulin detection. This biosensor demonstrates the voltage-driven ON/OFF switching of PEC and SERS signals, a phenomenon attributed to the plasmon resonance effect of Au NRs at different voltages, thereby influencing charge transfer. The detection of patulin in apples verified the applicability of the biosensor. The study offers an efficient approach to understanding semiconductor-metal interfaces and presents a new avenue for designing high-performance biosensors.

Regulation of Charge Transfer Pathway in Ag-ZnIn2S4 Nanowires for Visible Photodynamic Therapy on Candida Albicans Infections.

Photodynamic therapy (PDT) is receiving extensive attention as an antimicrobial strategy that does not cause drug resistance by reactive oxygen species (ROS). Herein, hierarchical Ag-ZnIn2S4 (Ag-ZIS) core-shell nanowires are synthesized by in situ Metal-Organic Framework derived method for efficient PDT of Candida albicans (C. albicans). The core-shell structure enables spatial synergy strategy to regulate the charge transfer pathway under visible light excitation, in which the Ag nanowires are like the highway for the photogenerated electrons. The enhanced charge carrier separation efficiency greatly increased the chances for the generation of ROS. As expected, the optimized Ag-ZIS nanowires exhibit excellent performance for inactivation of C. albicans under visible light irradiation (λ ≥ 420 nm, 15 min), and the effective sterilization concentration is as high as 107CFU mL-1. Moreover, in vivo infection experiments suggested that the PDT effect of Ag-ZIS nanowires on the mouse wound healing is better than that of the clinical Ketoconazole drug. The PDT antifungal mechanism of Ag-ZIS nanowires is also investigated, and superoxide anion is found to be the predominant active species to causes C. albicans damage. This work provides a new perspective for designing novel interface structures to regulate charge transfer to achieve efficient PDT antifungal therapy.

Phosphotungstic Acid Clusters Decorated Znln2S4 Nanoflowers as Molecular-Scale S-Scheme Heterojunctions for Simultaneous H2 Evolution and Benzyl Alcohol Upgrading.

Simultaneous utilization of photogenerated electrons and holes to achieve overall redox reactions is attractive but still far from practical application. The emerging step (S)-scheme mechanism has proven to be an ideal approach to inhibit charge recombination and supply photoinduced charges with highest redox potentials. Herein, a hierarchical phosphotungstic acid (H3PW12O40, HPW)@Znln2S4 (ZISW) heterojunction was prepared through one-pot hydrothermal method for simultaneous hydrogen (H2) evolution and benzyl alcohol upgrading. The fabricated HPW-based heterojunctions indicated much enhanced visible-light absorption, promoted photogenerated charge transfer and inhibited charge recombination, owing to hierarchical architecture based on visible-light responsive Znln2S4 microspheres, and S-scheme charge transfer pathway. The S-scheme mechanism was further verified by free-radical trapping electron spin resonance (ESR) spectra. Moreover, the wettability of composite heterojunction was improved by the modification of hydrophilic HPW, contributing to gaining active hydrogen (H+) from water sustainably. The optimal ZISW-30 heterojunction photocatalyst indicated an enhanced hydrogen evolution rate of 27.59 mmol g-1 h-1 in benzyl alcohol (10 vol. %) solution under full-spectrum irradiation, along with highest benzaldehyde production rate is 8.32 mmol g-1 h-1. This work provides a promising guideline for incorporating HPW into S-scheme heterojunctions to achieve efficient overall redox reactions.

Constructing an Asymmetric Covalent Triazine Framework to Boost the Efficiency and Selectivity of Visible-Light-Driven CO2 Photoreduction.

The photocatalytic reduction of CO2 represents an environmentally friendly and sustainable approach for generating valuable chemicals. In this study, a thiophene-modified highly conjugated asymmetric covalent triazine framework (As-CTF-S) is developed for this purpose. Significantly, single-component intramolecular energy transfer can enhance the photogenerated charge separation, leading to the efficient conversion of CO2 to CO during photocatalysis. As a result, without the need for additional photosensitizers or organic sacrificial agents, As-CTF-S demonstrates the highest photocatalytic ability of 353.2µmolg-1 and achieves a selectivity of ≈99.95% within a 4h period under visible light irradiation. This study provides molecular insights into the rational control of charge transfer pathways for high-efficiency CO2 photoreduction using single-component organic semiconductor catalysts.