Photoexcited Electrons Research Articles

Role of metal (Fe(III), Zn(II), and Co(III)) and porphyrin in enhancing photocatalytic performance of MTCPP/TiO2 photocatalysts

Metal-porphyrin complexes modified TiO2 photocatalyst, called MTCPP@P25, shows excellent photocatalytic activity under visible light irradiation. Metal-porphyrin is successfully utilized to broaden the photo response range of TiO2 from ultraviolet (3.2 eV) to visible light (2.43 eV to 2.65 eV) resulting in significant enhancement of photocatalytic efficiency. MTCPP@P25 exhibited the higher photocatalytic activity than bare TiO2. Additionally, introduction of different metals, like Fe, Zn, and Co into porphyrin ring can effectively adjust the photocatalytic activity of MTCPP@P25 due to the increasing the electron density of porphyrin rings. The degradation order for MB followed as FeTCPP@P25≧ZnTCPP@P25 > CoTCPP@P25. This finding demonstrated that FeTCPP@P25 and ZnTCPP@P25 possess higher photo-excited electrons under visible irradiation resulting in higher photocatalytic performance. Based on the PL and EIS analysis, FeTCPP@P25 exhibited longest lifetime and fast electron transition compared to ZnTCPP@P25. The spent FeTCPP@P25 were reusable after three cycles, the efficiency remained at approximately 80 %.

An ultrahigh hydrogen production rate of photocatalyst Fe2S2(CO)6/MoS2/CdS integrated mimic hydrogenase and capacitor for H2 evolution with longer lifetime of photoexcited electrons

The hydrogenase mimics provide an innovative strategy for photocatalytic hydrogen production; however, the efficiency mismatch between electron production and utilization results in low hydrogen production rate. Herein, we report the integration of non-noble metal cocatalyst MoS2 decorated with hydrogenase model complex Fe2S2(CO)6 and CdS QDs to assemble Fe2S2(CO)6/MoS2/CdS QDs, which exhibited an excellent hydrogen production rate of 10,836 μmol/g/h. This rate is 127.4, 9.1, and 1.6 times higher than that of CdS QDs, Fe2S2(CO)6/CdS QDs, and MoS2/CdS QDs, respectively. In comparison to CdS or MoS2/CdS, transient photovoltage (TPV) measurements revealed that the photovoltage response of Fe2S2(CO)6/MoS2/CdS increased numerically by 3.3 times; meanwhile, Fe2S2(CO)6/MoS2/CdS significantly extended the lifetime of photo-generated electrons. The excellent performance was attributed to the distinct capacitance effect and functional active site of Fe2S2(CO)6/MoS2/CdS, which boosted electron storage and redistribution at the interface to alleviate recombination losses and facilitate hydrogen production.

Synergistic redox reactions toward co‐production of H2O2 and value‐added chemicals: Dual‐functional photocatalysis to achieving sustainability

AbstractIntegrating H2O2 evolution with oxidative organic synthesis in a semiconductor‐driven photoredox reaction is highly attractive since H2O2 and high‐value chemicals can be concurrently produced using solar light as the only energy input. The dual‐functional photocatalytic approach, free from sacrificial agents, enables simultaneous production of H2O2 and high‐value organic chemicals. This strategy promises a green and sustainable organic synthesis with minimal greenhouse gas emissions. In this review, we first elucidate the fundamental principles of cooperative photoredox integration of H2O2 synthesis and selective organic oxidation with simultaneous utilization of photoexcited electrons and holes over semiconductor‐based photocatalysts. Afterwards, a thorough review on the recent advancements of cooperative photoredox synthesis of H2O2 and value‐added chemicals is presented. Notably, in‐depth discussions and insights into the techniques for unravelling the photoredox reaction mechanisms are elucidated. Finally, critical challenges and prospects in this thriving field are comprehensively discussed. It is envisioned that this review will serve as a pivotal guidance on the rational design of such dual‐functional photocatalytic system, thereby further stimulating the development of economical and environmentally benign H2O2 and high‐value chemicals production.

Facilitated Unidirectional Electron Transmission by Ru Nano Particulars Distribution on MXene Mo2C@g-C3N4 Heterostructures for Enhanced Photocatalytic H2 Evolution.

Precious metals exhibit promising potential for the hydrogen evolution reaction (HER), but their limited abundance restricts widespread utilization. Loading precious metal nanoparticles (NPs) on 2D/2D heterojunctions has garnered considerable interest since it saves precious metal consumption and facilitates unidirectional electron transmission from semiconductors to active sites. In this study, Ru NPs loaded on MXenes Mo2C by an in-site simple strategy and then formed 2D/2D heterojunctions with 2D g-C3N4 (CN) via electrostatic self-assembly were used to enhance photocatalytic H2 evolution. Evident from energy band structure analyses such as UV-vis and TRPL, trace amounts of Ru NPs as active sites significantly improve the efficiency of the hydrogen evolution reaction. More interestingly, MXene Mo2C, as substrates for supporting Ru NPs, enriches photoexcited electrons from CN, thereby enhancing the unidirectional electron transmission. As a result, the combination of Ru-Mo2C and CN constructs a composite heterojunction (Ru-Mo2C@CN) that shows an improved H2 production rate at 1776.4 μmol∙g-1∙h-1 (AQE 3.58% at 400 nm), which is facilitated by the unidirectional photogenerated electron transmission from the valence band on CN to the active sites on Ru (CN→Mo2C→Ru). The study offers fresh perspectives on accelerated unidirectional photogenerated electron transmission and saved precious metal usage in photocatalytic systems.

Novel superhydrophobic sponge with flower-like architecture for oily emulsion separation and organic pollutants photodegradation

Design functionalized absorbent materials that fulfillment complex requirements in sophisticated water-treatment fields remains challenging. In this paper, a novel superhydrophobic/superoleophilic sponge with flower-like channel structures and a photodegradation functionality was fabricated via in-situ chelation of zinc oxide (ZnO) and nano-Ag particles. After low surface energy modification with POTS, the as-prepared sponge displayed remarkable superwettability, with a water contact angle (WCA) of 158.8° ± 1.3°. This endowed it with the ultrafast, selective absorption of diverse oils that are 33.9–135.2 times of their own weight. The prepared sponge’s emulsified oil separation efficiency can reach 99.87%, owing to its superhydrophobic/superoleophilic properties and the electrostatic attraction demulsification, guiding effect of ZnO layer crystal plane. Furthermore, the construction of Schottky barrier at the ZnO@Ag interface reduced the recombination rate of photoexcited electrons and electron-holes. Thereby, the prepared sponge’s photodegradation efficiency reached up to 97.07% after 4 h sunlight irradiation. Notably, the stress attenuation of the prepared sponge was only 14.6% after 100 absorption cycles, indicating its excellent mechanical stability. Moreover, the prepared sponge showed excellent environmental tolerance under severe conditions with its WCA stably exceeding 150.0°. Thus, this durable superwetting sponge can be effectively used for oil/water emulsion separation and organic pollutant degradation.

Defective Cd0.3Zn0.7S / 1 T-2 H MoS2 Z-scheme heterojunctions: Rational design with efficient charge transfer for enhanced photocatalytic H2 generation

CdxZn1-xS photocatalysts have received increasing attention due to their better Photocatalytic hydrogen evolution. In this paper, Cd0.3Zn0.7S nanoparticles decorated by a small amount of 1 T-2 H mixed-phase MoS2 nanosheets ((X%) MoS2/Cd0.3Zn0.7S) were prepared by a secondary hydrothermal-hydrothermal precipitation method. The Z-scheme heterojunction between 2 H-MoS2 and Cd0.3Zn0.7S can effectively inhibit the recombination of photogenerated carriers in the photocatalysts, and 1 T-MoS2 with metallic properties in the mixed phase mainly acts as a bridge for the transfer of photoexcited electrons. Therefore, under UV–visible irradiation, when Na2S/Na2SO3 is used as the sacrificial agent, the photocatalytic hydrogen evolution reaction (HER) activity of 0.75% MoS2/Cd0.3Zn0.7S reaches 11172 umol.g−1.h−1, which is 1.8 fold higher than that of Cd0.3Zn0.7S. The apparent quantum yields of 0.75% MoS2/C3Z7S at 370 nm and 420 nm wavelength are 50.6% and 7.2%, respectively. There are no significant changes in the hydrogen production after three cycles, indicating that the 0.75% MoS2/C3Z7S sample has excellent stability. This study provides a facile and low-cost strategy for constructing composite photocatalysts with highly efficient steady hydrogen production activity.

Mediation of Interfacial Mo2C Bridging Effect in MoS2@Carbon Colloid Dots Featuring Improved Photovoltaic Performances of Si‐Based Hybrid Solar Cells

AbstractAdvances in silicon‐based hybrid solar cells with high photovoltaic performance, low synthetic cost, and sound environmental resistance are emerged as potential candidate for solar conversion. Solution‐processed few‐layer MoS2 sheets are regarded as compelling constitutes that paves ways for tailoring the solar harvesting capability; yet the improvement on charge separation of photoexcited carriers remains demanded, and the lack of environmental stability due to intentionally grabbing electrons from adsorbed moistures constrains the scope of practical assessment. In this work, the employment of MoS2/Mo2C/carbon colloid dots (CCDs) heterostructures within PEDOT:PSS matrix is invoked, where the transfer of photoexcited electrons from MoS2 is mediated with Mo2C electron‐transport channels, which further couple out the creation of positive trions by combining with defect‐bound excitons at CCD surfaces. These features dynamically involve with slow recombination probability and further improve the photovoltaic gain. Thus, the noticeable improvement of conversion efficiency of 16.1% with 1.6 times of efficiency enhancement outperforming the bare conventional hybrid solar cells is accomplished, and further exhibits a sound long‐term stability, which opens new avenues for exploiting the photophysical bound‐carrier transition on advanced photovoltaic applications.

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

Inductive effect in amino functionalized ionic liquids modified TS-1 nanosheets for efficiently sunlight-driven CO2 reduction

Photocatalytic technology for converting CO2 into useful chemicals or clean energy is an effective strategy to solve today's energy and environmental problems. In this study, we present a direct photocatalytic pathway for the conversion of CO2-to-CO involving the formation and activation of carboxyl intermediates over amino-functionalized ionic liquid (3-aminopiperidine hydrochloride, [3APip]Cl)-modified titanium silicalite-1 (TS-1) molecular sieve nanosheets. Various in-situ characterizations reveal that the key to activating this pathway lies in the CO2 adsorption capacity and the efficiency of photoexcited charge migration induced by [3APip]Cl in the hybrid catalyst. In the above catalytic pathway, CO2 molecules are first adsorbed on the surface of the [3APip]Cl/TS-1 hybrid catalyst under the induction of amino groups in the ionic liquid. Then, these adsorbed CO2 are activated and transformed into carboxyl intermediate, which can be further converted into CO and CH4 through photoexcited electrons captured by [3APip]Cl. Based on the results of CO2 reduction performance, the optimized [3APip]Cl/TS-1 hybrid catalyst achieves a 6-fold increase, and the CO selectivity is 83.0%. This research provides new insights into the CO2 reduction pathway in mild conditions and emphasizes the importance of the adsorption–activation tandem process for enhancing photoactivity and selectivity.

Electron injection and defect passivation for high-efficiency mesoporous perovskite solar cells.

Printable mesoscopic perovskite solar cells (p-MPSCs) do not require the added hole-transport layer needed in traditional p-n junctions but have also exhibited lower power conversion efficiencies of about 19%. We performed device simulation and carrier dynamics analysis to design a p-MPSC with mesoporous layers of semiconducting titanium dioxide, insulating zirconium dioxide, and conducting carbon infiltrated with perovskite that enabled three-dimensional injection of photoexcited electrons into titanium dioxide for collection at a transparent conductor layer. Holes underwent long-distance diffusion toward the carbon back electrode, and this carrier separation reduced recombination at the back contact. Nonradiative recombination at the bulk titanium dioxide/perovskite interface was reduced by ammonium phosphate modification. The resulting p-MPSCs achieved a power conversion efficiency of 22.2% and maintained 97% of their initial efficiency after 750 hours of maximum power point tracking at 55 ± 5°C.

Light Enables the Cathodic Interface Reaction Reversibility in Solid-State Lithium-Oxygen Batteries.

Limited triple-phase boundaries arising from the accumulation of solid discharge product(s) in solid-state cathodes (SSCs) pose a challenge to high-property solid-state lithium-oxygen batteries (SSLOBs). Light-assisted SSLOBs have been gradually explored as an ingenious system; however, the fundamental mechanisms of the SSCs interface behavior remain unclear. Here, we discovered that light assistance can enhance the fast inner-sphere charge transfer in SSCs and regulate the discharge products with spherical particles generated via the surface growth model. Moreover, the high photoelectron excitation and transportation capabilities of SSCs can retard cathodic catalytic decay by avoiding structural degradation of the cathode with a reduced charge voltage. The light-induced SSLOBs exhibited excellent stability (170 cycles) with a low discharge-charge polarization overpotential (0.27 V). Furthermore, transparent SSLOBs with exceptional flexibility, mechanical stability, and multiform shapes were fabricated for theory-to-practical applications in sunlight-induced batteries. Our study opens new opportunities for the introduction of solar energy into energy storage systems.

Light Enables the Cathodic Interface Reaction Reversibility in Solid‐State Lithium‐Oxygen Batteries

AbstractLimited triple‐phase boundaries arising from the accumulation of solid discharge product(s) in solid‐state cathodes (SSCs) pose a challenge to high‐property solid‐state lithium‐oxygen batteries (SSLOBs). Light‐assisted SSLOBs have been gradually explored as an ingenious system; however, the fundamental mechanisms of the SSCs interface behavior remain unclear. Here, we discovered that light assistance can enhance the fast inner‐sphere charge transfer in SSCs and regulate the discharge products with spherical particles generated via the surface growth model. Moreover, the high photoelectron excitation and transportation capabilities of SSCs can retard cathodic catalytic decay by avoiding structural degradation of the cathode with a reduced charge voltage. The light‐induced SSLOBs exhibited excellent stability (170 cycles) with a low discharge–charge polarization overpotential (0.27 V). Furthermore, transparent SSLOBs with exceptional flexibility, mechanical stability, and multiform shapes were fabricated for theory‐to‐practical applications in sunlight‐induced batteries. Our study opens new opportunities for the introduction of solar energy into energy storage systems.

Visible light-assisted S-scheme p- and n-type semiconductors anchored onto graphene for increased photocatalytic H2 production via water splitting

This work reports on photocatalytic hydrogen (H2) production via water splitting by synthesizing CuO and ZnO semiconductors anchored onto graphene by varying the mass ratios of CuO and ZnO into the graphene matrix. The high H2 production performance for binary nanocomposite (CuO/ZnO) compared to its components confirms the synergistic effect between ZnO and CuO nanoparticles. Introducing 10 wt% graphene into CuO and ZnO displayed the highest H2 production reaching to 37.2 mmol/g.h, which was 3.29 times higher than pristine binary nanocomposite (CuO/ZnO). The graphene played a critical role in enhancing the photocatalytic activity of CuO and ZnO towards H2 production, owing to the accelerated transport of photo-excited electrons between the semiconductors. Under the optimum conditions, H2 production by 10 % of graphene into CuO and ZnO reached a maximum value of 48.6 mmol/g.h when Na2S/Na2SO3 was used as a sacrificial agent. The charge transfer carriers were monitored to explain the photocatalytic H2 production mechanism based on the optical property characterizations and S-scheme heterojunction system. An excellent reusability was achieved after five consecutive cycles of H2 production reaction. The outcome of this research introduces a reusable and effective catalyst with a facile and easy configuration for energy production applications and confirms that the decoration of semiconductors on graphene could be a promising strategy for highly-efficient photocatalytic H2production. Furthermore, by offering a clean alternative to fossil fuels and reducing greenhouse gas emissions—especially when produced from renewable sources—hydrogen can significantly contribute to achieving sustainable development goal 7 (SDG 7), thus advancing toward a more sustainable, equitable future.

A general strategy for the enhanced H2 production performance of CdS/noble metal sulfide nanorods photocatalysts by cation exchange

In this work, we report a series of noble metal (Ag, Au, Pt, etc.) sulfides that act as co-catalysts anchoring on CdS nanorods (NRs) obtained via a cation exchange strategy to promote photocatalytic hydrogen evolution. CdS NRs are first generated via a hydrothermal routine, noble metal sulfides are then in-situ grown on CdS NRs by a cation exchange method. CdS/Ag2S, CdS/Au2S and CdS/PtS NRs show improved hydrogen production rates (2506.88, 1513.17 and 1004.54 μmol g−1h−1, respectively), approximately 18, 11 and 7 times higher than CdS NRs (138.27 μmol g−1h−1). Among CdS/noble metal sulfide NRs, CdS/Ag2S NRs present the best H2 production performance. The apparent quantum efficiency (AQE) of CdS/Ag2S NRs achieves 3.11 % at λ = 370 nm. The improved photocatalytic performance of CdS/noble metal sulfide NRs dues to the following points: i) Noble metal sulfides on CdS NRs are beneficial for elevating light-absorbing and light-utilizing capacities, contributing to generating more photoexcited charges; ii) Noble metal sulfides are in-situ grown on CdS NRs as electron acceptors by a cation exchange method, thus the photoexcited electrons generated by CdS NRs rapidly migrate to the surface of noble metal sulfides, successfully accelerating the carriers separation efficiency. This series of noble metal sulfides acting as co-catalysts anchoring on CdS NRs offer new insights into the construction principles of high-performance photocatalytic hydrogen evolution catalysts.

Soft synthesis and analysis of structural parameters upon photoactivity of visible-active BiVO4-based ternary heterojunctions

Cu2O/Pt–BiVO4 and Cu2O/Au–BiVO4 photocatalysts are synthesized using a mild reducing agent (ascorbic acid) by an in-situ chemical reduction method at 25 °C. Pt and Au nanoparticles with an approximate size from 15 to 25 nm were incorporated onto BiVO4 powders. Crystalline phases are refined with the Rietveld method to evidence whether structural parameters contribute to enhance the photoactivity of the composites. The influences of structural defects and deposited metal are investigated to establish a relationship with their photoactivities. The as-synthesized BiVO4-based ternary photocatalysts displayed a strong optical absorption from UV to visible light shorter than 514 nm, with a blue-shift compared to that of pure BiVO4, resulting from the addition of the Au and Pt nanoparticles. The photocatalytic activities of the as-synthesized materials are evaluated under visible-light irradiation using the mineralization of 4-chlorophenol (4-CP) and dicloxacillin (DCX). The mineralization percentages achieved with Cu2O/Pt-BVO4 and Cu2O/Au–BiVO4 after 240 min of irradiation were 85% for 4-CP and 33% for DCX. It is assumed that those levels of TOC removal are due to the lowest content of oxygen vacancies in the photocatalysts, decreasing hole trapping, and subsequently hindering their recombination with the photoexcited electrons. Under this premise, structural defects (i.e. oxygen deficiency) present a more important effect on the photoactivity of the BiVO4-based materials than crystallite size, or other structural parameters. Moreover, the activity can also be ascribed to the Z-scheme Cu2O/BiVO4 heterojunction enhancing redox potentials of charge carriers, the incorporation of Pt and Au nanoparticles, enhancing charge separation either by trapping photo-generated electrons, generating the electron sink effect.

DFT evaluation the photo-catalytic performance of g-C3N4 dots/ZnO with O/S doping

To develop the high-performance g-C3N4-based photo-catalysts and understand the mechanism of photo-catalytic degradation of volatile organic compounds (VOCs), we evaluated the photo-catalytic performance and corresponding catalytic mechanisms of g-C3N4 dots/ZnO (CNZO) systems using density functional theory (DFT) calculations. Our results showed that the combination of g-C3N4 dots and ZnO monolayer has a appropriate band gap and strong visible light absorption, significantly enhancing photoelectron excitation and immigration. We also observed that O/S doping exerted a significant impact on the band structure and interfacial coupling, thereby increasing the number of photoelectrons that move from the valence band (VB) of ZnO monolayer to the conduction band (CB) of g-C3N4 dots, thereby enhancing the separation of photo-generated electron-hole pairs in O/S-CNZO. Furthermore, the suitable CB and VB positions of O/S-CNZO encourage the adsorption of surface H2O and O2 molecules, leading to the generation of ·OH and ·O2− radicals crucial in VOCs degradation. This work introduces new approaches and perspectives for constructing novel photo-catalysts. Additionally, it involves a theoretical evaluation of the photo-catalytic performance of O/S-CNZO.

Tailoring photocatalytic water splitting activity of boron-thiophene polymer through pore size engineering.

Taking into account the electron-rich and visible light response of thiophene, first-principles calculations have been carried out to explore the photocatalytic activity of donor-acceptor polymers incorporating thiophene and boron. Honeycomb-kagome boron-thiophene (BTP) polymers with varying numbers of thiophene units and fixed B center atoms are direct bandgap semiconductors with tunable bandgaps ranging from 2.41 to 1.88eV and show high absorption coefficients under the ultraviolet and visible regions of the solar spectrum. Fine-tuning the band edges of the BTP polymer is efficiently achieved by adjusting the pore size through the manipulation of thiophene units between the B centers. This manipulation, achieved without excessive chemical functionalization, facilitates the generation of an appropriate quantity of photoexcited electrons and/or holes to straddle the redox potential of the water. Our study demonstrates that two units between B centers of thiophene in BTP polymers enable overall photocatalytic water splitting, whereas BTP polymers with larger pores solely promote photocatalytic hydrogen reduction. Moreover, the thermodynamics of hydrogen and oxygen reduction reactions either proceed spontaneously or need small additional external biases. Our findings provide the rationale for designing metal-free and single-material polymer photocatalysts based on thiophene, specifically for achieving efficient overall water splitting.

Interface engineering by constructing vertical junction for reduced noise and improved sensitivity in 2D photodetector

Two-dimensional (2D) materials have been widely demonstrated as promising candidates for next generation photodetectors, while the noticeable channel current is still a limiting factor for photodetection sensitivity. In this work, the interface engineering has been developed by constructing a vertical pn and Schottky junction in the 2D WS2 channel, resulting in a reduced dark current and noise spectral density, significantly improving the sensitivity. Specifically, the WS2 bottom surface is coupled with p-type tellurium (Te) nanoribbon and gold (Au) stripes, thus a vertical pn and Schottky junction can be constructed at WS2/Te and WS2/Au interface, respectively. In both device architectures, the dark current and electric noise are much suppressed due to the formation of depletion region in WS2 channel. Meanwhile, the out-of-plane built-in electric field at junction can facilitate the separation of photo-excited electron–hole pairs, which subsequently yields a faster temporal response. For the WS2/Au device, the incident light can be reflected by the bottom Au and propagate through the WS2 layer again, further boosting the photo-absorption, thus the photodetection sensitivity. The engineered WS2 photodetectors exhibit the noise spectral density as low as 5.36 × 10−14 A Hz−1/2 and high specific detectivity (D*) up to 1.12 × 1011 Jones, which has one–two orders of magnitude improvement compared to the pristine device. This work provides an effective and universal interface engineering strategy to achieve low noise and high sensitivity in 2D photodetectors.

High-efficiency photocatalytic CO2 reduction enabled by interfacial Ov and isolated Ti3+ of g-C3N4/TiO2 Z-scheme heterojunction

Exploring the real force that drives the separation of Coulomb-bound electron-hole pairs in the interface of heterojunction photocatalysts can establish a clear mechanism for efficient solar energy conversion efficiency. Herein, the formation of oxygen vacancy (Ov) and isolated Ti3+ was precisely regulated at the interface of g-C3N4/TiO2 Z-scheme heterojunction (g-C3N4/Ov-Ti3+-TiO2) by optimizing the opening degree of the calcination system, showing excellent production rate of CO and CH4 from CO2 photoreduction under visible light. This photocatalytic system also exhibited prominent stability. Combining theoretical calculation and characterization, the introduction of Ov and isolated Ti3+ on the interface could construct a charge transfer channel to break the forbidden transition of n → π*, improving the separation process of photoexcited electron-hole pairs. The photoexcited electrons weakened the covalent interaction of CO bonds to promote the activation of adsorbed inert CO2 molecules, significantly reducing the energy barrier of the rate-limiting step during CO2 reduction. This work demonstrates the great application potential of reasonably regulating heterojunction interface for efficient photocatalytic CO2 reduction.

Tailoring Charge Separation in ZnIn2S4@CdS Hollow Nanocages for Simultaneous Alcohol Oxidation and CO2 Reduction under Visible Light.

Artificial photosynthesis provides a sustainable strategy for producing usable fuels and fine chemicals and attracts broad research interest. However, conventional approaches suffer from low reactivity or low selectivity. Herein, we demonstrate that photocatalytic reduction of CO2 coupled with selective oxidation of aromatic alcohol into corresponding syngas and aromatic aldehydes can be processed efficiently and fantastically over the designed S-scheme ZnIn2S4@CdS core-shell hollow nanocage under visible light. In the ZnIn2S4@CdS heterostructure, the photoexcited electrons and holes with weak redox capacities are eliminated, while the photoexcited electrons and holes with powder redox capacities are separated spatially and preserved on the desired active sites. Therefore, even if there are no cocatalysts and no vacancies, ZnIn2S4@CdS exhibits high reactivity. For instance, the CO production of ZnIn2S4@CdS is about 3.2 and 3.4 times higher than that of pure CdS and ZnIn2S4, respectively. More importantly, ZnIn2S4@CdS exhibits general applicability and high photocatalytic stability. Trapping agent experiments, 13CO2 isotopic tracing, in situ characterizations, and theoretical calculations reveal the photocatalytic mechanism. This study provides a new strategy to design efficient and selective photocatalysts for dual-function redox reactions by tailoring the active sites and regulating vector separation of photoexcited charge carriers.