Photogenerated Charge Carriers Research Articles

Efficient water disinfection against antibiotic-resistant bacteria by visible-light heterogeneous photo-Fenton-like process with atomically dispersed Cu on graphitic carbon nitride as the catalyst

Waterborne microbial contamination poses significant environmental and health risks. Photocatalytic heterogeneous Fenton and Fenton-like processes can offer efficient pathogen removal, with benefits in recycling, solid–liquid separation, and byproduct avoidance. However, their low reaction efficiency and slow kinetics for low-valence metal regeneration are limitations. This study addresses these challenges by incorporating atomically dispersed Cu onto graphitic carbon nitride (g-CN) as a single-atom catalyst (SAC). The Cu atoms are stabilized by pyridinic N atoms through coordination, forming Cu-N4 catalytic sites that enhance photogenerated charge carrier transfer. This leads to a more efficient synergistic photocatalytic-Fenton-like reaction, generating more hydroxyl radicals and achieving effective water disinfection. Results show a 7-log bacterial inactivation of antibiotic-resistant Acinetobacter baumannii within 8 min, surpassing prior photocatalytic-Fenton-like disinfection systems. Density functional theory calculations confirm improved hydrogen peroxide adsorption, electron transport, and electron-hole separation in the Cu-N4 structure. The catalyst’s durability and stability were demonstrated through extensive cycling experiments, ion interference tests, and disinfection trials in various water matrices. Additionally, the Cu-SAC@CN catalyst, loaded onto a polytetrafluoroethylene membrane, achieved a 99% bacterial eradication rate within 20 min. This study provides valuable insights into the potential applications of heterogeneous photocatalytic-Fenton-like systems for efficient eradication of waterborne bacteria.

Controlling charge migration and CO2 conversion through surface decoration of 2D-hydrotalcite on bismuth oxybromide for enhanced artificial photosynthesis

Photocatalytic reduction of CO2 in pure H2O media to produce chemicals presents an appealing avenue for simultaneously alleviating energy and environmental crises. However, the rapid recombination of photogenerated charge carriers presents a significant challenge in this promising field. Heterojunction engineering has emerged as an effective approach to address this dilemma. Here, by decorating 2D NiAl-layered double hydroxides (NAL) onto bismuth oxybromide (BOB), we have created a S-scheme heterojunction (N1B1 composite). This catalyst affords CO2-to-CO yields of 102.30 μmol g−1 with a selectivity of 100 %. Ultraviolet photoelectron spectroscopy (UPS) and in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) reveal that charge transfer occurs efficiently from BOB to 2D-NAL upon light irradiation. The designed N1B1 heterojunction achieves 7.3-fold and 2.1-fold increase in the internal electric field strength compared to bare 2D-NAL and BOB, respectively, which should be accountable for the improved charge migration. Additionally, pulsed chemisorption and in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) show the presence of multiple carbonate intermediates with activated OCO bonds upon N1B1 composite, with *CO2− being identified as the most crucial species for CO production.

Investigation into the impact of anionic substitution on modulating the optical and catalytic properties of bismuth ferrite nanoparticles

Bismuth ferrite (BFO) nanoparticles have emerged as a non-toxic catalyst with remarkable potential for the photodegradation of various environmental pollutants. A notable departure from conventional approaches, where cations are added as dopant, this study achieved enhanced catalytic performance through anion substitution. Specifically, replacing oxygen atoms with nitrogen introduces spin-polarized defect states within the BFO’s energy gap, resulting in a notable reduction in the energy band gap. Nitrogen doping of bismuth ferrite yields a novel material with exceptional capabilities for the photodegradation of methylene blue dye and the reduction of 4-nitrophenol. Comprehensive characterization, including X-ray diffraction, Fourier-transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy, has unequivocally confirmed the successful incorporation of nitrogen into the BFO nanoparticle lattice. Interestingly, field emission scanning electron microscopy analysis revealed no significant alteration in nanoparticle size after nitrogen doping. Meanwhile, UV-diffuse reflectance spectroscopy unveiled a distinct decrease in the energy gap upon nitrogen incorporation. The observed improvements in catalytic activities can be attributed to nitrogen ions, introduced as substitutes, effectively occupying the oxygen defects within the sample, thereby diminishing recombination centers for photogenerated charge carriers and decreasing recombination rates. Additionally, adsorption kinetics studies underscore the efficacy of the catalyst surface in adsorbing methylene blue and/or 4-nitrophenol, conforming to the Ho pseudo-second-order model. This study not only highlights the exciting potential of nitrogen-doped bismuth ferrite nanoparticles in environmental remediation but also sheds light on the intricate interplay between anion substitution, band structure modification, and catalytic performance enhancement.Graphical

Comprehensively Modulated Sub-Attojoule Operated Optoelectronic Synapses for Image Encryption and Inpainting.

High-performance optoelectronic synaptic transistors play a crucial role in developing and emulating artificial visual systems. However, due to the predominant use of single-structure material modulation in optimizing optoelectronic synapses, their energy consumption significantly trails behind that of electronic synapses by several orders of magnitude. Herein, polymer dielectric layers and optimized contact strategies are adopted to realize the ultralow consumption optoelectronic synapses. Integration of polyimide dielectric significantly enhances photogenerated charge carrier dissociation, leading to substantial improvements in photoresponsivity (1.5 × 106 A·W-1), photodetectivity (6.9 × 1012 Jones), and external quantum efficiency (4.0 × 108%). Additionally, optimized contact properties augment their appeal for ultralow energy consumption in optoelectronic synapse applications. Excitatory postsynaptic current is triggered at an incredibly low voltage of 5 μV and boosts an impressively low energy consumption of 0.05 aJ, ranking among the best-reported results in this field. Next, we demonstrate an integrated system combining the MoS2 optoelectronic synapses with a recurrent neural network enabling 100% accurate recognition of optical signals, particularly in scenarios with aJ-leveled energy consumption. Finally, an image encryption system has been developed, in which images are encrypted by photoelectronic conversion of synapse arrays with random voltage settings and decrypted according to the recurrent neural network-based accuracy. More importantly, once partially damaged images are encrypted, through the decryption image inpainting can be realized due to the high accuracy. The proposed innovative approach holds promise for advancing artificial intelligence applications with improved energy efficiency, information security, and computational capabilities.

A universal molecular oxygen-mediated photocatalysis strategy to boost visible-light induced hydrogen evolution through partial water splitting

A universal oxygen-mediated, stepwise strategy is proposed for efficiently inducing visible-light photocatalytic partial water decomposition into hydrogen over various semiconductor photocatalysts with conduction band bottoms below the single-electron oxygen reduction potential. In this scenario, molecular O2 can be transformed into reactive oxygen species, serving as both an oxidant and a homogeneous catalyst for producing hydrogen from alkaline aqueous solution containing various organic substrates. Further enhancement the performance is achieved by doping with phosphorous and oxygen, which constructs a local internal electric field and introduces sulfur vacancies, thereby facilitating the transport of photogenerated charge carriers, particularly on a representative CdS photocatalyst. The optimal hydrogen evolution performance reaches 2321.4 and 8521.4 μmol·gcatatlyst−1·h−1 in methanol and formaldehyde solution systems, respectively, with an apparent quantum efficiency exceeding 59.4 % under 450 nm visible light irradiation. Mechanistic studies demonstrate that the oxygen-mediated, sequential single-electron transfer process can occur with virtually zero activation energy.

Impact of FeS on the TiO2 Layer As Support System in QDSCs.

We report on the passivation of titanium oxide with FeS from three molecular precursors with tin sulfide (SnS) photon absorbers that were fabricated and assembled to increase the performance of quantum dot sensitized solar cells (QDSSCs). FeS was loaded on the TiO2 surfaces, and then, SnS photosensitizer was deposited to form a ternary modified device. The morphology, structural structure, size distribution, chemical composition, and conversion efficiency were explored by FE-SEM, XRD, TEM, UV-vis, EDS, EIS, and J-V analysis. The CV, LSV, and stability state were also investigated for migration and separation of photogenerated charge carriers in the as-prepared cells labeled F-S-1, F-S-2, and F-S-3. The FE-SEM image of the F-S-2 cell is composed of FeS interconnected with SnS and FeS, which provided paths for electron movement compared with the F-S-1 and F-S-3 devices. The semicircle for the F/S-1 and F/S-3 solar device diameters illustrates that the high-medium frequency regain is greater than that of the F/S-2 device, implying that both cells have charge-transfer impedances and lower contact. Apparently, the F/S-2 device shows superior catalytic activity, which can be linked to the hybridization of TiO2/FeS/SnS due to the synergistic effect. The F/S-2/S-2l has a maximum efficiency η of 6.73% in comparison to F/S-1 and F/S-3, which have the same conversion efficiency of 3.82%. The results of the F/S-2 device follow a similar trend to the chronoamperometry analysis, CV, and LSV results from this study.

Copper benzene-1,3,5-tricarboxylate based metal organic framework (MOF) derived CuO/TiO2 nanofibers and their use as visible light active photocatalyst for the hydrogen production

Photocatalytic hydrogen generation through water splitting offers a sustainable and renewable approach to producing green and clean hydrogen fuel. However, it is crucial to explore low-cost semiconductor photocatalysts that can effectively capture a broad range of solar radiation. The present study aims to develop photocatalytic CuO/TiO2 nanofibers (NFs) with homogeneity of copper with titanium in the heterostructures through the metal–organic framework (MOF) assisted strategy via the electrospinning and subsequent calcination approach. The new methodology enables the fabrication of CuO-modified TiO2 NFs based on HKUST-1 (copper benzene-1,3,5-tricarboxylate, Hong Kong University of Science and Technology-1) as Cu-MOF varying the amounts of HKUST-1. Ultraviolet–visible light diffuses reflectance spectroscopy (DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), photoluminescence spectroscopy (PL), X-ray photoemission spectroscopy (XPS) and Raman spectroscopy are employed to assess the structural and morphological characteristics of the prepared NFs. The characterization revealed that the CuO-TiO2 NFs heterostructure was uniform. The bandgaps of the CuO-TiO2 NFs ranged from 3.08 to 2.83 eV based on the Kubelka–Munk function, which is considerable for improving the light-harvesting capacity. The photocurrent technique is used to confirm efficiency in charge separation and transfer, as well as a longer lifetime of photo-generated charge carriers effect in photocatalytic activity. In addition, density functional theory calculations were performed to analyze the impact of CuO on the geometric, electronic structure and photocatalytic properties of TiO2. The CuO/TiO2 photocatalyst containing 1.5 mol% of CuO exhibited the highest photocatalytic activity. The hydrogen production rate was exceptional at 45.6 mmol·g−1·h−1, which was a remarkable 400 times higher than that achieved with pure TiO2 nanofibers. Owing to the one-dimensionality of nanostructures, the prepared CuO-based TiO2 NFs had high recyclability without lessening the efficiencies of photocatalytic activity.

MoC nanoparticles embedded in superior thin g-C3N4 nanosheets for efficient photocatalytic activity

Photogenerated charge carrier transfer efficiency in graphitic carbon nitride (g-C3N4) based heterostructures depended strongly on the interface nature. In this paper, MoC nanoparticles less than 5 nm were implanted in superior thin g-C3N4 nanosheets to create high charge carrier separation and transfer efficiency. Cubic MoC in N-doped graphitic carbon was first fabricated using dicyandiamide and ammonium molybdate tetrahydrate at 800 °C. The MoC nanoparticles were homogeneously implanted in g-C3N4 nanosheets by further thermal polymerization of bulk g-C3N4 prepared using melamine and MoC/C composites to create a Schottky junction which was confirmed by band gap analysis and free radical capture test. Melamine and dicyandiamide also play important role to create highly efficient catalysts. The MoC nanoparticles revealed fine crystallinity. A well-developed interface between MoC and g-C3N4 was observed. Because of high conductivity of MoC, well-developed interface, and co-catalyst role of MoC, the MoC/g-C3N4 junction exhibited ideal photocatalytic activity for dye degradation and water splitting. The kinetic constant rate of Rhodamine B degradation using a MoC/g-C3N4 sample created by optimized conditions was 0.061 min−1 which was 8.7 times of that of pristine g-C3N4 nanosheets. In the case of without co-catalyst addition, the photocatalytic hydrogen generation rate using this composite sample was 233.0 μmol g−1 h−1 which was 15.2 times of that of initial g-C3N4 nanosheets. These results supply an efficient approach for the first time to homogeneously distribute small cubic MoC nanoparticles in superior thin g-C3N4 nanosheets to construct heterostructures and greatly reduce photogenerated charge carrier recombination.

Precursor-reforming protocol to hierarchical porous g-C3N4 with N defects for remarkable visible-light-driven hydrogen evolution

The photocatalytic activity of g-C3N4 can be enhanced through precise defect engineering. In this study, hierarchical porous g–C3N4–containing cyano groups and N vacancies was synthesized by thermally polymerizing dicyandiamide precursor in a hydrochloric acid solution of magnesium chloride. The resulting structure comprised crosslinked rod-shaped units with a high aspect ratio, facilitating efficient light transmission and absorption within the material. Furthermore, introducing N defects reduced the bandgap and optimized the electronic structure, thereby enhancing light absorption and exposing active sites effectively. The synergistic effects of N defects and the hierarchical porous structure disrupted the original electronic distribution of g-C3N4, leading to directional separation of photogenerated charge carriers and considerably enhancing hydrogen evolution performance. Consequently, the optimized hpCNX-0.05 sample exhibited markedly improved hydrogen evolution rates, achieving 1703.67 μmol g−1 h−1 under visible light irradiation, approximately 3.16 times higher than that of bulk g-C3N4. Overall, this paper presents a promising strategy for synthesizing hierarchical porous g-C3N4 with N defects to achieve highly efficient H2 production.

Boosting visible-light photocatalytic performance of graphitic carbon nitride by regulating its donor-acceptor structure via maleamide

Graphitic carbon nitride (GCN) has attracted much attention due to its many advantages as a kind of photocatalyst, including low cost, easy to prepare, eco-friendly and so on. However, GCN suffers from limited light-absorption capacity and rapid recombination of photogenerated charge carriers. Herein, a new kind of photocatalyst based on GCN has been synthesized by introducing a small molecule compound (maleamide) through a facile thermal polycondensation method (550 ℃ for 180 min) and applied it to photocatalytic removal of bisphenol A (BPA). The optimized GCN-20 (20 mg maleamide in 10 g urea) exhibits the best BPA degradation performance and good stability. The UV–vis test shows that the introduction of maleamide broadens the optical response threshold of GCN from 435 nm to 460 nm. The promoted photocatalytic performance is mainly attributed to enhanced donor-acceptor structure by electron-withdrawing group, which accelerates charge separation and inhibits recombination of free holes and electrons. The active species including superoxide radicals (⋅O2-), hydrogen peroxide (H2O2) and hydroxyl radicals (⋅OH), play dominant roles in the photocatalytic degradation process.

Insights for Precursors Influence on the Solar-Assisted Photocatalysis of Greenly Synthesizing Zinc Oxide NPs towards Fast and Durable Wastewater Detoxification

Herein, this study has examined the influence of Zn2+ sources during a biogenic-mediated pathway to synthesize ZnO nanoparticles with highly desirable solar-responsive catalytic properties. Salts of nitrate, acetate and chloride have been utilized. The ZnO powders underwent characterization using diverse analytical tools, including XRD, FTIR, Raman, BET, SEM, TEM with EDS/elemental mapping and UV-vis absorption/emission spectroscopic analyses. Accordingly, precursors have proved to affect crystallinity, morphology, surface characteristics, optical properties and the photocatalytic degradation of methylene blue (MB) model pollutant. It was observed that ZnO derived from zinc acetate precursor (Z-AC NPs) exhibits very fast photocatalytic degradation of MB at pH 11 with superior kinetic estimates of 0.314 min−1 and t1/2 = 2.2 min over many of recent reports. In contrast, the chloride precursor is not recommended along with the employed biogenic route. The intriguing findings could be directly correlated to the decreased crystal size, augmented surface area, the hexagonal morphology of the crystals, high potency in absorbing visible photons, high efficacy in separating photogenerated charge carriers and producing high amounts of •OH radicals. Further testing of Z-AC NPs in photocatalytic remediation of water samples from Dumat Aljandal Lake in Aljouf, Saudi Arabia, contaminated with MB and pyronine Y (PY) dyestuffs, showed high dye photodegradation. Therefore, this work could lead to an extremely fast avenue for decontaminating wastewater from hazmat dyestuff.

Pt Single Atoms Loaded on Thin-Layer TiO2 Electrodes: Electrochemical and Photocatalytic Features.

Recently, the use of Pt in the form of single atoms (SA) has attracted considerable attention to promote the cathodic hydrogen production reaction from water in electrochemical or photocatalytic settings. First, produce suitable electrodes by Pt SA deposition on Direct current (DC)-sputter deposited titania (TiO2)layers on graphene-these electrodes allow to characterization of the electrochemical properties of Pt single atoms and their investigation in high-resolution HAADF-STEM. For Pt SAs loaded on TiO2, electrochemical H2 evolution shows only a very small overpotential. Concurrent with the onset of H2 evolution, agglomeration of the Pt SAs to clusters or nanoparticles (NPs) occurs. Potential cycling can be used to control SA agglomeration to variable-size NPs. The electrochemical activity of the electrode is directly related to the SA surface density (up to reaching the activity level of a plain Pt sheet). In contrast, for photocatalytic H2 generation already a minimum SA density is sufficient to reach control by photogenerated charge carriers. In electrochemical and photocatalytic approaches a typical TOF of ≈100-150 H2 molecules per second per site can be reached. Overall, the work illustrates a straightforward approach for reliable electrochemical and photoelectrochemical investigations of SAs and discusses the extraction of critical electrochemical factors of Pt SAs on titania electrodes.

Enhanced photocatalytic hydrogen evolution of an imine-linked covalent triazine framework through the assistance of Ti3C2Tx

Imine-linked covalent triazine frameworks (CTFs) with high crystallinity and nano-morphologies are synthesized more easily compared to the CTFs with irreversible bonds. Nevertheless, their photocatalytic hydrogen evolution is usually less efficient due to the low utilization of photogenerated charge carriers. Herein, ultrathin Ti3C2Tx nanosheets with high conductivity and a good deal of terminal -O groups are employed to improve the photocatalytic hydrogen evolution of CTF-TFB through the fabrication of composites CTF-TFB/Ti3C2Tx (TM-x). And the broad-spectrum light absorption and photothermal effect of Ti3C2Tx nanosheets significantly enhance the utilization of visible light for CTF-TFB. Typically, Ti3C2Tx absorbing photogenerated electrons from CTF-TFB to achieve spatial separation of charge carriers, thereby TM-20 exhibiting an about 0.5-fold increase in AQYs at 420 nm and 450 nm compared to CTF-TFB. Meanwhile, the great photothermal effect of Ti3C2Tx brings a higher surface temperature for TM-20, leading to an additional 67 % increase in the photocatalytic hydrogen evolution rate of TM-20.

Nitrogen-Site Engineering in Covalent Organic Frameworks for H2O2 Photogeneration via Dual Channels of Indirect Two-Electron O2 Reduction.

Photocatalytic H2O2 production is a green and sustainable route, but far from meeting the increasing demands of industrialization due to the rapid recombination of the photogenerated charge carriers and the sluggish reaction kinetics. Effective strategies for precisely regulating the photogenerated carrier behavior and catalytic activity to construct high-performance photocatalysts are urgently needed. Herein, a nitrogen-site engineering strategy, implying elaborately tuning the species and densities of nitrogen atoms, is applied for H2O2 photogeneration performance regulation. Different nitrogen heterocycles, such as pyridine, pyrimidine, and triazine units, are polymerized with trithiophene units, and five covalent organic frameworks (COFs) with distinct nitrogen species and densities on the skeletons are obtained. Fascinatingly, they photocatalyzed H2O2 production via dominated two-electron O2 reduction processes, including O2-O2 •‒-H2O2 and O2-O2 •‒-O2 1-H2O2 dual pathways. Just in the air and pure water, the multicomponent TTA-TF-COF with the maximum nitrogen densities triazine nitrogen densities exhibited the highest H2O2 production rate of 3343µmol g-1 h-1, higher than most of other reported COFs. The theoretical calculation revealed the higher activity is due to the easy formation of O2 •‒ and O2 1 in different catalytic process. This study gives a new insight into designing photocatalysis at atomic level.

Enhanced sunlight-driven photocatalysis of non-metal doped zinc oxide via wet impregnation for the removal of organic compounds

Zinc oxide (ZnO), a commonly used photocatalyst, suffers from the rapid recombination of photogenerated charge carriers, and the inability to harvest visible light. Therefore, the green synthesized ZnO from Garcinia mangostana pericarp is modified via non-metal (X) doping of N, P, S, Br, and B with a mass content of 5 % to tackle the aforementioned. The obtained materials were characterized through various modern characterization techniques. The results reveal that amongst the X-doped sample, ZnO-B demonstrates the highest photocatalytic performance. The characteristics of ZnO include good crystallinity as well as a low band gap energy of 2.094 eV, revealing an enhanced visible light absorption activity of the sample. The photoactivity of surveyed ZnO-B was investigated through the degradation of malachite green, methyl orange, and tetracycline, achieving a removal rate of 96.29, 86.59, and 90.32 %, respectively. Simultaneously, the antibacterial properties of the ZnO-X were evaluated for Staphylococcus aureus under sunlight illumination. Moreover, the photocatalysis mechanism of the studied materials was elucidated through the band structure, toxicity, and total organic carbon removal of the post-catalysis solution. The selected boron-doped zinc oxide catalyst also showed excellent reusability after 10 cycles of photocatalysis, retaining ∼ 80 % of its original activity. The obtained results reveal the potential application of non-metal-doped zinc oxide in environmental remediation and water disinfection.

Constructing homo/hetero-nuclear carbon and oxygen atoms co-doped graphitic carbon nitride assisted by ionic liquid for photothermal synergistic catalytic oxidation of cyclohexane

The adoption of photothermal synergistic catalysis for cyclohexane oxidation can balance the advantages of high conversion of thermal catalysis and high selectivity of photocatalytic technology to achieve better catalytic performance. Here, we prepared functional carbon nitride (BCA-CN) by self-assembly strategy of ionic liquid [Bmim]CA (1-Butyl-3-methylimidazole citrate) with melamine and cyanuric acid utilizing abundant elements and anionic/cationic hydrogen bonding interactions. The introduction of [Bmim]CA embeds C-C (carbon and carbon band) and C-O-C (ether bond) structures into graphitic carbon nitride (g-C3N4) framework, significantly improving light absorption capacity and migration of photo generated charge carriers. Compared to g-C3N4, both BCA-CN increases cyclohexane conversion and KA oil (the mixture of cyclohexanol and cyclohexanone) selectivity by 1.3 times under photothermal catalysis. The surface reactions are facilitated by changing adsorption sites of cyclohexane to increase adsorption energy and obtaining more hydroxyl radicals and superoxide radicals. Furthermore, the enhanced selectivity is attributed to the difficulty in generating cyclohexanone radicals. This work offers the reference scheme for the development of efficient photothermal catalysts in the selective oxidation of cyclohexane.

Sulfur vacancies form charge transport channels on the S-type heterojunction engineered interface to enhance photocatalytic performance

This article presents the synthesis of an S-type heterojunction photocatalyst through a straightforward hydrothermal process, which involves the combination of FeWO4 with Zn0.5Cd0.5S containing sulfur vacancies (Zn0.5Cd0.5Ssv). The study delves into the intrinsic role of sulfur vacancies in enhancing the photocatalytic performance of the S-type heterojunction. The creation of sulfur vacancies effectively controls charge separation and triggers a rapid charge transfer pathway at the heterojunction, improving light absorption and permitting the formation of more photoinduced charges. The material demonstrates an impressive degradation efficiency, capable of breaking down 79.38% of IOH within just 40 minutes. It exhibits robust catalytic activity under both mildly acidic and mildly basic conditions, showing notable resistance to various anions and cations present in water, as well as a significant tolerance to high concentrations of humic acid. Further, trapping experiments reveal that hydroxyl radicals (•OH) and superoxide radicals (•O2⁻) are the predominant reactive species driving the photocatalytic process. This research sheds new light on the modulation of photogenerated charge carrier dynamics at the heterointerface, offering valuable guidance for the development of high-performance S-type photocatalysts.

Coating of CoS on hybrid anode electrode with enhance performance in hybrid dye-sensitized solar cells

Improvement of the power generation performance of dye-sensitized solar cells (DSSCs) remains a key task, as charge transfer and charge separation are efficiently achieved at the photoanode and between the polysulfide electrolyte interface and the counter-electrode. We synthesized the metal sulfides from dithiocarbamate complexes and used them to fabricate a new modified cell by passivating the photoanode electrode with CoS nanoparticles and SnS as photosensitizer in a two-step deposition approach. They were used as FTO-TiO2/CoS/SnS/HI-30/FTO-Pt, known as C-S-1, C-S-2 and C-S-3. SEM images show that the C-S-1 and C-S-2 are uniform, without cracks and have a dense surface morphology covering the surface area. Thus, confirming the successively passivation by CoS and sensitization of SnS, forming FTO-TiO2/CoS/SnS heterostructure. The η of 8.79% and 9.43% are much higher than that of C-S-2, with 0.23% affirm the roles of the Co, Sn and S ratio on both devices. The EIS Nyquist plot for the C-S-2 device shows a semicircle radius smaller than the C-S-1 and C-S-3, which indicates more efficient inhibition of electron/hole pairs and faster transportation of photogenerated charge carriers. The enhanced performance of both devices shows that the passivation of the electrodes ensures that maximum absorption is achieved through a higher absorption coefficient of SnS. Also, both devices reach a steady state within about 200–300 s and remain at the steady state current for a long duration for C-S-1 and C-S-3. The enhanced performance of both devices shows that the passivation of the electrodes ensures that maximum absorption is achieved through a higher absorption co-efficient of SnS.

Broad-spectrum responsive MOF-derived Z-scheme heterojunction for dual-functional photocatalysis of cooperative hydrogen evolution and benzylamine oxidation coupling

The construction of synchronous cooperative redox dual-functional photocatalysts is an efficient strategy for enhancing catalytic ability. It not only reduces organic pollution and waste of photogenerated holes from sacrificial electron donors but also integrates with biomass conversion for the generation of valuable chemicals. Herein, broad-spectrum responsive dual-functional NiS/MnCdS photocatalysts are developed by constructing Z-scheme heterojunction for efficient hydrogen evolution and synergistic benzylamine oxidation coupling. The NS/MCS-100 obtained exhibits remarkable photocatalytic performance under visible light, with a hydrogen evolution rate of 1.61 mmol·h−1·g−1, benzylamine conversion rate exceeding 90 %, and an approximate selectivity towards N-benzylbenzaldimine of 99 %, which is seven times higher than that of pure MnCdS. Subsequently, experimental characterizations and DFT calculations confirm that the construction of Z-scheme heterojunctions maintains a high redox potential for catalysts, enhancing the redox ability and thereby improving photocatalytic efficiency to achieve coordinated dual-function catalysis. In addition, the advantages of MOF template-derived strategy in structure and defect engineering for effective separation of photogenerated charge carriers have enhanced the photocatalytic performance of this composite catalyst. This work not only reveals a strategy to construct Z-scheme heterojunctions with broad-spectrum response without any sacrificing agents to enhance photocatalytic performance but also demonstrates its significant potential for the application of other highly efficient synergistic dual-functional photocatalytic reactions.

Schottky-Barrier-Free Plasmonic Photocatalysts for Solar-Driven Ammonia Synthesis

Ammonia is not only an indispensable feedstock to produce essential industrial chemicals like fertilizers, but it is also a potential hydrogen energy carrier owing to its high energy density and hydrogen capacity. Currently, most ammonia required for humans comes from the Haber–Bosch process, which contributes more than 90% of the annual global ammonia output. However, the harsh reaction conditions of this process result in serious energy and environmental issues. According to the relevant statistics, the ammonia industry consumes about 2% of the total energy and generates about 1.6% of the total CO2 emission annually in the world.It is therefore crucial to develop a green and sustainable strategy for ammonia synthesis. Among various alternative technologies of the Haber–Bosch process, artificial photosynthesis has attracted wide research interests and has been regarded as a promising, environmentally friendly, and energy-saving process. Photocatalytic ammonia synthesis can utilize renewable solar energy to drive the reaction and operate under mild conditions, which possesses the benefits of the simple reaction system, low cost, and safety. Although numerous photocatalysts have been explored over the past several decades, their activity and efficiency have still been low and far from the practical application requirements. It is therefore a huge challenge to design efficient photocatalysts for ammonia synthesis.Localized surface plasmon resonance (LSPR) has recently drawn enormous attention. LSPR can not only endow plasmonic nanomaterials with large absorption cross-sections and intense local field enhancement but also generate energetic hot electrons and hot holes. Owing to the appealing features of LSPR, plasmonic photocatalysis has shown great potential in ammonia synthesis. Plasmonic photocatalysts are usually composed of noble metals and wide bandgap semiconductors. However, the Schottky barrier will form at the metal–semiconductor interface in such hybrid structures due to the mismatch of the band structures between plasmonic metals and semiconductors. Hence, a large portion of the hot electrons cannot cross the Schottky barrier and get lost in the metal through the recombination with the holes. To overcome the drawbacks caused by the Schottky barrier, it is strongly desirable to develop a new type of plasmonic semiconductor photocatalysts, i.e., Schottky-barrier-free plasmonic photocatalyst.The Schottky-barrier-free plasmonic photocatalysts are usually degenerately doped semiconductors containing lattice oxygen vacancies. They possess high free electron densities and strong plasmon resonance because of the high-level doping, which results in abundant hot charge carriers upon plasmon excitation. Moreover, they also have appropriate surface sites that can adsorb reactant molecules and activate them. The photogenerated plasmonic hot charge carriers can get trapped at the defect sites and thereafter drive redox reactions. Compared with traditional metal–semiconductor hybrid plasmonic photocatalysts, Schottky-barrier-free plasmonic photocatalysts enable hot charge carriers to be transported nearly freely in the material, resulting in high charge utilization and photocatalytic efficiency.We have demonstrated the synthesis of Schottky-barrier-free plasmonic MoO3−x nanospheres (NSs) with remarkably high oxygen vacancy (OV) contents by aerosol-spray. The MoO3−x NSs can achieve efficient ammonia photosynthesis through a “killing two birds with one stone” mechanism. On the one hand, the OVs can serve as chemisorption sites for N2 molecules and participate in their activation. On the other hand, the introduction of OVs generates a large number of free electrons near the conduction band, which induces a broad absorption band from the visible to the NIR region owing to the plasmon resonance. The Schottky-barrier-free nature of this plasmonic semiconductor allows free transportation of the plasmonic hot charge carriers, while the defect states introduced by the OVs can effectively trap the hot electrons to prevent rapid electron–hole recombination. As expected, the as-prepared material exhibits a superior ammonia production rate, with the highest apparent quantum efficiency (AQE) of 1.24% at 808 nm and an appreciable solar-to-ammonia conversion efficiency (SACE) of 0.057% for NH3 production. Besides MoO3−x , WO3−x is also an excellent candidate for Schottky-barrier-free plasmonic photocatalysts. We have synthesized square WO3−x nanoplates hydrothermally. The WO3-x nanoplates possess regular morphology, wide light absorption, and great ammonia production performance. Furthermore, by introducing doping elements (Mo, V, Fe, Bi) into WO3−x nanoplates, the N2 activation and dissociation can be improved by refining the defect states. The Mo-doped WO3−x nanoplates exhibit the highest ammonia production rate of 145.50 μmol g−1 h−1 with SACE of 0.011% since the Mo species can promote the chemisorption and polarization of N2 molecules and significantly reduce the reaction barrier. Notably, Mo-doped WO3−x nanoplates are a dual-function photocatalyst that can oxidize water to hydrogen peroxide in a stoichiometric ratio while synthesizing ammonia. Figure 1