Efficient Charge Transfer Research Articles

Construction of S-scheme heterojunction via coating ZIF-8-derived Zn0.7Cd0.3S on Ni2P hydrangea for efficient photocatalytic hydrogen evolution coupled with benzyl alcohol oxidation

Coupling light-driven hydrogen (H2) evolution with benzyl alcohol (BA) oxidation is regard as a prospective strategy for obtaining value-added fuels as well as chemicals to deal with energy and environment crisis. In this contribution, a series of dual-functional noble metal-free S-scheme heterojunctions (Zn1-xCdxS@yNi2P) with spatially separated and precise redox sites were constructed by synthesizing Zn1-xCdxS with regular morphology uniformly coated on Ni2P nanosheets via the template method for coupling H2 evolution with BA oxidation. The optimized Zn0.7Cd0.3S@15 %Ni2P photocatalytic produced H2 (40.33 mmol g−1 h−1) and benzaldehyde (BAD) (43.38 mmol g−1 h−1), remarkably exceeding pure Ni2P and Zn0.7Cd0.3S. Notably, the Zn0.7Cd0.3S@15 %Ni2P gave a significant advantage in coupling H2 evolution and BA oxidation performance than the catalysts reported previously. The S-scheme heterojunction constructed between Zn0.7Cd0.3S and Ni2P was demonstrated by Density functional theory (DFT) calculations, in-situ radiation X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscope (KPFM) and electron paramagnetic resonance (EPR). The effect of S-scheme heterointerfaces and internal electric field promoted photo-induced charge separation and transfer efficiency, greatly enhancing the photocatalysis performance. This work emphasizes the significance of rational engineering of heterojunctions, providing an enlightening guidance on synthesis of dual-functional photo-redox catalysts to improve economical solar fuel exploitation and production of value-added chemicals.

Cocatalysts engineering promotes photocatalytic CO2 reduction of hollow TiO2 nanospheres: From Cu nanoparticles to CuAg species

Hollow-structured TiO2 is promising for photocatalytic CO2 reduction due to its high surface area and light absorption. This study aims to enhance its photocatalytic activity through the engineering of Cu and CuAg alloy cocatalysts. Hollow TiO2 was synthesized by a hard template method, followed by Cu loading and CuAg alloy formation via a chemical replacement reaction. The optimal 7 % Cu loading achieved the highest CH4 yield of 2.47 μmol g−1 h−1 among the TiO2-Cu composites. Introducing Ag further enhanced the performance, with the Cu:Ag = 9:1 alloy boosting the CH4 yield to 6.72 μmol g−1 h−1, approximately 14 times that of pure TiO2. Characterization techniques such as XRD, SEM, and XPS were also employed to analyze the phase composition, microstructure, and photoelectrochemical properties of the synthesized materials. The experimental findings indicate that the introduction of the CuAg alloy significantly promotes charge separation and transfer efficiency, and increases the effective active sites on the TiO2 surface, thereby greatly enhancing the efficiency of the photocatalytic reaction. These findings offer insights into the design of efficient photocatalytic materials for sustainable energy applications.

Enhancement of BiVO4 photoanode surface oxygen evolution kinetics via Ni-Fe-ZIF derived bimetallic NiFeOx co-catalyst for water oxidation

The water oxidation kinetics on the surface of bismuth vanadate (BiVO4) photoanode is slow and the surface charge recombination is serious which hindering the photoelectrochemical (PEC) water splitting process. To enhance the PEC performance of BiVO4 and expedite the water oxidation process, in this work, a straightforward electrostatic adsorption and pyrolysis methods were devised to convert bimetallic Ni-Fe-zeolitic imidazolate frameworks (Ni-Fe-ZIF) molecular sieve into NiFeOx oxygen evolution co-catalyst and modified on BiVO4 photoanode surface (NiFeOx/BiVO4). The optimized NiFeOx/BiVO4 photoanode showed a high optical photocurrent density of 3.57 mA/cm2 at 1.23 V compared with reversible hydrogen electrode under AM 1.5G illumination with 4.4 times compared to the pure BiVO4 photoanode. The NiFeOx/BiVO4 composites photoanodes also exhibited the higher charge transfer efficiency of more than 77.8 % than the pure BiVO4 photoanode, indicating that the NiFeOx has excellent co-catalytic properties during PEC process. The improvement of photoelectric conversion efficiency can be attributed to the presence of NiFeOx layer with oxygen vacancies and more metal active sites on the BiVO4 surface which promoted the separation and transport of photoelectron-hole pairs and the surface oxygen evolution kinetics, thus significantly improving the photocurrent density.

Construction of bifunctional MOF-based composite electrocatalysts promoting oxygen evolution reaction and glucose oxidation reaction and its kinetic deciphering

The climate crisis and the need for green and sustainable energy drive the rapid development of hydrogen production from water electrolysis. Improvements in the kinetics of the anode reaction, which governs the efficiency of water electrolysis, are essential for efficient hydrogen production and key to effectively addressing global environmental and energy challenges. Hence, we focus on improving the kinetics of the anode oxidation reaction. The multi-walled carbon nanotubes coupled with bimetallic organic framework (CoFe-MOF-74) composite electrocatalysts (CoFe-MOF-74@MWCNT) were fabricated for OER and the kinetically more favorable glucose oxidation reaction (GOR). Compared to commercial RuO2, CoFe-MOF-74@MWCNT showed superior OER catalytic performance, exhibiting a lower overpotential (273 mV) and a lower Tafel slope (55 mV dec−1) at a current density of 10 mA cm−2. Moreover, after adding glucose to the anode, the potential required of 10 mA cm−2 was only 1.291 V (vs. RHE), a reduction of 212 mV compared to the OER potential. This reduction in potential demonstrates the efficiency of our catalysts and signifies significant energy savings. The characterization results and theoretical calculations indicated that the superior OER/GOR performance of CoFe-MOF-74@MWCNT can be ascribed to the synergistic effect between MWCNT and the mixed metal nodes of the bimetallic organic framework. The doping of MWCNT promoted the catalyst charge transfer efficiency (Rct was only 5.56 Ω) in the OER process. The mixed metal nodes of CoFe-MOF-74@MWCNT provided more active sites for the electrocatalytic reaction, and promoted the bond-breaking of critical intermediates in the oxidation process, significantly reducing the free energy of catalytic intermediates and accelerating reaction kinetics. This work provides a strategy for designing multifunctional electrocatalysts for OER and biomass small molecule oxidation and highlights the potential for significant energy savings in practical applications.

N/S co-doped nanocomposite of graphene oxide and graphene-like organic molecules as all-carbonaceous anode material for high-performance Li-ion batteries

In this study, to enhance the electrochemical performance of graphene-based anodes for Li-ion batteries (LIBs), we synthesized an all-carbonaceous N/S co-doped nanocomposite of graphene oxide (GO) and graphene-like small organic molecules (GOM) using a mild, eco-friendly, one-step hydrothermal method with thiourea (CH4N2S) (denoted as h-N/S-GO/GOM). The thiourea facilitated N/S co-doping and π−π bonding, which improved the interaction between hydrophilic GO and hydrophobic GOM in aqueous solution. Notably, the formation of π−π bonds between GO and GOM created pathways that enhanced electron transfer, thereby promoting efficient Li-ion transport from the electrolyte through the channels during rapid charge–discharge cycles. Additionally, the functional groups resulting from N/S co-doping increased the number of active sites within the nanocomposite. Consequently, the h-N/S-GO/GOM anode demonstrated superior electrochemical performance, achieving an average reversible capacity of 1265 mAh g−1 at 0.1 A g−1 and retaining 83.0 % of its capacity after 200 cycles. Furthermore, the nanocomposite exhibited excellent long-term cycling stability, maintaining a capacity of 688 mAh g−1 even after 1000 cycles at a high current density of 1.0 A g−1. The hierarchical network structure of the all-carbonaceous h-N/S-GO/GOM anode facilitated efficient charge transfer between the electrode and electrolyte through shorter diffusion paths for Li-ion transport and provided additional active sites, contributing to its outstanding electrical performance. The h-N/S-GO/GOM nanocomposite represents a promising alternative to traditional graphite-based anodes, offering a path toward high-performance, eco-friendly LIBs suitable for applications such as electric vehicles and energy storage systems.

Engineering a Zn-NC electron bridge boosting charge transfer in ZnO/C3N4 Z-scheme heterojunction for efficient photocatalytic disinfection

Although photocatalytic disinfection can avoid secondary pollution and other shortcomings compared to traditional disinfection methods, its development is seriously hindered by poor charge separation and transfer efficiency. Herein, we design a Zn-NC (single Zn atoms embedded in nitrogen-doped carbon) bridged ZnO/C3N4 Z-scheme heterojunction (ZnO/Zn-NC/C3N4) with robust interface contact by a multi-interfacial engineering strategy to achieve highly efficient separation and transfer of charge. Experimental and theoretical analyses demonstrate that the tightly integrated interface and excellent electrical conductivity of Zn-NC electron bridges ensure effective transfer of photogenerated charge carriers. Compared to ZnO/C3N4, the introduction of Zn-NC electron bridges induces charge rearrangement at the interface, generating a strong built-in electric field in the ZnO/Zn-NC/C3N4 Z-scheme heterojunction to facilitate the separation and transfer of photogenerated charge carriers. Furthermore, Zn-NC electron bridges effectively promote the adsorption and activation of oxygen on the surface of ZnO/Zn-NC/C3N4, enhancing the generation of reactive oxygen species for rapid bacteria elimination in water. Consequently, the ZnO/Zn-NC/C3N4 Z-scheme heterojunction, at a concentration of 100 ppm, achieves 99.9 % antibacterial efficiency against methicillin-resistant Staphylococcus aureus, Staphylococcus aureus, and Escherichia coli at a bacterial concentration of ∼ 107 CFU/mL under AM 1.5G simulated sunlight irradiation for 60 min, which is approximately 1.05 times higher than that of ZnO/C3N4. Moreover, ZnO/Zn-NC/C3N4 maintains a 99.9 % bactericidal efficiency for natural water treatment using a homemade microreactor, demonstrating its potential for water disinfection.

Visible-light driven S-scheme Bi2WO6/graphitic carbon nitride heterojunction for efficient simultaneous removal of TC and Cr(VI)

The application of photocatalysts in water governance has attracted extensive attention, and past research efforts often focused on single pollutant removal. Simultaneous removal of multiple pollutants from wastewater by a single processing unit is highly desirable, realistic, and challenging. The use of band-matched semiconductors to form heterojunctions is an important way to achieve this technology. In this work, we have designed a Bi2WO6/g-C3N4 heterojunction via an in-situ growth method. The in-suit XPS was used to verify the electron transfer pathway which conforms to the S-scheme mechanism. Under visible light irradiation, the removal rates of Cr(VI) and TC are 97.7 % and 96.0 % respectively. In addition to the excellent photocatalytic performance, the catalyst showed a high degree of stability during the five cycles. The formation mechanism of S-scheme heterojunction is discussed based on DFT calculation and physicochemical characterization. Liquid chromatography-mass spectrometry (LC-MS) and Quantitative Structure-Activity Relationship (QSAR) were used to analyze and predict the degradation pathways, intermediates, and toxicity. The efficient performance of the photocatalyst is attributed to the more efficient photogenerated charge transfer efficiency brought about by the formation of the built-in electric field, and the improvement of the photogenerated carrier recombination rate to provide more reactive sites with a large specific surface area. We provide a practicable strategy for the efficient treatment of inorganic and organic co-pollutants in environmental water by constructing an S-scheme heterojunction photocatalyst.

Copper Nanoclusters Imparted Metalloporphyrin Based Metal-Organic Frameworks for Enhanced CO2 Electroreduction.

Strategies that can introduce catalytic auxiliary into electrocatalysts to boost the performance of electrocatalytic CO2 reduction reaction (CO2RR) are meaningful in exploring hybrid electrocatalytic systems. Here, a series of hybrid electrocatalysts (Cu NCs@MOF-545-M, M=Fe, Co and Ni) have been prepared by assembly Cu NCs with MOF-545-M (M=Fe, Co and Ni) and successfully applied in electrocatalytic CO2RR. In the obtained MOF-545-M (M=Fe, Co and Ni), the integration of Cu NCs with MOF-545-M (M=Fe, Co and Ni) can create a hybrid electrocatalytic system that enhances the charge transfer efficiency and electrocatalytic CO2RR activity. Specifically, the optimal Cu NCs@MOF-545-Co presents remarkable FECO over a wide potential range (-0.7 V to -1.0 V), high CO generation rate (8.2 mol m-2 h-1) and excellent maximum energy efficiency (69 %, -0.7 V), which is superior to Cu NCs and MOF-545-Co, and represented to be one of the best performances to date. This work demonstrates a facile approach to significantly improve the FECO by loading metal nanoclusters into MOFs, providing a valuable reference for future studies on hybridization strategies to enhance the performance of electrocatalysts.

Nitrogen-Doped Graphene-Supported Tungsten Oxynitride Nanoparticles as an Efficient Bidirectional Polysulfide Convertor for Advanced Lithium-Sulfur Batteries.

Catalytic materials are considered pivotal in addressing the sluggish kinetics and shuttle effect in lithium-sulfur batteries (LSBs). However, effectively harnessing the utilization rate of active sites within catalytic materials remains a pivotal challenge. In this study, a novel conductive nitrogen-doped graphene-loaded tungsten oxynitride nanoparticle (WNO/NG) with abundant active sites is prepared through a polymer-assisted templating method for serving as a sulfur host. Electrochemical analysis coupled with in situ XRD confirm the dual-directional electrocatalytic behavior of WNO/NG for accelerating the conversion of lithium polysulfide (LiPSs). Theoretical calculations demonstrate that the intrinsic mechanism underlying the performance enhancement is attributed to the high inherent conductivity of WNO/NG and the efficient interface charge transfer with LiPSs. The assembled 500 mAh pouch cell delivers a 97% capacity retention after 25 cycles. This strategy provides valuable insights for designing catalytic materials with abundant activity sites and sheds light on the mechanisms of catalytic enhancement in Li-S chemistry.

Carbon Nanotube-Phenyl Modified g-C3N4: A Visible Light Driven Efficient Charge Transfer System for Photocatalytic Degradation of Rhodamine B.

In this study, we report the synthesis and characterization of a novel photocatalyst composite composed of functionalized carbon nanotubes (f-CNT) and phenyl-modified graphitic carbon nitride (PhCN). The incorporation of the phenyl group extends the absorption range into the visible spectrum compared to pure g-C3N4. Additionally, the formation of the heterostructure in the f-CNT/PhCN composite exhibits improved charge transfer efficiency, facilitating the separation and transfer of photogenerated electron-hole pairs and reducing recombination rates. The photocatalytic performance of this composite was evaluated by the degradation of Rhodamine B (RhB) under visible light irradiation. The f-CNT/PhCN composite exhibits remarkable efficiency in degrading RhB, achieving 60% degradation after 4 h, and 100% after 24 h under low-power white LED excitation. This represents a substantial improvement over the non-functionalized CNT/PhCN composite, which shows much lower performance. In contrast, pure PhCN demonstrates very little activity. Structural and optical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, and UV-Vis spectroscopy. Time-resolved photoluminescence measurements were used to study the behavior of photoexcited carriers, confirming that the composite improves charge transfer efficiency for photogenerated carriers by approximately 30%. The results indicate that the functionalization of CNTs significantly enhances the photocatalytic properties of the composite, making f-CNT/PhCN a promising candidate for environmental remediation applications, particularly in the degradation of organic pollutants in wastewater.

Optimizing Reversible Phase-Transformation of FeS2 Anode via Atomic-Interface Engineering Toward Fast-Charging Sodium Storage: Theoretical Predication and Experimental Validation.

Sodium-storage performance of pyrite FeS2 is greatly improved by constructing various FeS2-based nanostructures to optimize its ion-transport kinetics and structural stability. However, less attention has been paid to rapid capacity degradation and electrode failure caused by the irreversible phase-transition of intermediate NaxFeS2 to FeS2 and polysulfides dissolution upon cycling. Under the guidance of theoretical calculations, coupling FeS2 nanoparticles with honeycomb-like nitrogen-doped carbon (NC) nanosheet supported single-atom manganese (SAs Mn) catalyst (FeS2/SAs Mn@NC) via atomic-interface engineering is proposed to address above challenge. Systematic electrochemical analyses and theoretical results unveil that the functional integration of such two type components can significantly enhance ionic conductivity, accelerate charge transfer efficiency, and improve Na+-adsorption capability. Particularly, SAs Mn@NC with Mn-Nx coordination center can reduce the decomposition barrier of Na2S and NaxFeS2 to further accelerate reversible phase transformation of Fe/Na2S→NaFeS2→FeS2 and polysulfides decomposition. As predicted, such FeS2/SAs Mn@NC showcases outstanding rate capability and fascinating cyclic durability. A sequence of kinetic studies and ex situ characterizations provide the comprehensive understanding for ion-transport kinetics and phase-transformation process. Its practical use is further demonstrated in sodium-ion full cell and capacitor with impressive electrochemical capability and excellent energy-density output.

Sputtering induced the architecture of “needle mushroom” shaped Cu2O–NiCo2O4 heterostructure with novel morphology and abundant interface for high-efficiency electrochemical water oxidation

Oxygen evolution reaction (OER) is widely recognized as a bottleneck in the kinetics and activity of decomposition water. Unique geometric design and compositional regulation are important technologies for achieving significant activity and excellent kinetics, but they continue to face obstacles in reaction thermodynamics and kinetic response. Here, a “needle mushroom” shaped Cu2O–NiCo2O4 heterostructure with abundant active sites and optimized conductivity that is grown on the Nickel-foam (NF) (labeled as Cu2O–NiCo2O4/NF-2) is prepared using advanced magnetron sputtering strategies for electrochemical water oxidation. Based on the excellent geometric advantages and efficient charge transfer capabilities, the catalyst of Cu2O–NiCo2O4/NF-2 shows superior electrocatalytic activity (low overpotential) and kinetics (low electrochemical impedance) compared with nanoneedle shaped Cu2O–NiCo2O4/NF-1 and NiCo2O4/NF for OER in alkaline medium. This work demonstrates a practical and economical strategy toward the fabrication of ternary transition metal oxides for water oxidation.

High-throughput and high-sensitive direct detection for pathogenic bacteria of urinary tract infections mediated by block-based design of flexible non-metallic composite SERS substrate

It remains a huge challenge to realize a high-throughput direct detection for pathogenic bacteria with high-sensitivity in practice. Here, we develop a typical two-dimensional (2D) composite semiconductor of BP@MoS2 with special synergistic chemical enhancement-mediated surface-enhanced Raman scattering (SERS) activity. The relative proportion of MoS2 and BP was rationally adjusted in the hydrothermal reaction to screen a composite sample with high charge transfer efficiency. Furthermore, the optimal BP@MoS2 nanocomposites were integrated with polydimethylsiloxane (PDMS) film based on a hydrophilic-hydrophobic scheme to improve the collection and on-site monitoring capability of SERS substrate. Unlike the conventional detection chip, this hydrophilic-hydrophobic model could facilitate the block design of active areas on the PDMS matrix, which was benefit for the high-throughput detection. More importantly, this SERS substrate was applied to directly monitor urinary tract pathogens of Escherichia coli, facilitating satisfactory recoveries between 90% and 110%. Overall, the as-proposed PDMS-BP@MoS2 SERS substrate exhibited advantages in the collection, quantification, and high-throughput fingerprint recognition of pathogenic bacteria, offering a new avenue for the clinical detection.

A Covalent Triazine Framework for Photocatalytic Anti‐Markovnikov Hydrofunctionalizations

AbstractPorous materials‐based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)‐based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C−N and C−O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron‐donating and ‐withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late‐stage functionalization of bio‐active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.

A Covalent Triazine Framework for Photocatalytic Anti-Markovnikov Hydrofunctionalizations.

Porous materials-based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)-based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C-N and C-O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron-donating and -withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late-stage functionalization of bio-active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.

FAPbI3-nanoparticles with ligands act synergistically in absorbent layers for high-performance and stable FAPbI3 based perovskite solar cells

The performance of perovskite solar cells (PSCs) depends on the quality of the perovskite absorber layer. In this study, oleic acid (OA) and oleylamine (OAm) ligand-capped formamidinium lead iodide (FAPbI3) nanoparticles (NPs) were incorporated into the formamidinium iodide (FAI) solution, which is one of the precursors for the sequential deposition of the FAPbI3 layer. The synergistic effect of the FAPbI3-NPs and the capped ligand substantially improves the crystallinity, uniformity, and morphology of the bulk FAPbI3 perovskite films. The enhancements lead to a reduction in charge recombination and a boost in charge transfer efficiency, enabling the optimized PSCs to achieve a remarkable peak power conversion efficiency (PCE) of 25.68 %. Moreover, these PSCs show good stability, with unencapsulated devices maintaining 93 % of the peak performance under ambient air (RH 50 %) for 1000 hours.

Triphenylamine-based D-A-π-A dyes for DSSC applications: Theoretical study on the impact of auxiliary acceptor groups and π-bridges on photovoltaic performance using DFT and TD-DFT calculations

In this study, a series of eight D-Ai-πi-A organic dyes designed by chemically modifying a previously synthesized D-π-A-type organic dye, called DPA-azo-A (R), were examined to assess the impact of the inclusion of different auxiliary acceptor groups (Ai, i = 4) and the substitution of the anthracene π-spacer group by thionothiophene/furofuran πi-bridge on their performance in dye-sensitized solar cells (DSSCs). Density functional theory (DFT) and time-dependent DFT (TD-DFT) computational methods were used to investigate geometrical structures, optoelectronic properties, and some key short-circuit current-related parameters, such as light-harvesting efficiency (LHE), electron injection driving force (ΔGinject), electron regeneration energy (ΔGreg), excitation lifetime (τ) and chemical reactivity. In addition, we identified the most stable TiO2-dye complex. The results showed that these new dyes show a reduced gap, significant absorption, strong adsorption, excellent light harvesting efficiency and better intramolecular charge transfer properties than the reference dye, translating into better photovoltaic performance. Consequently, this theoretical study breaks new ground by offering valuable guidance for the experimental synthesis of highly efficient triphenylamine-based organic dyes for DSSC applications.

Photocatalytic Seawater Splitting by Earth-Abundant Catalysts: Metal-Semiconductor Metamaterials Made of Plasmonic Magnesium Diboride and Transitional Metal Dichalcogenides.

Metal-semiconductor metamaterials hold great promise for photocatalytic water splitting due to their excellent light harvesting in a broad spectral range as well as efficient charge carrier generation and transfer. In the majority of such metamaterials, semiconductors are used to initiate the water splitting reaction, while their metal counterparts are employed to improve light harvesting through plasmonic effects. Here, we describe for the first time an exceptional reversed case of metal-semiconductor photocatalysts in which metals are used to initiate the water splitting reaction and semiconductors are employed to improve light harvesting through the blackbody effect and serve as co-catalysts. The studied photoanodes are made of non-noble plasmonic MgB2 combined with transition metal dichalcogenides (TMDCs). The plasmonic resonances of the MgB2 component contribute to field confinement, plasmon-exciton coupling, and hot-electron transfer providing an enhancement of photoactivity in the entire solar spectrum capable of water splitting. The TMDC component provides impedance matching and enhances light absorption by the metal catalyst. We demonstrate seawater splitting with MgB2-TMDCs photoanodes attaining current densities of ~3 mA cm-2 at solar radiation. The overall efficiency of hydrogen production in seawater splitting by sunlight with the help of the studied photoanodes is 3 % at a bias voltage of Vbias=0.3 V.

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

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

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

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