Comparative study of the photocatalytic activity of g-C3N4/MN4 (M = Mn, Fe, Co) for water splitting reaction: A theoretical study.

In this study, nanocomposites of g-C3N4/MN4 (where M is Mn, Fe and Co) have been designed using advanced density functional theory (DFT) calculations. A comprehensive analysis was conducted on the geometry, electronic, optical properties, work function, charge transfer interaction and adhesion energy of the g-C3N4/MN4 heterostructures and concluded that g-C3N4/FeN4 and g-C3N4/CoN4 heterojunctions exhibit higher photocatalytic performance than individual units. The better photocatalytic activity can be attributed mainly by two facts; (i) the visible light absorption of both g-C3N4/FeN4 and g-C3N4/CoN4 interfaces are higher compared to its isolated analogs and (ii) a significant enhancement of band gap energy in g-C3N4/FeN4 and g-C3N4/CoN4 heterostructures limited the electron-hole recombination significantly. The potential of the g-C3N4/MN4 heterojunctions as a photocatalyst for the water splitting reaction was assessed by examining its band alignment for water splitting reaction. Importantly, while the electronic and magnetic properties of MN4 systems were studied, this is the first example of inclusion of MN4 on graphene-based material (g-C3N4) for studying the photocatalytic activity. The state of the art DFT calculations emphasis that g-C3N4/FeN4 and g-C3N4/CoN4 heterojunctions are half metallic photocatalysts, which is limited till date.

Tailoring Mott-Schottky RuO2/MgFe-LDH Heterojunctions in Electrospun Microfibers: A Bifunctional Electrocatalyst for Water Electrolysis.

Hydrogen is a fuel of the future that has the potential to replace conventional fossil fuels in several applications. The quickest and most effective method of producing pure hydrogen with no carbon emissions is water electrolysis. Developing highly active electrocatalysts is crucial due to the slow kinetics of oxygen and hydrogen evolution, which limit the usage of precious metals in water splitting. Interfacial engineering of heterostructures has sparked widespread interest in improving charge transfer efficiency and optimizing adsorption/desorption energetics. The emergence of a built-in-electric field between RuO2 and MgFe-LDH improves the catalytic efficiency toward water splitting reaction. However, LDH-based materials suffer from poor conductivity, necessitating the design of 1D materials by integration of RuO2/ MgFe-LDH to enhance catalytic properties through large surface areas and high electronic conductivity. Experimental results demonstrate lower overpotentials (273 and 122 mV at 10 mA cm-2) and remarkable stability (60 h) for the RuO2/MgFe-LDH/Fiber heterostructure in OER (1 m KOH) and HER (0.5 m H2SO4) reactions. Density functional theory (DFT) unveils a synergistic mechanism at the RuO2/MgFe-LDH interface, leading to enhanced catalytic activity in OER and improved adsorption energy for hydrogen atoms, thereby facilitating HER catalysis.

Stimulating Electron Delocalization of Lanthanide Elements through High-Entropy Confinement to Promote Electrocatalytic Water Splitting.

High-entropy alloys (HEAs) have aroused extensive attention in the field of catalysis. However, due to the integration of multiple active sites in HEA, it exhibits excessive adsorption behavior resulting in difficult desorption of active species from the catalyst surfaces, which hinders the catalytic efficiency. Therefore, adjusting the adsorption strength of the active site in HEA to enhance the catalytic activity is of great importance. By introducing rare-earth (RE) elements into the high-entropy alloy, the delocalization of 4f electrons can be achieved through the interaction between the multimetal active site and RE, which benefits to regulate the adsorption strength of the HEA surface. Herein, the RE Ce-modified hexagonal-close-packed PtRuFeCoNiZn-Ce/C HEAs are synthesized and showed an excellent electrocatalytic activity for hydrogen evolution reaction and oxygen evolution reaction with ultralow overpotentials of 4, 7 and 156, 132 mV, respectively, to reach 10 mA cm-2 in 0.5 M H2SO4 and 1.0 M KOH solutions, and the assembled water electrolysis cell only requires a voltage of 1.43 V to reach 10 mA cm-2, which is much better than the performance of PtRuFeCoNiZn/C. Combined with the results of in situ attenuated total reflection infrared spectroscopy and density functional theory (DFT), the fundamental reasons for the improvement of catalyst activity come from two aspects: (i) local lattice distortion of HEA caused by the introduction of RE with large atomic radius induces 4f orbital electron delocalization of RE elements and enhances electron exchange between RE and active sites. (ii) The electronegativity difference between the RE element and the active site forms a surface dipole in HEA, which optimizes the adsorption of the active intermediate by the HEA surface site. This study provides an insightful idea for the rational design of high-performance HEA- and RE-based electrocatalysts.

Hematene Nanoplatelets with Enhanced Visible Light Absorption; the Role of Aromatic Molecules.

Hematite has been considered an important candidate for the development of an efficient photoelectrocatalytic water-splitting system. One of the most serious obstacles that limits the efficiency of hematite is low absorption capacity in visible light. Herein, we report the production of hematene nanoplatelets from hematite ore with yields of up to 60%, using a low-cost, sustainable method that is based on the ultrasonic treatment of hematite ore in a water solution of a series of organic aromatic compounds. We show that the chemisorption of molecules with increased aromaticity on the surface of hematene resulted in the significant improvement of its visible light absorptivity, with an increase of up to 200%. As a result, using a water solution of terephthalaldehyde as a liquid medium, hematite ore was exfoliated to hematene nanoplatelets with a yield of 40% and remarkable stability in water. Due to this, hematene was easily drop-casted on glass forming homogenous thin films with strong absorptivity in the visible region.

Hybridization of bimetallic cobalt-molybdenum oxide multihole nanosheets with selenium adulteration as advanced bifunctional electrocatalysts for boosting overall water splitting.

Electrocatalytic water splitting produces green and pollution-free hydrogen as a clean energy carrier, which can effectively alleviate energy crisis. In this paper, bimetallic and selenium doped cobalt molybdate (Se-CoMoO4) nanosheets with rough surface are resoundingly prepared. The multihole Se-CoMoO4 nanosheets display ultrathin and rectangular architecture with the dimensions of âˆ¼ 3.5 µm and 700 nm for length and width, respectively. The Se-CoMoO4 electrocatalyst shows remarkable water electrolysis activity and stability. The overpotentials of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are 270 and 63.3 mV at 10 mA cm-2, along with low Tafel slopes of 51.6 and 62.0 mV dec-1. Furthermore, the Se-CoMoO4 couple electrolyzer merely requires a cell voltage of 1.48 V to achieve 10 mA cm-2 current density and presents no apparent attenuation for 30 h. This investigation declares that the hybridization of transition bimetallic oxide with nonmetallic adulteration can afford a tactic for the preparation of bifunctional non-precious metal-based electrocatalysts.

Cobalt nanoparticles intercalation coupled with tellurium-doping MXene for efficient electrocatalytic water splitting.

Nowadays, the inherent re-stacking nature and weak d-p hybridization orbital interactions within MXene remains significant challenges in the field of electrocatalytic water splitting, leading to unsatisfactory electrocatalytic activity and cycling stability. Herein, this work aims to address these challenges and improve electrocatalytic performance by utilizing cobalt nanoparticles intercalation coupled with enhanced π-donation effect. Specifically, cobalt nanoparticles are integrated into V2C MXene nanosheets to mitigate the re-stacking issue. Meanwhile, a notable charge redistribution from cobalt to vanadium elevates orbital levels, reduces π*-antibonding orbital occupancy and alleviates Jahn-Teller distortion. Doping with tellurium induces localized electric field rearrangement resulting from the changes in electron cloud density. As a result, Co-V2C MXene-Te acquires desirable activity for hydrogen evolution reaction and oxygen evolution reaction with the overpotential of 80.8 mV and 287.7 mV, respectively, at the current density of -10 mA cm-2 and 10 mA cm-2. The overall water splitting device achieves an impressive low cell voltage requirement of 1.51 V to obtain 10 mA cm-2. Overall, this work could offer a promising solution when facing the re-stacking issue and weak d-p hybridization orbital interactions of MXene, furnishing a high-performance electrocatalyst with favorable electrocatalytic activity and cycling stability.

Catalytic Water Electrolysis by Co-Cu-W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry.

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co-Cu-W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co2+ (octahedral), Cu+/2+ (tetrahedral/square-planar), and W6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co3+ and Cu0 are the active catalytic sites involved in the OER and HER, respectively, while Cu2+ and W6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co-Cu-W MMO system. These results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co3+ hydroperoxide, whose formation is accompanied by changes in the Cu-O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

Protecting TiS3 Photoanodes for Water Splitting in Alkaline Media by TiO2 Coatings.

Titanium trisulfide (TiS3) nanoribbons, when coated with titanium dioxide (TiO2), can be used for water splitting in the KOH electrolyte. TiO2 shells can be prepared through thermal annealing to regulate the response of TiS3/TiO2 heterostructures by controlling the oxidation time and growth atmosphere. The thickness and structure of the TiO2 layers significantly influence the photoelectrocatalytic properties of the TiS3/TiO2 photoanodes, with amorphous layers showing better performance than crystalline ones. The oxide layers should be thin enough to transfer photogenerated charge through the electrode-electrolyte interface while protecting TiS3 from KOH corrosion. Finally, the performance of TiS3/TiO2 heterostructures has been improved by coating them with various electrocatalysts, NiSx being the most effective. This research presents new opportunities to create efficient semiconductor heterostructures to be used as photoanodes in corrosive alkaline aqueous solutions.

Anchoring Ni(OH)2-CeOx Heterostructure on FeOOH-Modified Nickel-Mesh for Efficient Alkaline Water-Splitting Performance with Improved Stability under Quasi-Industrial Conditions.

Developing low-cost and industrially viable electrode materials for efficient water-splitting performance and constructing intrinsically active materials with abundant active sites is still challenging. In this study, a self-supported porous network Ni(OH)2-CeOx heterostructure layer on a FeOOH-modified Ni-mesh (NiCe/Fe@NM) electrode is successfully prepared by a facile, scalable two-electrode electrodeposition strategy for overall alkaline water splitting. The optimized NiCe0.05/Fe@NM catalyst reaches a current density of 100 mA cm-2 at an overpotential of 163 and 262 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1.0 m KOH with excellent stability. Additionally, NiCe0.05/Fe@NM demonstrates exceptional HER performance in alkaline seawater, requiring only 148 mV overpotential at 100 mA cm-2. Under real water splitting conditions, NiCe0.05/Fe@NM requires only 1.701 V to achieve 100 mA cm-2 with robust stability over 1000 h in an alkaline medium. The remarkable water-splitting performance and stability of the NiCe0.05/Fe@NM catalyst result from a synergistic combination of factors, including well-optimized surface and electronic structures facilitated by an optimal Ce ratio, rapid reaction kinetics, a superhydrophilic/superaerophobic interface, and enhanced intrinsic catalytic activity. This study presents a simple two-electrode electrodeposition method for the scalable production of self-supported electrocatalysts, paving the way for their practical application in industrial water-splitting processes.

Solar-Driven Sustainability: III-V Semiconductor for Green Energy Production Technologies.

Long-term societal prosperity depends on addressing the world's energy and environmental problems, and photocatalysis has emerged as a viable remedy. Improving the efficiency of photocatalytic processes is fundamentally achieved by optimizing the effective utilization of solar energy and enhancing the efficient separation of photogenerated charges. It has been demonstrated that the fabrication of III-V semiconductor-based photocatalysts is effective in increasing solar light absorption, long-term stability, large-scale production and promoting charge transfer. This focused review explores on the current developments in III-V semiconductor materials for solar-powered photocatalytic systems. The review explores on various subjects, including the advancement of III-V semiconductors, photocatalytic mechanisms, and their uses in H2 conversion, CO2 reduction, environmental remediation, and photocatalytic oxidation and reduction reactions. In order to design heterostructures, the review delves into basic concepts including solar light absorption and effective charge separation. It also highlights significant advancements in green energy systems for water splitting, emphasizing the significance of establishing eco-friendly systems for CO2 reduction and hydrogen production. The main purpose is to produce hydrogen through sustainable and ecologically friendly energy conversion. The review intends to foster the development of greener and more sustainable energy source by encouraging researchers and developers to focus on practical applications and advancements in solar-powered photocatalysis.

Constructing CoP/Ni2P Heterostructure Confined Ru Sub-Nanoclusters for Enhanced Water Splitting in Wide pH Conditions.

Developing efficient electrocatalysts for water splitting is of great significance for realizing sustainable energy conversion. In this work, Ru sub-nanoclusters anchored on cobalt-nickel bimetallic phosphides (Ru-CoP/Ni2P) are constructed by an interfacial confinement strategy. Remarkably, Ru-CoP/Ni2P with low noble metal loading (33.1 µg cm-2) shows superior activity for hydrogen evolution reaction (HER) in all pH values, whose turnover frequency (TOF) is 8.7, 15.3, and 124.7 times higher than that of Pt/C in acidic, alkaline, and neutral conditions, respectively. Meanwhile, it only requires the overpotential of 171 mV@10 mA cm-2 for oxygen evolution reaction (OER) and corresponding TOF is 20.3 times higher than that of RuO2. More importantly, the Ru-CoP/Ni2P||Ru-CoP/Ni2P displays superior mass activity of 4017 mA mgnoble metal -1 at 2.0 V in flowing alkaline water electrolyzer, which is 105.1 times higher than that of Pt/C||IrO2. In situ Raman spectroscopy demonstrates that the Ru sites in Ru-CoP/Ni2P play a key role for water splitting and follow the adsorption evolution mechanism toward OER. Further mechanism studies disclose the confined Ru atom contributes to the desorption of H2 during HER and the formation of O-O bond during OER, leading to fast reaction kinetics. This study emphasizes the importance of interface confinement for enhancing electrocatalytic activity.

Constructing Hydrangea-Like Iron-Cobalt Phosphides via Boron-Assisted strategy as an Efficient Catalyst for Water Splitting at High Current Density.

Finding suitable bifunctional catalysts for industrial hydrogen production is the key to fully building a hydrogen energy society. Here we report a modulation of the surface morphology of electrodeposited CoP to form hydrangea-like Cobalt-Iron bimetallic phosphide (B-CoFeP@CoP) via ion-exchange and NaBH4-assisted methods. This catalyst exhibited excellent bifunctional catalytic capability at high current densities, achieving a current density of 500 mA cm-2 at a small overpotential (387 mV for OER and 252 mV for HER). When assembled into an OWS electrolyzer, this catalyst showed a fairly low cell voltage (≈1.88 V) at 500 mA cm-2 current density.，Furthermore, B-CoFeP@CoP shows ceaseless durability over 120 h in both freshwater and seawater with almost no change in the cell voltage. A combined experimental and theoretical study identified that the unique hydrangea-like structure provided a larger electrochemically active surface area and more effective active sites. Further analysis indicates that during the OER process, phosphides ensure that bimetallic active sites adsorb more OOH * intermediates and further DFT calculations showed that B-Fe2P and B-Co2P acted as active centers for dissociation of H2O and desorption of H2, respectively, to synergistically catalyze the HER process.

Strong Vertical Piezoelectricity and Broad-pH-Value Photocatalyst in Ferroelastic Y2Se2BrF Monolayer.

With the development of miniaturized devices, there is an increasing demand for 2D multifunctional materials. Six ferroelastic semiconductors, Y2Se2XX' (X, X' = I, Br, Cl, or F; X ≠ X') monolayers, are theoretically predicted here. Their in-plane anisotropic band structure, elastic and piezoelectric properties can be switched by ferroelastic strain. Moderate energy barriers can prevent the undesired ferroelastic switching that minor interferences produce. These monolayers exhibit high carrier mobilities (up to 104 cm2 V-1 s-1) with strong in-plane anisotropy. Furthermore, their wide bandgaps and high potential differences make them broad-pH-value and high-performance photocatalysts at pH value of 0-14. Strikingly, Y2Se2BrF possesses outstanding d33 (d33 = -405.97 pm/V), greatly outperforming CuInP2S6 by 4.26 times. Overall, the nano Y2Se2BrF is a hopeful candidate for multifunctional devices to generate a direct current and achieve solar-free photocatalysis. This work provides a new paradigm for the design of multifunctional energy materials.

First-Principles Computational Screening of Two-Dimensional Polar Materials for Photocatalytic Water Splitting.

The band gap constraint of the photocatalyst for overall water splitting limits the utilization of solar energy. A strategy to broaden the range of light absorption is employing a two-dimensional (2D) polar material as photocatalyst, benefiting from the deflection of the energy level due to their intrinsic internal electric field. Here, by using first-principles computational screening, we search for 2D polar semiconductors for photocatalytic water splitting from both ground- and excited-state perspectives. Applying a unique electronic structure model of polar materials, there are 13 photocatalyst candidates for the hydrogen evolution reaction (HER) and 8 candidates for the oxygen evolution reaction (OER) without barrier energies from the perspective of the ground-state free energy variation calculation. In particular, Cu2As4Cl2S3 and Cu2As4Br2S3 can catalyze HER and OER simultaneously, becoming promising photocatalysts for overall water splitting. Furthermore, by combining ground-state band structure calculations with excited-state charge distribution and transfer calculated by linear-response time-dependent density functional theory (LR-TDDFT) and time-dependent ab initio nonadiabatic molecular dynamics (NAMD), respectively, the rationality of the 2D polar material model has been manifested. The intrinsic built-in electric field promotes the separation of charge carriers while suppressing their recombination. Therefore, our computational work provides a high-throughput method to design high-performance photocatalysts for water splitting.

Single Atom Ag Bonding Between PF3T Nanocluster and TiO2 Leads the Ultra-Stable Visible-Light-Driven Photocatalytic H2 Production.

Atomic Ag cluster bonding is employed to reinforce the interface between PF3T nano-cluster and TiO2 nanoparticle. With an optimized Ag loading (Ag/TiO2 = 0.5 wt%), the Ag atoms will uniformly disperse on TiO2 thus generating a high density of intermediate states in the band gap to form the electron channel between the terthiophene group of PF3T and the TiO2 in the hybrid composite (denoted as T@Ag05-P). The former expands the photon absorption band width and the latter facilitates the core-hole splitting by injecting the photon excited electron (from the excitons in PF3T) into the conduction band (CB) of TiO2. These characteristics enable the high efficiency of H2 production to 16 580 µmol h-1 g-1 and photocatalysis stability without degradation under visible light exposure for 96 h. Compared to that of hybrid material without Ag bonding (TiO2@PF3T), the H2 production yield and stability are improved by 4.1 and 18.2-fold which shows the best performance among existing materials in similar component combination and interfacial reinforcement. The unique bonding method offers a new prospect to accelerate the development of photocatalytic hydrogen production technologies.

Promoting the Photoelectrochemical Properties of BiVO4 Photoanode via Dual Modification with CdS Nanoparticles and NiFe-LDH Nanosheets.

Bismuth vanadate (BiVO4) has long been considered a promising photoanode material for photoelectrochemical (PEC) water splitting. Despite its potential, significant challenges such as slow surface water evolution reaction (OER) kinetics, poor carrier mobility, and rapid charge recombination limit its application. To address these issues, a triadic photoanode has been fabricated by sequentially depositing CdS nanoparticles and NiFe-layered double hydroxide (NiFe-LDH) nanosheets onto BiVO4, creating a NiFe-LDH/CdS/BiVO4 composite. This newly engineered photoanode demonstrates a photocurrent density of 3.1 mA cm-2 at 1.23 V vs. RHE in 0.1 M KOH under AM 1.5 G illumination, outperforming the singular BiVO4 photoanode by a factor of 5.8 and the binary CdS/BiVO4 and NiFe-LDH/BiVO4 photoanodes by factors of 4.9 and 4.3, respectively. Furthermore, it exhibits significantly higher applied bias photon-to-current efficiency (ABPE) and incident photon-to-current efficiency (ICPE) compared to pristine BiVO4 and its binary counterparts. This enhancement in PEC performance is ascribed to the formation of a CdS/BiVO4 heterojunction and the presence of a NiFe-LDH OER co-catalyst, which synergistically facilitate charge separation and transfer efficiencies. The findings suggest that dual modification of BiVO4 with CdS and NiFe-LDH is a promising approach to enhance the efficiency of photoanodes for PEC water splitting.

Sulfurization of bimetallic (Co and Fe) oxide and alloy decorated on multi-walled carbon nanotubes as efficient bifunctional electrocatalyst for water splitting.

The advancement in electrocatalysis, particularly in the development of efficient catalysts for hydrogen and oxygen evolution reactions (HER and OER), is crucial for sustainable energy generation through processes like overall water splitting. A notable bifunctional electrocatalyst, CoFe2O4/Co7Fe3, has been engineered to facilitate both OER and HER concurrently, aiming to reduce overpotentials. In the pursuit of further enhancing catalytic efficiency, a morphological transformation has been achieved by introducing a sulphur source and multi-walled carbon nanotubes (MWCNTs) into the catalyst system, resulting in S-CoFe2O4/Co7Fe3/MWCNTs. This modification has significantly improved the activity for both OER and HER. An onset overpotential of 250 mV@10 mAcm-2 for the OER and 270 mV@50 mAcm-2 for the HER, indicating efficient catalytic activity at relatively low overpotentials. S-CoFe2O4/Co7Fe3/MWCNTs display an outstanding long-term stability in alkaline electrolytes, with minimal Tafel slopes of 77 mV/dec for the OER and 70 mV/dec for the HER, suggesting sustained catalytic performance over extended periods. Furthermore, when employed as both the cathode and anode in the context of complete water splitting, S-CoFe2O4/Co7Fe3/MWCNTs demonstrate an impressive cell voltage of 1.52 V at a current density of 10 mA cm-2 in a 1 M KOH solution, showcasing its viability for practical applications. Given its cost-effectiveness and superior activity, S-CoFe2O4/Co7Fe3/MWCNTs hold significant promise for widespread applications in overall water splitting electrocatalysis, contributing to the advancement of cleaner and sustainable fuel generation technologies.

Promoted surface reconstruction of pentlandite via phosphorus-doping for enhanced oxygen evolution reaction.

The pentlandite Fe5Ni4S8(abbreviated as FNS) is not efficient for water splitting because of its inferior performance for the oxygen evolution reaction (OER). This issue originates from the low activity and instability of FNS during the OER process but can be solved through appropriate doping. Herein, a P-doping strategy based on annealing in the presence of NaH2PO2as a phosphorus source upstream was employed on FNS to enhance its activity and stability toward OER. The results demonstrated fine-tuned electronic structures of Fe and Ni in FNS through P-doping, resulting in suppressed Fe leaching,improved electrical conductivity of FNS, and easier formation of NiOOH on the surface of the catalyst. In turn, these features enhanced the OER activity and stability. The optimal P-doped FNS catalyst FNSP-40 exhibited a 4-fold greater electrochemical surface area compared to that of FNS, accompanied by an overpotential of 235 mV at 10 mA cm-2. The optimized FNSP-40 catalyst was used as an anode, and platinum-decorated FNS was used as a cathode. This combination demonstrated an electrolysis performance with a cell voltage of 1.57 V, reaching a current density of 100 mA cm-2,which indicates efficient operation. The advantages of P-doping engineering were also verified in simulated seawater with enhanced OER performance. Overall, the proposed strategy looks promising for the fabrication of pentlandite-structured catalysts for efficient alkaline water and seawater oxidation.

A review on development and modification strategies of MOFs Z-scheme heterojunction for photocatalytic wastewater treatment, water splitting, and DFT calculations.

Increasing water pollution and decreasing energy reserves have emerged as growing concerns for the environment. These pollution are due to the dangerous effects of numerous pollutants on humans and aquatic organisms, such as hydrocarbons, biphenyls, pesticides, dyes, pharmaceuticals, and metal ions. On the other hand, the need for a clean environment, finding alternatives to fossil and renewable fuels is very important. Hydrogen (H2) is regarded as a viable and promising substitute for fossil fuels, and a range of methodologies have been devised to generate this particular source of energy. Metal-organic frameworks (MOFs) are a new generation of nanoporous coordination polymers whose crystal structure is composed of the juxtaposition of organic and inorganic constituent units. Due to their flexible nature, regular structure, and high surface area, these materials have attracted much attention for removing various pollutants from water and wastewater, and water splitting. MOFs Z-scheme heterojunctions have been identified as an economical and eco-friendly method for eliminating pollutants from wastewater systems, and producing H2. Their low-cost synthesis and unique properties increase their application in various energy and environment fields. The heterojunctions possess diverse properties, such as exceptional surface area, making them ideal for degradation and separation. The development and formulation of Z-scheme heterojunctions photocatalytic systems using MOFs, which possess stable and potent redox capability, have emerged as a successful approach for addressing environmental pollution and energy shortages in recent times. Through the utilization of the benefits offered by MOFs Z-scheme heterojunctions photocatalysts, such as efficient separation and migration of charge carriers, extensive spectrum of light absorption, among other advantages, notable enhancements can be attained. This review encompasses the synthesis techniques, structure, and properties of MOFs Z-scheme heterojunctions, and their extensive use in treating various wastewaters, including dyes, pharmaceuticals, and heavy metals, and water splitting. Also, it provides an overview of the mechanisms, pathways, and various theoretical and practical aspects for MOFs Z-scheme heterojunctions. Finally, it thoroughly assesses existing challenges and suggests further research on the promising applications of MOFs Z-scheme in industrial-scale wastewater treatment.

Dual Hole Transport Layers Heterojunction and Band Alignment Engineered Mo:BiVO4 Photoanodes for Efficient Water Splitting.

BiVO4-based photoanode is one of the most promising photoanodes for photoelectrocatalytic water splitting. However, the serious problem of interface charge recombination limits its further development. Here, a Mo:BiVO4/NiOx/CPF-TCzB/NiCoBi photoanode is constructed with double hole transport layer and an energy level gradient to achieve an effective photo-generated holes extraction and accumulation at the surface electrocatalyst. The conjugated polycarbazole framework CPF-TCzB is used as hole transport layer to eliminate the charge recombination center between Mo:BiVO4 and NiCoBi electrocatalyst and realize the extraction and storage of photo-generated hole; NiOx nanoparticles are further inserted between Mo:BiVO4 and CPF-TCzB to form a gradient energy level, eliminating the energy level barrier and optimizing band alignment. As a result, Mo:BiVO4/NiOx/CPF-TCzB/NiCoBi achieves a much higher photocurrent densities of 3.14 mA cm-2 than that of Mo:BiVO4 (0.42 mA cm-2) at 0.6 V versus RHE. This work provides an specific way to adjust the band structure of BiVO4-based photoanodes and realize efficient hole extraction and storage for PEC water splitting.