Charge Separation Research Articles

Recent Developments in Immobilized Photocatalyst for Hydrogen Production

AbstractSolar‐driven water splitting for hydrogen production has emerged as one of the most promising methods for addressing environmental and energy crises. The utilization of immobilized photocatalyst for hydrogen production has attracted significant attention in recent years due to its excellent stability, high photocatalytic efficiency, and ease of recovery and reuse. Hence, a comprehensive review of the development of immobilized photocatalyst appears exceedingly significant. Herein, we initially analyze the advantages of the immobilized photocatalytic system in aspects such as light absorption, photon utilization, and charge separation. Subsequently, we introduce various assembly techniques for immobilized photocatalyst and elaborate on some representative characteristics of this immobilized system. Furthermore, we cite the examples of the application of immobilized photocatalyst in large‐scale hydrogen production to envision its future prospects. Finally, we discuss the remaining issues in this field and outline future directions of development and challenges therein. This review holds great promise for prompting the advancement of immobilized photocatalyst in the field of photocatalysis.

Organic thermoelectric device utilizing charge transfer interface as the charge generation by harvesting thermal energy

We propose an organic thermoelectric device having a new power generation mechanism that extracts small-scale thermal energy, i.e., a few tens of millielectronvolts, at room temperature without a temperature gradient. We demonstrate a new operating mechanism based on an organic thermoelectric power generation architecture that uses the charge separation capabilities of organic charge transfer (CT) interfaces composed of copper (II) phthalocyanine and copper (II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine as the donor and acceptor, respectively. With the optimized device architecture, values of open-circuit voltage VOC of 384 mV, short-circuit current density JSC of 1.1 μA/cm2, and maximum output Pmax of 94 nW/cm2 are obtained. The temperature characteristics of the thermoelectric properties yield activation energy values of approximately 20–60 meV, confirming the low-level thermal energy’s contribution to the power generation mechanism. Furthermore, from surface potential analysis using a Kelvin probe, we confirm that charges are generated at the CT interface, and the electrons and holes are diffused to the counter-electrodes with the aid of Fermi-level alignment between adjacent layers.

Tracking Charge Carrier Paths in Freestanding GaN/AlN Nanowires on Si(111).

Functional and abundant substrate materials are relevant for applying all sophisticated semiconductor-based device components such as nanowire arrays. In the case of GaN nanowires grown by metalorganic vapor phase epitaxy, Si(111) substrates are widely used, together with an AlN interlayer to suppress the well-known Ga-based melt-back-etching. However, the AlN interlayer can degrade the interfacial conductivity of the Si(111) substrate. To reveal the possible impact of this interlayer on the overall electrical performance, an advanced analysis of the electrical behavior with suitable spatial resolution is essential. For the electrical investigation of the nanowire-to-substrate junction, we used a four-point probe measurement setup with sufficiently high spatial resolution. The charge separation behavior of the junction is also demonstrated by an electron beam-induced current mode, while the n-GaN nanowire (NW) core exhibits good electrical conductivity. The charge carrier-selective transport at the NW-to-substrate junction can be attributed to different, local material compositions by two main effects: the reduction of Ga adatoms by shadowing of the lower part of the NW structure by the top part during growth, i.e. the protection of the pedestal footprint from Ga adsorption. Our combination of investigation methods provides direct insight into the nanowire-to-substrate junction and leads to a model of the conductivity channels at the nanowire base. This knowledge is crucial for all future GaN bottom-up grown nanowire structure devices on conductive Si(111) substrates.

Piezo-photocatalysis synergy in γ-GeSe for highly efficient oxygen evolution reaction

Solar-driven semiconductor photocatalysts are highly appealing in applications of environmental remediation and energy conversion. However, photocatalytic reactions, particularly oxygen evolution reaction (OER), are often constrained by the swift recombination of electron–hole pairs, thereby resulting in low reaction efficiency. Although it is effective to separate charge carriers by constructing heterojunctions to form built-in electric field, the lattice mismatch and inefficient interlayer charge transfer of heterojunctions in the photocatalysts limit their further development. Here, we propose a new strategy by constructing an internal electric field for OER through an individual piezoelectric two-dimensional material. The results indicate that the piezoelectric effect regulates the electronic structure, reduces bandgap, improves light absorption efficiency, and that the displacement of positive and negative charge centers is the key factor in the enhanced OER. This research indicates the feasibility of combining piezoelectric properties of two-dimensional materials with OER (1.19 eV), providing new insights and guidance for applying the piezoelectric effect in the OER and opening up a way to promote efficient separation of charge carriers.

Hydroxymethylfurfural adsorption modulating charge separation characteristics of carbon-rich carbon nitrides for simultaneous photocatalytic hydrogen evolution and 2,5-diformylfuran production

Carbon-rich melon-based carbon nitrides (CNs), in which the sp2 N atoms and the terminal C–NH2 within the heptazine rings are partially replaced by the graphitic carbon atoms and C–H terminals, respectively, are synthesized through the condensation of 2,4,6-triaminopyrimidine-added supramolecular complexes comprising melamine and cyanuric acid. Optical characterizations reveal that increasing the C/N ratio in CNs improves their light-harvesting and charge-separation capabilities. Nevertheless, the photocatalytic activities of carbon nitrides reach an optimal level at an appropriate C/N ratio for simultaneous H2 evolution and 2,5-diformylfuran (DFF) production from 5-(hydroxymethyl)furfural (HMF) aqueous solution. Hydrogen evolution from water and DFF production by selective HMF oxidation are driven by photogenerated electrons and holes, respectively. Density functional theory calculations suggest that the adsorption of HMF on carbon-CN dramatically influences the molecular orbital contributions to the lowest singlet excited state, altering its charge separation character and, consequently, the photocatalytic activity. The improvement of charge separation in the optimized CN by HMF adsorption is further confirmed by experimental measurements.

Enhancing NO2 sensing performance through interface engineering in Cs2AgBiBr6/SnO2/ZnO-NRs sensor

Developing sensors that operate under ambient conditions with minimal energy consumption, ensuring a robust response and efficient recovery to toxic NO2 gas, can help take appropriate and corrective measures to protect human health from exposure to hazardous environments. In this study, we have successfully designed a gas sensor device based on a sandwich structure of Cs2AgBiBr6/SnO2/ZnO-nanorods (CABB/SnO2/ZnO-NRs) for detecting NO2 at room temperature. The insertion of the SnO2 layer between the CABB and ZnO-NRs, which works as a hole blocker, not only improves significantly the sensor stability from a few hours to more than a month but also offers the energy step for electron transfer from ZnO-NRs to CABB. The CABB layer further enhances the charge separation, transport, and conductivity from the perovskite to the ZnO surface, actively participating in the gas-sensitive reaction. The response of CABB/SnO2/ZnO-NRs sensors to 100 ppm NO2 is about 9 times higher than that of ZnO-NRs, showing a significantly improved NO2 sensing performance.

Introduction of a Hydroxyl Self-Sacrificing Surface on Ultrathin Poly(heptazine imide) Nanosheets by KCl Grafting: A New Strategy to Improve the Photocatalytic Production of H2O2.

The generation of H2O2 through photocatalysis is increasingly recognized as a viable approach for addressing the energy and environmental challenges encountered in industrial production processes. In this research, we synthesized ultrathin (1 nm) poly(heptazine imide) (PHI) nanosheets as a photocatalyst by a one-step KCl molten salt process. The utilization of Fourier transform infrared and X-ray photoelectron spectroscopy substantiated that the interlayer-bonded potassium atoms induce polarization in water molecules, facilitating the attachment of hydroxyl groups on the surfaces of nanosheets. These groups serve as self-sacrificing entities, promoting the reaction that leads to the generation of H2O2. The preparation temperature and KCl doping amount factors for the H2O2 generation rate were investigated, and the mechanism of the KCl-bonded structure on photogeneration charge separation transport was analyzed. Owing to the elevated crystallization and the presence of surface self-sacrificing hydroxyl groups, the rate of H2O2 production reaches 6117.5 and 308.35 μmol·g-1·h-1 under visible-light irradiation (λ ≥ 420 nm) in isopropanol solution and pure water, respectively. These rates are 30 and 18.7 times higher than those observed for bulk g-C3N4, respectively. The photocatalytic kinetic processes for H2O2 formation and decomposition were also calculated to investigate the catalyst activities.

Configuration Interaction in Frontier Molecular Orbital Basis for Screening the Spin-Correlated, Spatially Separated Triplet Pair State 1(T···T) Formation.

In the theoretical screening of Singlet Fission rates in molecular aggregates, often the frontier molecular orbital model for dimers is employed. However, the dimer approach fails to account for recent experimental findings that suggest singlet fission progresses through a further intermediate state featuring two spatially separated, spin-correlated triplets, specifically a 1(T···T) state. We address this limitation by generalizing the often used frontier molecular orbital model for singlet fission by incorporation of both separated Charge Transfer (C···T) and 1(T···T) states as well as mixed triplet-charge transfer states, delivering analytic expressions for the diabatic matrix elements. Applying the methodology to the perylene diimide trimer, we examine the packing dependence of competing formation pathways of the 1(T···T) state by evaluation of diabatic matrix elements.

Heteronanotrimers by Selective Photodeposition of Gold Nanodots on Janus-Type Cu2‒ xS/CuInS2 Heteronanocrystals.

This study focuses on the development of environmentally friendly Au-Cu2-xS/CuInS2 heteronanotrimers. The chosen strategy relies on the laser photodeposition of a single gold nanodot (ND) onto Janus Cu2- xS/CuInS2 heteronanocrystals (HNCs). This method offers precise control over the number, location, and size (5 to 8nm) of the Au NDs by adjusting laser power for the career production, concentration of hole scavenger for charge equilibration in redox reactions, and gold precursor concentration, and exposure time for the final ND size. The photoreduction of gold ions onto HNCs starts systematically at the Cu2- xS tip. The Au deposition then depends on the CuInS2 segment length. For short HNCs, stable Au-Cu2- xS/CuInS2 heteronanotrimers form, while long HNCs undergo a secondary photo-induced step: the initial Au ND is progressively oxidized, with concomitant deposition of a second gold ND on the CuInS2 side, to yield Au2S-Cu2- xS/CuInS2-Au heteronanotrimers. Results are rationalized by quantitative comparison with a model that describes the growth kinetics of NDs and Au-Cu2- xS transformation and emphasizes the importance of charge separation in predicting selective deposition in heteronanotrimer production. The key parameter controlling Au-Cu2‒ xS/CuInS2 HNCs is the photoinduced electric field gradient generated by charge separation, which is tailored by controlling the CuInS2 segment size.

Loop quantum gravity effects on electromagnetic properties of charged leptons

The efforts in this contribution consist in reassessing a modified Dirac equation that incorporates a γ0γ5\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\gamma ^0 \\gamma _5$$\\end{document}-Lorentz-symmetry violating (LSV) term induced as a Loop Quantum Gravity (LQG) effect. Originally, this equation has been applied and considered as a good scenario for describing a number of investigations on the flight time of cosmic neutrinos, which suggests that the speed, in vacuum, in connection with the geometry that describes a granular space-time, takes the energy-dependent form, e.g., v(E)=1±E/ELSV\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$v(E) =1 \\pm E/E_{\ ext {\ iny LSV}}$$\\end{document}, with ELSV≈6,5×1017\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$E_{\ ext {\ iny LSV}} \\approx 6,5 \ imes 10^{17}$$\\end{document} GeV for neutrinos. Once LQG provides a viable way to understand this picture consistently, we pursue an analysis of this effective Dirac equation to inspect some of its properties. These include: the derivation of the modified fermionic propagator, attainment of the Gordon decomposition of the vector current with minimal electromagnetic coupling to obtain information on the form factors, examination of the non-relativistic limit of the equation, evaluation of the spin- and velocity-dependent corrections to the Coulomb potential due to LQG effects, and the modified Hamiltonian in the low-relativistic regime. The study of the form factors may open up paths to set up bounds on the LQG parameters from the precision measurements of electromagnetic attributes of the charged leptons, such as their respective electric and magnetic dipole moments.

Improvement of photocatalytic CO2 reduction with conjugated organic polymers by rational modulation of donor, acceptor and bonding method.

The use of metal-free catalysts to convert CO2 into valuable chemicals is very challenging. Here, we synthesized a conjugated organic polymer (TpTf-1) featuring 2,4,6-Triphenyl-1,3,5-Triazine as the acceptor unit, triphenylamine as the donor unit, and vinylidene bond as the linkage. The local structure of donor-acceptor (D-A) forms an intramolecular electric field that can promote the separation of photogenerated electrons and charges, meanwhile, the vinylidene bond can further change the charge distribution to promote exciton dissociation. Without the use of photosensitizers, the TpTf-1 exhibits outstanding selectivity of CO of up to 91.96%, with a production rate of 45.2 μmol·g-1·h-1 at visible light, which is 3.4-fold than TaTf-1 with the same D-A structure but linking in imine bond and is 2.8-fold than TpTf-2 linking in vinylidene bond but with a different donor unit. Moreover, TpTf-1 has a CO production rate of up to 117.3 μmol·g-1·h-1 under full wavelength light irradiation.

Integration of Perylene Diimide into a Covalent Organic Framework for Photocatalytic Oxidation.

Perylene diimides (PDIs) have garnered considerable attention due to its immense potential in photocatalysis. However, manipulating the molecular packing within their aggregates and enhancing the efficiency of photogenerated carrier recombination remain significant challenges. In this study, we demonstrate the incorporation of a PDI unit into a covalent organic framework (COF), named PDI-PDA, by linking an ortho-substituted PDI with p-phenylenediamine (PDA) to control its intermolecular aggregation. The incorporation enables precise modulation of electron transfer dynamics, leading to a ten-fold increase in the efficiency of photocatalytic oxidation of thioether to sulfoxide with PDI-PDA compared to the PDI molecular counterpart, achieving yields exceeding 90%. Electron property studies and density functional theory calculations show that the PDI-PDA with its well-defined crystal structure, enhances π-π stacking and lowers the electron transition barrier. Moreover, the strong electron-withdrawing ability of the PDI unit promotes the spatial separation of the valency band maximum and conduction band minimum of PDI-PDA suppressing the rapid recombination of photogenerated electron-hole pairs and improving charge separation efficiency to give high photocatalytic efficiency. This study provides a brief yet effective way for the improvement of the photocatalytic efficiency of commonly used PDI-based dyes by integrating them into a framework skeleton.

Integration of Perylene Diimide into a Covalent Organic Framework for Photocatalytic Oxidation

AbstractPerylene diimides (PDIs) have garnered considerable attention due to their immense potential in photocatalysis. However, manipulating the molecular packing within their aggregates and enhancing the efficiency of photogenerated carrier recombination remain significant challenges. In this study, we demonstrate the incorporation of a PDI unit into a covalent organic framework (COF), named PDI‐PDA, by linking an ortho‐substituted PDI with p‐phenylenediamine (PDA) to control its intermolecular aggregation. The incorporation enables precise modulation of electron‐transfer dynamics, leading to a ten‐fold increase in the efficiency of photocatalytic oxidation of thioether to sulfoxide with PDI‐PDA compared to the PDI molecular counterpart, with yields exceeding 90 %. Electron property studies and density functional theory calculations show that the PDI‐PDA with its well‐defined crystal structure, enhances π–π stacking and lowers the electron transition barrier. Moreover, the strong electron‐withdrawing ability of the PDI unit promotes the spatial separation of the valency band maximum and conduction band minimum of PDI‐PDA, suppressing the rapid recombination of photogenerated electron‐hole pairs and improving the charge‐separation efficiency to give high photocatalytic efficiency. This study provides a brief but effective way for improving the photocatalytic efficiency of commonly used PDI‐based dyes by integrating them into a framework skeleton.

Precisely Constructing Molecular Junctions in Hydrogen-Bonded Organic Frameworks for Efficient Artificial Photosynthetic CO2 Reduction.

The development of artificial photocatalysts to convert CO2 into renewable fuels and H2O into O2 is a complex and crucial task in the field of photosynthesis research. The current challenge is to enhance photogenerated charge separation, as well as to increase the oxidation capability of materials. Herein, a molecular junction-type porphyrin-based crystalline photocatalyst (Ni-TCPP-TPyP) was successfully self-assembled by incorporating a nickel porphyrin complex as a reduction site and pyridyl porphyrin as an oxidation site via hydrogen bonding and π-π stacking interactions. The resulting material has a highly crystalline structure, and the formation of inherent molecular junctions can accelerate photogenerated charge separation and transport. Thus, Ni-TCPP-TPyP achieved an excellent CO production rate of 309.3 μmol g-1 h-1 (selectivity, ~100%) without the use of any sacrificial agents, which is more than ten times greater than that of single-component photocatalyst (Ni-TCPP) and greater than that of the most organic photocatalysts. The structure-function relationship was investigated by femtosecond transient absorption spectroscopy and density functional theory calculations. Our work provides new insight for designing efficient artificial photocatalysts, paving the way for the development of clean and renewable fuels through the conversion of CO2 using solar energy.

Built-in electric field mediated S-scheme high-quality charge separation in BiVO4/NiAl-LDH heterojunction for highly efficient photocatalytic degradation of antibiotics

As an up and coming technology for antibiotics removal from water, photocatalysis required well-pleasing charge isolation, migration, and utilization efficiency to come true an efficaciously photocatalytic performance, but developing affordable and high-efficiency photocatalyst remains a great challenging. Herein, an emerging S-scheme BiVO4/NiAl-LDH heterojunction was ingeniously fabricated by mulberry-like BiVO4 microrods immobilized onto the surfaces of flower-like NiAl-LDH microspheres. The physicochemical properties of the BiVO4/NiAl-LDH heterojunctions were analyzed by multiple techniques. Expectedly, the manufactured BiVO4/NiAl-LDH heterojunction endowed a significantly strengthened removal rate of tetracycline compared to mono-component BiVO4 and NiAl-LDH under visible light. Specifically, the optimized BVO-NAL-3 manifested the exceptional tetracycline removal efficiency with an apparent rate constant of up to 0.0409 min−1, which was close to 34.1 and 4.4 times more rapid than those of neat NiAl-LDH and BiVO4, severally. This signal enhancement was centrally related to the creation of S-scheme heterojunction, which accelerated high-quality charge separation and strengthened redox capacity under the force of created a built-in electric field, which was corroborated by experiments results together with density functional theory calculations. Besides, the generation of superoxide radicals and photogenerated holes played an imperative role in the tetracycline degradation over BVO-NAL-3. Noteworthily, BVO-NAL-3 expressed the satisfactory stability and exceptional resistance to environmental interferences. More amazingly, other refractory antibiotics including ciprofloxacin, levofloxacin and amoxicillin were also efficaciously eliminated by BVO-NAL-3. Ultimately, the possible degradation mechanism and pathways of tetracycline were logically inferred. This work unveils a valuable afflatus for the reasonable layout and establishment of S-scheme heterojunction with high-quality charge separation for the eradication of antibiotics.

Orientation-Dependent Photocatalysis of Imine-Linked Covalent Organic Frameworks Based on Thienothiophenes for Oxidation of Amines to Imines.

Toward visible light photocatalysis, covalent organic frameworks (COFs) have recently garnered growing attention. The effect of different orientations of imine of imine-linked COFs on photocatalysis should be elucidated. Here, two COFs are developed with 2,5-diphenylthieno[3,2-b]thiophene (DPTT) and 1,3,6,8-tetraphenylpyrene (Py) linked by imine, affording DPTT-Py-COF and Py-DPTT-COF, respectively. Distinctly, DPTT-Py-COF and Py-DPTT-COF have high crystallinity and porosity, paving the way to highly efficient photocatalysis. Theoretical calculations demonstrate that both DPTT-Py-COF and Py-DPTT-COF are of similar bandgaps but of varied energy positions due to the different orientations of imine. Besides, characterizations disclose that DPTT-Py-COF delivers more enhanced charge separation and transfer than Py-DPTT-COF. Probed by the oxidation of amine to imine, DPTT-Py-COF exhibits a blue light photocatalytic performance superior to that of Py-DPTT-COF. DPTT-Py-COF, a highly recyclable photocatalyst, enables the oxidation of various amines to imines with oxygen. This work highlights that tuning the microenvironment of COFs unravels tenable performances in photocatalysis.

Precisely Constructing Molecular Junctions in Hydrogen‐Bonded Organic Frameworks for Efficient Artificial Photosynthetic CO2 Reduction

AbstractThe development of artificial photocatalysts to convert CO2 into renewable fuels and H2O into O2 is a complex and crucial task in the field of photosynthesis research. The current challenge is to enhance photogenerated charge separation, as well as to increase the oxidation capability of materials. Herein, a molecular junction‐type porphyrin‐based crystalline photocatalyst (Ni‐TCPP‐TPyP) was successfully self‐assembled by incorporating a nickel porphyrin complex as a reduction site and pyridyl porphyrin as an oxidation site via hydrogen bonding and π–π stacking interactions. The resulting material has a highly crystalline structure, and the formation of inherent molecular junctions can accelerate photogenerated charge separation and transport. Thus, Ni‐TCPP‐TPyP achieved an excellent CO production rate of 309.3 μmol g−1 h−1 (selectivity, ~100 %) without the use of any sacrificial agents, which is more than ten times greater than that of single‐component photocatalyst (Ni‐TCPP) and greater than that of the most organic photocatalysts. The structure‐function relationship was investigated by femtosecond transient absorption spectroscopy and density functional theory calculations. Our work provides new insight for designing efficient artificial photocatalysts, paving the way for the development of clean and renewable fuels through the conversion of CO2 using solar energy.

Completely Multipolar Model as a General Framework for Many-Body Interactions as Illustrated for Water.

We introduce a general framework for many-body force fields, the Completely Multipolar Model (CMM), that utilizes multipolar electrical moments modulated by exponential decay of electron density as a common functional form for all terms of an energy decomposition analysis of intermolecular interactions. With this common functional form, the CMM model establishes well-formulated damped tensors that reach the correct asymptotes at both long- and short-range while formally ensuring no short-range catastrophes. CMM describes the separable EDA terms of dispersion, exchange polarization, and Pauli repulsion with short-ranged anisotropy, polarization as intramolecular charge fluctuations and induced dipoles, while charge transfer describes explicit movement of charge between molecules, and naturally describes many-body charge transfer by coupling into the polarization equations. We also utilize a new one-body potential that accounts for intramolecular polarization by including an electric field-dependent correction to the Morse potential to ensure that CMM reproduces all physically relevant monomer properties including the dipole moment, molecular polarizability, and dipole and polarizability derivatives. The quality of CMM is illustrated through agreement of individual terms of the EDA and excellent extrapolation to energies and geometries of an extensive validation set of water cluster data.

Sunlight-driven charge separation for a heterojunction of nano-pyramidal CuWO4-MOF modified TiO2 nanoflakes for photocatalytic degradation of ciprofloxacin

The study presents a breakthrough of a balanced charge separation for heterojunction CuWO4-TiO2 cocatalyst to efficiently enhance visible light photocatalytic degradation of ciprofloxacin (CIP). A solvothermal-synthesized nanopyramid-like CuWO4 semiconductor was assembled before sol–gel treatment with TiO2 precursors to generate CuWO4-TiO2 nanocomposites. The optical, structural, and morphological properties of CuWO4-TiO2 were elucidated using UV–Vis DRS, XRD, FTIR, Raman spectroscopy, and TEM/SEM techniques. The UV–Vis DRS spectroscopy of as-synthesized CuWO4-TiO2 cocatalyst demonstrated enhanced visible light absorbance. The XRD patterns of CuWO4-TiO2 revealed a triclinic phase nanocrystal. The O-Ti–O functionality was confirmed by FTIR spectroscopy. The photoactive bands corresponding to anatase redshift were observed from Raman spectroscopy of CuWO4-TiO2 nanocomposite. The PL studies attributed this redshift to the elevated extra energy bands that aid electron/hole pair charge separation in a co-catalyst heterojunction CuWO4-TiO2 nanocomposite afforded by embedding CuWO4-MOF within TiO2 crystalline. The TEM showed that un-sintered CuWO4.MOF mimicked a pyramidal shape and converted to nanoflakes upon sintering, while TiO2 and CuWO4-TiO2 retained a tetragonal shape. The photocatalytic activity of CuWO4-TiO2 cocatalyst was studied using CIP, as a model pollutant. The innovative design of 5CuWO4-TiO2 charge separation nanocomposite completely degraded 10 mg L−1 CIP solution at pH = 6.31 (natural pH) and 9 under 120 min of sunlight irradiation.

Hedgehog Zinc Oxide-Graphene Quantum Dot Heterostructures as Photocatalysts for Visible-Light-Driven Water Splitting.

The development of efficient photocatalysts for sustainable hydrogen production via water splitting is vital for advancing renewable energy technologies. In this study, we present the synthesis and characterization of a novel visible-light-active photocatalyst comprising hedgehog-shaped zinc oxide (ZnO) nanostructures coupled with graphene quantum dots (GQDs). Optical properties assessed by UV-visible and photoluminescence (PL) spectroscopy revealed that the ZnO/GQDs heterostructure possessed a reduced band gap (2.86 eV) compared with pristine ZnO (3.10 eV), resulting in improved light absorption and charge separation. Electrochemical analyses indicated a significantly higher photocurrent response and lower charge transfer resistance for the ZnO/GQDs heterostructure compared with the pristine ZnO nanostructure. Photocatalytic tests demonstrated that the ZnO/GQDs heterostructure achieved over 3-fold higher hydrogen (H2) production rates, with an apparent quantum yield (AQY) of 1.51% at 440 nm, and maintained stable activity over prolonged reaction periods. These results highlight the enhanced photocatalytic efficiency and stability of the ZnO/GQDs heterostructure, underscoring its potential as a high-performance photocatalyst for sustainable hydrogen generation. The synergistic effects between ZnO nanostructures and GQDs offer valuable insights into the design of advanced photocatalytic materials for renewable energy applications.