Role In Photocatalysis Research Articles

Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis

Graphitic carbon nitride (C3N4) is a promising photocatalyst due to its suitable band gap and polymer properties, but its efficiency is limited by the poor separation of photoinduced electron/hole (e–/h+) pairs. To address this issue, we propose creating N vacancies within the layers and bridging K single-atoms between the C3N4 layers through the self-assembly of potassium citrate and melamine–urea monomers. The introduction of N vacancies disrupts the symmetry of C3N4, promoting electron transfer along the delocalized π-conjugated network, while the presence of K atoms provides channels for electron transfer between the layers by forming N–K–N bridges, thereby leading to significant enhancement in the separation and transfer of e–/h+ pairs across spatial dimension. As expected, the co-modified C3N4, with N vacancies and K single-atoms (designated as CN-K-VN), exhibits excellent photocatalytic performance, with reaction rate constant of 9.69×10–2 min–1 (7.39×10–2 min–1 in real water environment) for tetracycline, achieving 80% degradation of tetracycline within 20 minutes. The reaction mechanism, as well as the toxicity of the degradation intermediates, is deeply discussed. This study provides a strategy to enhance the spatial separation of electrons for photocatalyst, highlighting its significance role in photocatalysis.

Boosting photocatalytic NO remove and H2 production by Co(ii,iii)-modified carbon dots assembly into metal–organic frameworks: The Co(ii,iii)-modified carbon dots location matters

Inhibiting electron-hole recombination and improving the utilization efficiency of photogenerated carriers perform a central role in photocatalysis. Herein, a “ship-in-a-bottle” strategy and an impregnation method were employed to incorporate highly active Co(II,III)-modified carbon dots (Co-CDs) inside or supported on a representative metal–organic framework (i.e., NH2-MIL-125), denoted as Co-CDs-N-MIL and Co-CDs/N-MIL, respectively, for photocatalytic removal of NO and H2 production. Compared with pure NH2-MIL-125, the photocatalytic activities of both Co-CDs-N-MIL and Co-CDs/N-MIL were significantly enhanced but distinctly different, suggesting that the photocatalytic efficiency closely correlates with the Co-CDs location relative to the NH2-MIL-125. A series of characterizations confirmed that Co-CDs-N-MIL shortens the electron transport distance to some extent, which is conducive to the suppression of electron-hole complexation, and thus has a better efficiency than Co-CDs/N-MIL.

Tuning Stark effect by defect engineering on black titanium dioxide mesoporous spheres for enhanced hydrogen evolution

Defects can strongly affect the lattice, strain, and electronic structures of nanomaterials photocatalysts, like a double-edged sword of both positive significance and negative influence on photocatalytic performances. To date, most studies into defects only partially elucidated their beneficial or detrimental roles in photocatalysis. However, a quantitative understanding of the photocatalytic performances modulated by defect concentration still needs to be discovered. Here, a series of TiO2−X mesoporous spheres (MS) with different oxygen vacancy concentrations for photocatalytic applications were prepared by high-temperature chemical reduction. The link between oxygen vacancy concentration and photocatalytic performance was successfully established. The localization of carriers dominated by the Stark effect is first enhanced and then weakened with increasing oxygen vacancy concentration, which is a crucial factor in explaining the double-edged sword role of defect concentration in photocatalysis. As the reduction temperature rises to 300 °C, carrier localization dominated by the quantum-confined Stark effect maximizes the separation ability of photo generated electron hole pairs, thus exhibiting the best catalytic performance for photocatalytic hydrogen production and the degradation of organic pollutants, as demonstrated by a hydrogen evolution rate of 523.7 µmol g-1 h-1 and a ninefold higher RhB photodegradation rate compared to TiO2 MS. The work offers excellent flexibility for precisely constructing high-performance photocatalysts by understanding vacancy engineering.

Unraveling the nature of local field distortion-induced dual electron-trapping centers for efficient photocatalytic fuel evolution

Active electron-trapping centers play significant roles in photocatalysis. Herein, we synergize local field distortion and defects in nanocrystals to produce dual electron-trapping centers and unravel the nature of aluminum doping in porous ZnO with tunable amounts of heteroatoms and oxygen vacancies. The introduced Al atoms in the structural domain induce local field distortion and trigger the movement of Zn2+ from a singlet low spin state to a stable triplet state, resulting in the generation of free carriers trapping centers and optimized electronic energy band structure. Dual active electron-trapping centers of heteroatoms and oxygen vacancies promote the Separation of photo-generated charge carriers and reduce the adsorption energies of H* species. Furthermore, the d-band center of Al-doped ZnO with oxygen vacancies shifts to a higher energy position, thus promoting the adsorption and desorption of hydrogen intermediates and exhibiting 4-fold the photocatalytic H2 efficiency of pristine ZnO. This study provides new insights into the rational design of highly efficient oxide-based photocatalysts toward sustainable solar fuel evolution.

Synthesis of a novel biomass waste-based photocatalyst for degradation of high concentration organic pollutants under visible light: Optimization of synthesis condition and operational parameters via RSM-CCD

Reducing electron-hole pair recombination rate under visible light and preventing α-Fe2O3/WO3 nanoparticle aggregation enhances the photocatalytic efficiency. Herein, a novel heterojunction-activated carbon-based photocatalyst (α-Fe2O3/WO3/AC) was successfully synthesized from Rosa Canina seeds and characterized by PL, EIS, Photocurrent, ESR, XPS, LC-MS, FTIR, XRD, SEM, EDS-map, TEM, and BET analyses. Investigating the influence of significant parameters, including impregnation ratio (1–5), activation temperature (400–600 °C), and α-Fe2O3/WO3 loading (10–90 wt.%) by RSM method resulted in optimal photocatalyst synthesis (50 wt.%: FeW/AC3–500) evidenced by its capability for doxycycline degradation. The maximum doxycycline degradation (98.01 %) was achieved under optimal conditions with a degradation rate constant of 0.03 min−1. Trapping experiments revealed that •OH and •O2− played crucial roles in photocatalysis. The possible doxycycline degradation pathway of (50 wt.%: FeW/AC3–500) photocatalyst is proposed. Based on the transient photocurrent measurements and EIS results, the 50 wt.% FeW/AC3–500 composite exhibited a significant enhancement in photocatalytic activity, which can be attributed to the efficient speed of electron-hole separation. Overall, an innovative approach was introduced to design an efficient AC-based photocatalytic process, which enhances the performance of wastewater treatment and environmental remediation.

Carbon Dots: Synthesis, Characterizations, and Recent Advancements in Biomedical, Optoelectronics, Sensing, and Catalysis Applications.

Carbon nanodots (CNDs), a fascinating carbon-based nanomaterial (typical size 2-10 nm) owing to their superior optical properties, high biocompatibility, and cell penetrability, have tremendous applications in different interdisciplinary fields. Here, in this Review, we first explore the superiority of CNDs over other nanomaterials in the biomedical, optoelectronics, analytical sensing, and photocatalysis domains. Beginning with synthesis, characterization, and purification techniques, we even address fundamental questions surrounding CNDs such as emission origin and excitation-dependent behavior. Then we explore recent advancements in their applications, focusing on biological/biomedical uses like specific organelle bioimaging, drug/gene delivery, biosensing, and photothermal therapy. In optoelectronics, we cover CND-based solar cells, perovskite solar cells, and their role in LEDs and WLEDs. Analytical sensing applications include the detection of metals, hazardous chemicals, and proteins. In catalysis, we examine roles in photocatalysis, CO2 reduction, water splitting, stereospecific synthesis, and pollutant degradation. With this Review, we intend to further spark interest in CNDs and CND-based composites by highlighting their many benefits across a wide range of applications.

Electron spin-states reconfiguration induced by alternating temperature gradient for boosting photocatalytic hydrogen evolution on hollow core-shell FeS2/CuCo2O4 Z-scheme heterostructure

The pyroelectric effect and electron spin-state reconfiguration play a critical role in photocatalysis but are seldom investigated. This work is the first to exploit the fluctuating temperature (ΔT) between the cold-hot alternation in photocatalysis to drive the pyroelectric effect and electron spin-sate reconfiguration. FeS2/CuCo2O4 (FS/CCO) hollow core-shell heterojunctions were prepared using hydrothermal and heating treatment methods. The FeS2 (FS) can generate heat under near-infrared (NIR) light to provide the elevated temperature end required for the pyroelectric effect of CuCo2O4 (CCO) under the influence of ΔT. With this thermoelectric and pyroelectric effect, CCO can release surface charges, generating spontaneous polarization, changing the electron (eg) filling number on Co surface sites, reversing the spin electron state, thus controlling the carriers' migration direction and enhancing their separation and migration rate, and finally prolonging their lifetime. As a result, the as-designed FS/CCO-15 composites yielded up to 19.5 mmol g−1 h−1 extraordinary photocatalytic performance, i.e., 10.2 and 6.45-fold of the pure FS (1.92 mmol g−1 h−1) and CCO (3.02 mmol g−1h−1) under simulated sunlight, respectively. It also yielded up to 19.8% average apparent quantum yield. This work thoroughly explored the distinctive impact of the pyroelectric effect, electron spin-state reconfiguration, orbital coupling effect, and hydrogen evolution, guiding us and creating more possibilities for photocatalytic technology and efficiency using NIR light.

Effect of natural non-metallic impurities on the electronic structure and optical properties of sphalerite ZnS

Impurity-bearing sphalerite is widely found in nature and plays a vital role in photocatalysis. A systematic theoretical study of the crystal structure, band gap and optical properties of ZnS containing Si, Se and P impurities, respectively, is carried out using density functional theory calculations. The results show that non-metallic atoms in the interstices narrow the ZnS bandgap, improving the electrical conductivity of sphalerite. Analysis of the optical properties reveals that ZnS containing non-metallic impurities produces light absorption at higher energies. Meanwhile, the presence of all three impurities leads to a red shift in the absorption band edge of ZnS, which favors the extension of the light absorption range of sphalerite. The effect of the Si impurity is greater than that of the remaining two impurities, with the highest red shift. This research contributes to the application of sphalerite (ZnS) containing natural impurities in the field of new luminescent materials.

An unexpected and robust nickel (II)-based ether-bonded homogeneous system: Effective for photocatalytic CO2-to-CO transformation in visible light

Three halogen-containing pyridine carboxylic acid ligands (6-fluoropicolinic acid, 6-chloropicolinic acid, and 6-bromopicolinic acid) were combined with nickel to form three types of complexes: Ni-O ((6,6′-oxydipicoline acid) Ni(H2O)2), Ni-(OH)2((6,6′-hydroxydipicoline acid) Ni(H2O)2) and Ni-Br2((6,6′-bromodipicoline acid) Ni(H2O)2). Interestingly, the nickel salt reacted with 6-fluoropicolinic acid to form the ether-type complex Ni-O, with 6-chloropicolinic acid to form the hydroxy-type complex Ni-(OH)2, and with 6-bromopicolinic acid to form a Ni-Br2 complex with unchanged ligands. The Ni-O and Ni-(OH)2 complexes are novel in structure and especially the Ni-O show an excellent catalytic performance on reduction of CO2 to CO. After 12 h of irradiation, the Ni-O complexes attained a CO turnover number (TON) of 5664.3 and 86.7 % selectivity. The configurations of the complex catalysts have been demonstrated to play a major role in photocatalysis, by integrating analysis of high resolution mass spectrometry (HRMS) as well as density-functional theory (DFT). A potential proton-coupled electron transfer (PCET) mechanism of two-stage photocatalytic process is proposed.

Construction of two-dimensional zinc indium sulfide/bismuth titanate nanoplate with S-scheme heterojunction for enhanced photocatalytic hydrogen evolution

Improving the separation efficiency of photogenerated carriers plays an important role in photocatalysis. In this study, two-dimensional (2D)/2D zinc indium sulfide (ZnIn2S4)/bismuth titanate (Bi4Ti3O12) nanoplate heterojunctions were synthesized to alter the Bi4Ti3O12 morphology, modulate the bandgap of Bi4Ti3O12, and enhance the utilization of light. Meanwhile, the construction of the S-scheme heterojunction establishes an internal electric field at the ZnIn2S4/Bi4Ti3O12 heterojunctions interface and achieves the spatial separation of photogenerated charges. The hydrogen production rate of ZnIn2S4/Bi4Ti3O12 nanoplate with the optimal ratio reaches 27.50 mmol h−1 g−1, which is 1.5 times higher than that of ZnIn2S4/Bi4Ti3O12 nanoflower (18.28 mmol h−1 g−1) and 2.4 times higher than that of ZnIn2S4 (11.69 mmol h−1 g−1). The apparent quantum efficiency of ZnIn2S4/Bi4Ti3O12 nanoplate reached 57.9 % under a single wavelength of light at 370 nm. This work provides insights into the study of new materials for photocatalytic hydrogen production.

Excitonic Effects of the Excited-State Photocatalytic Reaction at the Molecule/Metal Oxide Interface.

Excitonic effects caused by the Coulomb interaction between electrons and holes play a crucial role in photocatalysis at the molecule/metal oxide interface. As an ideal model for investigating the excitonic effect, coadsorption and photodissociation of water and methanol molecules on titanium dioxide involve complex ground-state thermalcatalytic and excited-state photocatalytic reaction processes. Herein, we systemically investigate the excited-state electronic structures of the coadsorption of H2O and CH3OH molecules on a rutile TiO2(110) surface by linear-response time-dependent density functional theory calculations and probe the reaction path for generating HCOOH or CO2, from ground-state and excited-state perspectives. The reaction barriers in excited-state calculations are significantly different from those in ground-state calculations during three processes, with the largest decrease being 0.94 eV for the Ti5c-O-CH2-O-Ti5c formation process.

The Role of Water Molecules on Polaron Behavior at Rutile (110) Surface: A Constrained Density Functional Theory Study.

Understanding the behavior of a polaron in contact with water is of significant importance for many photocatalytic applications. We investigated the influence of water on the localization and transport properties of polarons at the rutile (110) surface by constrained density functional theory. An excess electron at a dry surface favors the formation of a small polaron at the subsurface Ti site, with a preferred transport direction along the [001] axis. As the surface is covered by water, the preferred spatial localization of the polarons is moved from the subsurface to the surface. When the water coverage exceeds half a monolayer, the preferred direction of polaron hopping is changed to the [110] direction toward the surface. This characteristic behavior is related to the Ti3d-orbital occupations and crystal field splitting induced by different distorted structures under water coverage. Our work describes the reduced sites that might eventually play a role in photocatalysis for rutile (110) surfaces in a water environment.

Dual interfacing with metallic cobalt boosts the electron shuttle of CdS-carbide nanoassemblies

Harnessing accelerated interfacial redox, thus boosting charge separation, is of great importance in photocatalytic solar hydrogen generation. In effect, nanoassembling non-noble metallic phases in CdS-based systems and elucidating their role in photocatalysis hold the key to eventually boosting electron shuttle in the field. Here we combine an efficient in-situ exsoluted metallic Co0 nanoparticles on a carbides matrix (CMG) with CdS (CdS@CoCMG) for photogeneration of hydrogen. The metallic cobalt phase exhibits strong binding at the CdS-carbide dual interfaces, forming the accelerated “electron converter” mechanism validated by charge transfer kinetics and achieving two orders of magnitude faster hydrogen production (44.42 mmol g−1 h−1) relative to CdS (0.43 mmol g−1 h−1). We propose that the unique catalyst configuration enable the directional electron-relay photocatalysis via harnessing interfaces between Co0 phase, carbides, and CdS clusters, which eventually boosts the redox process and charge separation of the integrated system, leading to high H2 production rates in the suspension.

Synthesis of pure and highly doped (II-VI) semiconductor nanoparticles of Nickel for effective environmental remediation of Rhodamine-B dye from wastewater streams

In this project, Nickle (Ni) nanoparticles (NPs) were synthesized by co-precipitation methodology using nickel acetate as precursor and methanol, ethylene glycol and 1,2-Butanediol as solvents. Resulting products were analyzed by XRD and SEM, which revealed the morphological changes occurring by varying conditions of solvents, synthesis temperature and time. Alteration in solvents results in change of morphology of NPs that transformed from irregular and anisotropic to spherical one that was evident by SEM mircographs. After that, these samples catalytic potentials were explored by using them for photocatalysis of Rhodamine B dye in batch mode and kinetic investigation of data indicated their feasibility to be employed as catalyst like standard NaBH4 in conventional method following pseudo first order kinetics. Radical scavenger experiments indicated that .OH radicals play main role in photocatalysis of Rh B using Ni NPs.

Unraveling the potential of sonochemically achieved DyMnO3/Dy2O3 nanocomposites as highly efficient visible-light-driven photocatalysts in decolorization of organic contamination

In the present day, the widespread presence of lingering contaminants in ecosystems has prompted scientists to develop novel semiconductor nanoarchitectures that assist in photocatalytic reactions mediated by visible light. As a result, we propose to prepare a series of Dy-Mn-O based nano-catalysts using a sonochemical approach utilizing various ionic phases of surfactants as structure-directing agents. In this study, X-ray diffraction (XRD) and Rietveld refinement techniques were used to explore the fundamental effects of surfactants on the compositional-structural features of the materials. In terms of morphological profiles, DyMnO3/Dy2O3 (DM) nanostructures fabricated with Triton X-80 as a structure-directing agent showed the best uniformity with an acceptable size range between 14.14 and 52.35 nm. In the visible-light-driven photocatalytic domain, these nanocomposites provide high responsiveness based on their optical band gap value of 2.0 eV. According to our findings, two individual factors affect dye activity, namely dye type and concentration, which is why a high decomposition efficiency of 78.8% was obtained for 10 ppm Acid violet (AV) using DyMnO3/Dy2O3 nanocomposites after 120 min of exposure to visible light. Furthermore, radical quenching test confirmation confirmed the mechanistic behind the degradation process. This indicates that active species of O2•− and •OH may play a significant role in photocatalysis. As a result of repeated processes over three consecutive cycles, binary DyMnO3/Dy2O3 nanocomposites had an efficiency of 64.4% in removing dyes from the environment, indicating their high stability.

Eosin Y-Based Metal-Organic Framework Synergistic with Cobalt(II) Complex for Hydrogen Evolution through Photoinduced Intermolecular Electron Transfer.

Photocatalytic hydrogen evolution reaction (HER) is a promising approach for producing clean energy and has the potential to play an important role in the transition toward a more sustainable and environmentally friendly energy system. Optimizing the photoinduced electron transfer (PET) process and increasing visible-light utilization play a central role in photocatalysis. Herein, we built a novel Eosin Y-based metal-organic framework (Zn-EYTP) by synergizing a cobalt(II) complex for boosting the H2 evolution efficiency through photoinduced intermolecular electron transfer. Under optimized conditions, the maximum H2 evolution efficiency for Zn-EYTP was determined to be a turnover number (TON) value of 11,100 under green LED irradiation. And the synthesized Zn-EYTP photocatalysts could be easily recycled to restore the initial photocatalytic activity even after 3 cycles. Detailed studies reveal that the significantly enhanced HER activity in Zn-EYTP could be ascribed to the effective separation of photogenerated charges and the synergistic intermolecular interaction between Zn-EYTP and [Co(bpy)3]Cl2. The present work enables a deeper understanding of the importance of the PET process for enhanced HER photocatalytic activities, which will provide a viable strategy for the development of highly efficient photocatalysts.

Recent Progresses of Polarons: Fundamentals and Roles in Photocatalysis and Photoelectrocatalysis.

Photocatalysis and photoelectrocatalysis are promising ways in the utilization of solar energy. To address the low efficiency of photocatalysts and photoelectrodes, in-depth understanding of their catalytic mechanism is in urgent need. Recently, polaron is considered as an influential factor in catalysis, which brings researchers a new approach to modify photocatalysts and photoelectrodes. In this review, brief introduction of polaron is given first, followed by which models and recent experimentally observations of polarons are reviewed. Studies about roles of polarons in photocatalysis and photoelectrocatalysis are listed in order to provide some inspiration in exploring the mechanism and improving the efficiency of photocatalysis and photoelectrocatalysis.

Al/Nb Co-Doped La2Ti2O7 As an Efficient Photocatalyst for H2 Production from Water

Al/Nb co-doped La2Ti2O7 has been prepared by a facile sol-gel method and investigated as the photocatalyst for H2 evolution. Optimal photocatalytic H2 production is achieved at the sample of La2Ti1.6Al0.2Nb0.2O7 with a production rate of ~37 µmolg-1h-1, which is ~ 2.5 fold higher than that of pristine sample. Further analysis the substitution of Al and Nb in B-site inhibits the growth of grain size, which helps increase the number of active sites. In addition, the introduction of Al and Nb decrease the Ti3+ species, which plays a negative role in photocatalysis as they could provide recombination spot for the photogenerated charges and thus shorten the electron lifetime.

Linker Engineering of Sandwich-Structured Metal-Organic Framework Composites for Optimized Photocatalytic H2 Production.

While the microenvironment around catalytic sites is recognized to be crucial in thermocatalysis, its roles in photocatalysis remain subtle. Herein, a series of sandwich-structured metal-organic framework (MOF) composites, UiO-66-NH2 @Pt@UiO-66-X (X means functional groups), have been rationally constructed for visible-light photocatalytic H2 production. By varying -X groups of UiO-66-X shell, the microenvironment of Pt sites and photosensitive UiO-66-NH2 core can be simultaneously modulated. Significantly, the MOF composites with identical light absorption and Pt loading present distinctly different photocatalytic H2 production rates, following -X group sequence of -H > -Br > -NA (naphthalene) > -OCH3 > -Cl > -NO2 . UiO-66-NH2 @Pt@UiO-66-H demonstrates H2 production rate up to 2708.2μmol g-1 h-1 , ∼222 times that of UiO-66-NH2 @Pt@UiO-66-NO2 . Mechanism investigations suggest that the variation of -X group can balance the charge separation of UiO-66-NH2 core and proton reduction ability of Pt, leading to the optimal activity of UiO-66-NH2 @Pt@UiO-66-H at the equilibrium point. This article is protected by copyright. All rights reserved.

Microtubular cellulose-derived kapok fibre as a solid electron donor for boosting photocatalytic H2O2 production over C-doped g-C3N4 hybrid complexation

Cellulose continues to play an important and emerging role in photocatalysis, and its favourable properties, such as electron-rich hydroxyl groups, could enhance the performance of photocatalytic reactions. For the first time, this study exploited the kapok fibre with microtubular structure (t-KF) as a solid electron donor to enhance the photocatalytic activity of C-doped g-C3N4 (CCN) via ligand-to-metal-charge-transfer (LMCT) to improve hydrogen peroxide (H2O2) production performance. As confirmed by various characterisation techniques, the hybrid complex consisting of CCN grafted on t-KF was successfully developed in the presence of succinic acid (SA) as a cross-linker via a simple hydrothermal approach. The complexation formation between CCN and t-KF results in the CCN-SA/t-KF sample displaying a higher photocatalytic activity than pristine g-C3N4 to produce H2O2 under visible light irradiation. The enhanced physicochemical and optoelectronic properties of CCN-SA/t-KF imply that the LMCT mechanism is crucial in improving photocatalytic activity. This study promotes utilising the unique t-KF material's properties to develop a low-cost and high-performance cellulose-based LMCT photocatalyst.