Photocatalytic System Research Articles

Visible-Light-Driven Photocatalytic H2 Production Using Composites of Co-Al Layered Double Hydroxides and Graphene Derivatives.

The direct conversion of solar energy into chemical energy represents an enormous challenge for current science. One of the commonly proposed photocatalytic systems is composed of a photosensitizer (PS) and a catalyst, together with a sacrificial electron donor (ED) when only the reduction of protons to H2 is addressed. Layered double hydroxides (LDH) have emerged as effective catalysts. Herein, two Co-Al LDH and their composites with graphene oxide (GO) or graphene quantum dots (GQD) have been prepared by coprecipitation and urea hydrolysis, which determined their structure and so their catalytic performance, giving H2 productions between 1409 and 8643 μmol g-1 using a ruthenium complex as PS and triethanolamine as ED at 450 nm. The influence of different factors, including the integration of both components, on their catalytic behavior, has been studied. The proper arrangement between the particles of both components seems to be the determining factor for achieving a synergistic interaction between LDH and GO or GQD. The novel Co-Al LDH composite with intercalated GQD achieved an outstanding catalytic efficiency (8643 μmol H2 g-1) and exhibited excellent reusability after 3 reaction cycles, thus representing an optimal integration between graphene materials and Co-Al LDH for visible light driven H2 photocatalytic production.

Life Cycle Assessment of Immobilised and Slurry Photocatalytic Systems for Removal of Natural Organic Matter in Water

This study investigates the environmental impacts caused by the scaling up of the photocatalytic purification of drinking water using ultraviolet light-emitting diode technology. The life cycle assessment methodology was utilised to estimate the environmental impacts of two different reactor setups commonly used in lab-scale studies: an immobilised and a suspended TiO2 catalytic system. The functional unit adopted was the treatment of 1 L of water with an initial 7.8 mg/L concentration of natural organic matter, achieving a final 1 mg/L concentration. The use of a suspended photocatalyst was found to have an environmental footprint that was 87% lower than that of the immobilised one. From the sensitivity analysis, the environmental hotspots of the treatment process were the electricity usage and immobilised catalyst production. Therefore, alternative scenarios investigating the use of a renewable electricity mix and recyclable materials were explored to enhance the environmental performance of the photocatalytic treatment process. Using a renewable electricity mix, a decrease of 55% and 15% for the suspended and immobilised catalyst, respectively, was observed. Additionally, the process of recycling the glass used to support the immobilised catalyst achieved a maximum reduction of 22% in the environmental impact from the original scenario, with 100 glass reuses appearing to provide diminishing returns on the environmental impact savings.

A high-efficiency photocatalytic hydrogen evolution system based on nickel-quinoxaline dithiolate complexes and water-soluble CdSe quantum dots

Photocatalytic water splitting of water for hydrogen evolution is one of the effective methods to obtain clean hydrogen energy. In the present work, the following materials were synthesized: two nickel quinoxaline thiolate complexes [NBu4]2 [Ni(qdt)2] (1, Bu = n-butyl, qdt = quinoxaline-dithiol), [NBu4]2 [Ni(qdt)2(NO2)2] (2) and water-soluble MPA-CdSe quantum dots (MPA-CdSe QDs, MPA = 3-mercaptopropionic acid). Subsequently, an efficient three-component photocatalytic hybrid system for hydrogen evolution was developed and tested under visible light irradiation, in which one of the target complex 1 or 2 was used as the catalyst, triethylamine (TEA) was used as the sacrificial electron donor, and MPA-CdSe QDs were used as the light harvesting reagent. The turnover numbers (TON) for H2 evolution of 8974 (vs. complex 1) and 6532 (vs. complex 2) were obtained under the optimal conditions with TEA concentration of 5 %, pH = 12, and concentration of complex 1 or 2 of 1 × 10−5 mol L−1 after 13 h of irradiation (λ > 420 nm) in pure water. The mechanism investigation indicated that critical steps of hydrogen production was formation of hydride intermediates Ni(II)-H and Ni(I)-H spices, followed by the reaction of two Ni(II)-H or Ni(I)-H species with protons generating H2 molecules and regenerating the catalyst Ni(II).

Hollow g-C3N4@Ag3PO4 Core-Shell Nanoreactor Loaded with Au Nanoparticles: Boosting Photothermal Catalysis in Confined Space.

Low solar energy utilization efficiency and serious charge recombination remain major challenges for photocatalytic systems. Herein, a hollow core-shell Au/g-C3N4@Ag3PO4 photothermal nanoreactor is successfully prepared by a two-step deposition method. Benefit from efficient spectral utilization and fast charge separation induced by the unique hollow core-shell heterostructure, the H2 evolution rate of Au/g-C3N4@Ag3PO4 is 16.9 times that of the pristine g-C3N4, and the degradation efficiency of tetracycline is increased by 88.1%. The enhanced catalytic performance can be attributed to the ordered charge movement on the hollow core-shell structure and a local high-temperature environment, which effectively accelerates the carrier separation and chemical reaction kinetics. This work highlights the important role of the space confinement effect in photothermal catalysis and provides a promising strategy for the development of the next generation of highly efficient photothermal catalysts.

Interfacial Design of Particulate Photocatalyst Materials for Green Hydrogen Production.

Green hydrogen production using particulate photocatalyst materials has attracted much attention in recent years because this process could potentially lead to inexpensive and scalable solar-to-chemical energy conversion systems. Although the development of efficient particulate photocatalysts enabling one-step overall water splitting (OWS) with solar-to-hydrogen efficiencies in excess of 10% remains challenging, promising photocatalyst candidates exhibiting OWS activity have been demonstrated. This review provides a comprehensive introduction to the solar-to-hydrogen energy conversion process of semiconductor photocatalyst materials and highlights recent advances in photocatalytic OWS via both one-step and two-step photoexcitation processes. The review also covers recent developments in the photocatalytic OWS of SrTiO3, including the establishment of large-scale photocatalytic systems, interfacial design using cocatalysts to enhance water splitting activity, and its photoelectrochemical (PEC) properties at the electrified solid/liquid interface. In addition, there is a special focus on visible-light-absorbing oxynitride and oxysulfide particulate photocatalysts with absorption edges near 600 nm. Methods for photocatalyst preparation and surface modification, as well as PEC properties, are also discussed. The semiconductor properties of particulate photocatalysts obtained from photoelectroanalytical evaluations using particulate photoelectrodes are evaluated. This review is intended to provide guidelines for the future development of particulate photocatalysts capable of efficient and stable OWS.

Dual-mode harvest solar energy for photothermal Cu2-xSe biomineralization and seawater desalination by biotic-abiotic hybrid

Biotic-abiotic hybrid photocatalytic system is an innovative strategy to capture solar energy. Diversifying solar energy conversion products and balancing photoelectron generation and transduction are critical to unravel the potential of hybrid photocatalysis. Here, we harvest solar energy in a dual mode for Cu2-xSe nanoparticles biomineralization and seawater desalination by integrating the merits of Shewanella oneidensis MR-1 and biogenic nanoparticles. Photoelectrons generated by extracellular Se0 nanoparticles power Cu2-xSe synthesis through two pathways that either cross the outer membrane to activate periplasmic Cu(II) reduction or are directly delivered into the extracellular space for Cu(I) evolution. Meanwhile, photoelectrons drive periplasmic Cu(II) reduction by reversing MtrABC complexes in S. oneidensis. Moreover, the unique photothermal feature of the as-prepared Cu2-xSe nanoparticles, the natural hydrophilicity, and the linking properties of bacterium offer a convenient way to tailor photothermal membranes for solar water production. This study provides a paradigm for balancing the source and sink of photoelectrons and diversifying solar energy conversion products in biotic-abiotic hybrid platforms.

Surface plasmon resonance-mediated photocatalytic H2 generation.

The limited yield of H2 production has posed a significant challenge in contemporary research. To address this issue, researchers have turned to the application of surface plasmon resonance (SPR) materials in photocatalytic H2 generation SPR, arising from collective electron oscillations, enhances light absorption and facilitates efficient separation and transfer of electron-hole pairs in semiconductor systems, thereby boosting photocatalytic H2 production efficiency. However, existing reviews predominantly focus on SPR noble metals, neglecting non-noble metals and SPR semiconductors. In this review, we begin by elucidating five different SPR mechanisms, covering hot electron injection, electric field enhancement, light scattering, plasmon-induced resonant energy transfer, and photo-thermionic effect, by which SPR enhances photocatalytic activity. Subsequently, a comprehensive overview follows, detailing the application of SPR materials-metals, non-noble metals, and SPR semiconductors-in photocatalytic H2 production. Additionally, a personal perspective is offered on developing highly efficient SPR-based photocatalysis systems for solar-to-H2 conversion in the future. This review aims to guide the development of next-gen SPR-based materials for advancing solar-to-fuel conversion.

Engineering Spatially Adjacent Redox Sites with Synergistic Spin Polarization Effect to Boost Photocatalytic CO2 Methanation.

The integration of oxidation and reduction half-reactions to amplify their synergy presents a considerable challenge in CO2 photoconversion. Addressing this challenge requires the construction of spatially adjacent redox sites while suppressing charge recombination at these sites. This study introduces an innovative approach that utilizes spatial synergy to enable synergistic redox reactions within atomic proximity and employs spin polarization to inhibit charge recombination. We incorporate Mn into Co3O4 as a catalyst, in which Mn sites tend to enrich holes as water activation sites, while adjacent Co sites preferentially capture electrons to activate CO2, forming a spatial synergy. The direct H transfer from H2O at Mn sites facilitates the formation of *COOH on adjacent Co sites with remarkably favorable thermodynamic energy. Notably, the incorporation of Mn induces spin polarization in the system, significantly suppressing the recombination of photogenerated charges at redox sites. This effect is further enhanced by applying an external magnetic field. By synergizing spatial synergy and spin polarization, Mn/Co3O4 exhibits a CH4 production rate of 23.4 μmol g-1 h-1 from CO2 photoreduction, showcasing a 28.8 times enhancement over Co3O4. This study first introduces spin polarization to address charge recombination issues at spatially adjacent redox sites, offering novel insights for synergistic redox photocatalytic systems.

Multi-Variable Multi-Metric Optimization of Self-Assembled Photocatalytic CO2 Reduction Performance Using Machine Learning Algorithms.

The sunlight-driven reduction of CO2 into fuels and platform chemicals is a promising approach to enable a circular economy. However, established optimization approaches are poorly suited to multivariable multimetric photocatalytic systems because they aim to optimize one performance metric while sacrificing the others and thereby limit overall system performance. Herein, we address this multimetric challenge by defining a metric for holistic system performance that takes multiple figures of merit into account, and employ a machine learning algorithm to efficiently guide our experiments through the large parameter matrix to make holistic optimization accessible for human experimentalists. As a test platform, we employ a five-component system that self-assembles into photocatalytic micelles for CO2-to-CO reduction, which we experimentally optimized to simultaneously improve yield, quantum yield, turnover number, and frequency while maintaining high selectivity. Leveraging the data set with machine learning algorithms allows quantification of each parameter's effect on overall system performance. The buffer concentration is unexpectedly revealed as the dominating parameter for optimal photocatalytic activity, and is nearly four times more important than the catalyst concentration. The expanded use and standardization of this methodology to define and optimize holistic performance will accelerate progress in different areas of catalysis by providing unprecedented insights into performance bottlenecks, enhancing comparability, and taking results beyond comparison of subjective figures of merit.

Boosting photothermal-assisted photocatalytic H2 production over black g-C3N4 nanosheet photocatalyst via incorporation with carbon dots

Although photocatalytic H2 production based on semiconductor materials has a wide potential application, it still facing challenges such as slow reaction kinetics or complex synthesis processes. To meet these challenges, the carbon dots loaded black g-C3N4 (CN-B-CDs) was synthesized by simple calcination method to achieve efficient photothermal-assisted photocatalytic H2 production. Photothermal imaging experiments confirmed the photothermal effect of CN-B and CDs as dual heat sources to increase the temperature of the composite system, thus improving the effective separation of photo-generated charges. In addition, multiple photocatalytic H2 production tests exhibited that CN-B-CDs photocatalysts not only have strong stability but also can accommodate a variety of complex water bodies, which displayed the potential for industrial application. This study combined the photothermal effect and the mechanism by which the CDs promote the charge transfer to design a new photocatalytic H2 production system and provided a new scheme for achieving efficient photothermal-assisted photocatalytic H2 production using carbon-based materials.

Visible-Light Photocatalytic C-H Amination of Arenes Utilizing Acridine-Lewis Acid Complexes.

This report describes the development of a visible-light photocatalytic system for C(sp2)-H amination that leverages in situ-generated photocatalysts. We demonstrate that the combination of acridine derivatives and Lewis acids forms potent photooxidants that promote the C-H amination of electronically diverse arenes upon irradiation with visible-light (440 nm). A first-generation photocatalyst composed of Sc(OTf)3 and acridine effects the C-H amination of substrates with oxidation potentials ≤ +2.5 V vs SCE with pyrazole, triazole, and pyridine nucleophiles. Furthermore, the simplicity and modularity of this system enable variation of both Lewis acid and acridine to tune reactivity. This enabled the rapid identification of two second-generation photocatalysts (derived from (i) Al(OTf)3 and acridine or (ii) Sc(OTf)3 and a pyridinium-substituted acridine) that catalyze a particularly challenging transformation: C(sp2)-H amination with benzene as the limiting reagent.

Innovations in Photocatalytic and Photoelectrocatalytic Water Splitting: Pathways to Efficiently Convert Biomass into Renewable Energy and Chemicals

AbstractThis review comprehensively explores the integration of photocatalytic (PC) and photoelectrocatalytic (PEC) technologies for hydrogen production via water splitting, in synergy with the efficient conversion of biomass resources. This synergistic strategy significantly boosts hydrogen production rates in both PC and PEC systems and enhances solar energy conversion efficiency. Furthermore, it enables selective conversion of cost‐effective biomass via precise modulation of catalyst structures, paving a novel pathway for green hydrogen generation and synthesis of high‐value chemicals. Specifically, the manuscript highlights recent progress in the oxidation and coupling reactions of biomass derivatives, such as methanol, ethanol, glycerol, and 5‐hydroxymethylfurfural, in PC/PEC systems. It reveals their potential to enhance hydrogen production efficiency and the synthesis of high‐value organic compounds. Future research should focus on employing in‐situ characterization techniques and theoretical simulations to deeply understand reaction mechanisms, thus advancing the field of biomass conversion through photocatalytic/photoelectrocatalytic methods.

Harmonising light and structure: exploring ZnO/MOF composite photocatalysts for environmental remediations

Harmonising light and structure: exploring ZnO/MOF composite photocatalysts for environmental remediations

Abundant Edge Active Sites-Modified High-Crystalline g-C3N5 for Hydrogen Peroxide Production from Pure-Water via a Quasi-Homogeneous Photocatalytic Process.

Ultrathin carbon nitride pioneered a paradigm that facilitates effective charge separation and acceleration of rapid charge migration. Nevertheless, the dissociation process confronts a disruption owing to the proclivity of carbon nitride to reaggregate, thereby impeding the optimal utilization of active sites. In response to this exigency, the adoption of a synthesis methodology featuring alkaline potassium salt-assisted molten salt synthesis is advocated in this work, aiming to craft a nitrogenated graphitic carbon nitride (g-C3N5) photocatalyst characterized by thin layer and hydrophilicity, which not only amplifies the degree of crystallization of g-C3N5 but also introduces a plethora of abundant edge active sites, engendering a quasi-homogeneous photocatalytic system. Under visible light irradiation, the ultra-high H2O2 production rate of this modified high-crystalline g-C3N5 in pure water attains 151.14µmh-1. This groundbreaking study offers a novel perspective for the innovative design of highly efficient photocatalysts with a quasi-homogeneous photocatalytic system.

Solvothermally Grown Oriented WO3 Nanoflakes for the Photocatalytic Degradation of Pharmaceuticals in a Flow Reactor.

Contamination by pharmaceuticals adversely affects the quality of natural water, causing environmental and health concerns. In this study, target drugs (oxazepam, OZ, 17-α-ethinylestradiol, EE2, and drospirenone, DRO), which have been extensively detected in the effluents of WWTPs over the past decades, were selected. We report here a new photoactive system, operating under visible light, capable of degrading EE2, OZ and DRO in water. The photocatalytic system comprised glass spheres coated with nanostructured, solvothermally treated WO3 that improves the ease of handling of the photocatalyst and allows for the implementation of a continuous flow process. The photocatalytic system based on solvothermal WO3 shows much better results in terms of photocurrent generation and photocatalyst stability with respect to state-of-the-art WO3 nanoparticles. Results herein obtained demonstrate that the proposed flow system is a promising prototype for enhanced contaminant degradation exploiting advanced oxidation processes.

Photocatalytic Nitrogen Fixation Coupled with the Generation of Value-Added Chemicals from N2 and Cellulose over MoO3 Nanosheets.

Photocatalytic nitrogen fixation from N2 provides an alternative strategy for ammonia (NH3) production, but it was limited by the consumption of a sacrificial electron donor for the currently reported half-reaction system. Here, we use naturally abundant and renewable cellulose as the sacrificial reagent for photocatalytic nitrogen fixation over oxygen-vacancy-modified MoO3 nanosheets as the photocatalyst. In this smartly designed photocatalytic system, the photooxidation of cellulose not only generates value-added chemicals but also provides electrons for the N2 reduction reaction and results in the production of NH3 with a maximum rate of 68 μmol·h-1·g-1. Also, the oxygen vacancies provide efficient active sites for both cellulose oxygenolysis and nitrogen fixation reactions. This work represents useful inspiration for realizing nitrogen fixation coupled with the generation of value-added chemicals from N2 and cellulose through a photocatalysis strategy.

Defect‐Rich Graphdiyne Quantum Dots as Efficient Electron‐Donors for Hydrogen Generation

AbstractDownsizing the graphdiyne (GDY) network to shape quantum dots (QDs) will provide attractive optical and electronic properties associated with quantum confinement and edge effects. Here, it is demonstrated that quantum confinement and defect introduction allow using GDY in donor–acceptor photocatalytic systems for solar‐to‐hydrogen conversion. The defect‐rich GDY QDs (GDYO‐QDs) exhibit a blue‐to‐green excitation‐dependent photoluminescence behavior, demonstrating their ability to harvest light over a wide energy range. Quantum‐chemical calculations evidenced an increase in the electronic bandgap of GDY upon quantum confinement and defect introduction without the appearance of trap states that can hamper charge transport properties. Such a unique optical behavior of QDs is used in photocatalytic hydrogen generation through the hybridization with TiO2 as a model photocatalyst. Theoretical and experimental results demonstrate that the donor−acceptor system tremendously boosts the photocatalytic performance, reaching 5288 µmol g−1 after 4 h of illumination at a constant rate of 1322 µmol g−1 h−1, using a low volume of a sacrificial electron donor (6% v/v). The QDs act as efficient chromophores harvesting UV and visible light while injecting electrons into the TiO2. This work opens a new area of using GDYO‐QDs as an efficient chromophore in developing donor–acceptor systems for photocatalysis and future photovoltaic devices.

Single-Atom based Metal-Organic Framework Photocatalysts for Solar-Fuel Generation.

The growing demand for fossil fuels and subsequent CO2 emissions prompted a search for alternate sources of energy and a reduction in CO2. Photocatalysis driven by solar light has been found as a potential research area to tackle both these problems. In this direction, SAC@MOF (Single-atom loaded MOFs) photocatalysis is an emerging field and a promising technology. The unique properties of single-atom catalysts (SACs), such as high catalytic activity and selectivity, are leveraged in these systems. Photocatalysis, focusing on the utilization of Metal-Organic Frameworks (MOFs) as platforms for creating single-atom catalysts (SACs) characterized by metal single-atoms (SAs) as their active sites, are noted for their unparalleled atomic efficiency, precisely defined active sites, and superior photocatalytic performance. The synergy between MOFs and SAs in photocatalytic systems is meticulously examined, highlighting how they collectively enhance photocatalytic efficiency. This review examines SAC@MOF development and applications in environmental and energy sectors, focusing on synthesis and stabilization methods for SACs on MOFs and also characterization techniques vital for understanding these catalysts. The potential of SAC@MOF in CO2 Photoreduction and Photocatalytic H2 evolution is highlighted, emphasizing its role in green energy technologies and advances in materials science and Photocatalysis.

Harnessing the Power of Light: The Synergistic Effects of Crystalline Carbon Nitride and Ti3C2Tx MXene in Photocatalytic Hydrogen Production

AbstractPhotocatalytic hydrogen evolution is an environmentally friendly means of energy generation. Although g‐C3N4 possesses fascinating features, its inherent shortcomings limit its photocatalytic applications. Therefore, modifying the intrinsic properties of g‐C3N4 and introducing cocatalysts are essential to ameliorate the photocatalytic efficiency. To achieve this, metal‐like Ti3C2Tx is integrated with crystalline g‐C3N4 via a combined salt‐assisted and freeze‐drying approach to form crystalline g‐C3N4/Ti3C2Tx (CCN/TCT) hybrids with different Ti3C2Tx loading amounts (0, 0.2, 0.3, 0.4, 0.5, 1, 5, 10 wt.%). Benefiting from the crystallization of CN, as evidenced by the XRD graph, and the marvelous conductivity of Ti3C2Tx supported by EIS plots, CCN/TCT/Pt loaded with 0.5 wt.% Ti3C2Tx displays an elevated H2 (2) should be subscripted evolution rate of 2651.93 µmol g−1 h−1 and a high apparent quantum efficiency of 7.26% (420 nm), outperforming CN/Pt, CCN/Pt, and other CCN/TCT/Pt hybrids. The enhanced performance is attributed to the synergistic effect of the highly crystalline structure of CCN that enables fleet charge transport and the efficient dual cocatalysts, Ti3C2Tx and Pt, that foster charge separation and provide plentiful active sites. This work demonstrates the potential of CCN/TCT as a promising material for hydrogen production, suggesting a significant advancement in the design of CCN heterostructures for effective photocatalytic systems.

Ionic Liquid Modified Fe-Porphyrinic Metal-Organic Frameworks as Efficient and Selective Photocatalysts for CO2 Reduction.

Porphyrin-based metal-organic frameworks (MOFs) are ideal platforms for heterogeneous photocatalysts toward CO2 reduction. To further explore photocatalytic MOF systems, it is also necessary to consider their ability to fine-tune the microenvironments of the active sites, which affects their overall catalytic operation. Herein, a kind of ionic liquid (IL, here is 3-butyric acid-1-methyl imidazolium bromide, BAMeImBr) was anchored to iron-porphyrinic Zr-MOFs with different amounts to obtain ILx@MOF-526 (MOF-526 = Zr6O4(OH)4(FeTCBPP)3, FeTCBPP = iron 5,10,15,20-tetra[4-(4'-carboxyphenyl)phenyl]-porphyrin, x = 100, 200, and 400). ILx@MOF-526 series was designed to investigate the effects of the microenvironmental and electronic structural modification on the efficiency and selectivity of the photochemical reduction of CO2 after introducing IL fragments. Compared to parent MOF-526, the production and selectivity of CO were greatly improved in the absence of any photosensitizer under visible light by the ILx@MOF-526 series. Among them, the CO yield of IL200@MOF-526 was up to 14.0 mmol g-1 within 72 h with a remarkable CO selectivity of 97%, which is superior to that of MOF-526 without BAMeIm+ modification and other amounts of BAMeIm+ loaded. Furthermore, density functional theory calculations were performed to study the mechanism of the CO2 reduction.