Novel strategies to tailor the photocatalytic activity of metal–organic frameworks for hydrogen generation: a mini-review

This review provides a recompilation of the most important and recent strategies employed to increase the efficiency of metal–organic framework (MOF)-based systems toward the photocatalytic hydrogen evolution (PHE) reaction through specific strategies: tailoring the photocatalytic activity of bare MOFs and guest@MOF composites, formation of heterojunctions based on MOFs and various photocatalysts, and inorganic photocatalysts derived from MOFs. According to the data reported in this mini-review, the most effective strategy to improve the PHE of MOFs relies on modifying the linkers with new secondary building units (SBUs). Although several reviews have investigated the photocatalytic activity of MOFs from a general point of view, many of these studies relate this activity to the physicochemical and catalytic properties of MOFs. However, they did not consider the interactions between the components of the photocatalytic material. This study highlights the effects of strength of the supramolecular interactions on the photocatalytic performance of bare and MOF-based materials during PHE. A thorough review and comparison of the results established that metal–nanoparticle@MOF composites have weak van der Waals forces between components, whereas heterostructures only interact with MOFs at the surface of bare materials. Regarding material derivatives from MOFs, we found that pyrolysis destroyed some beneficial properties of MOFs for PHE. Thus, we conclude that adding SBUs to organic linkers is the most efficient strategy to perform the PHE because the SBUs added to the MOFs promote synergy between the two materials through strong coordination bonds.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Metal-organic framework as a photocatalyst: Progress in modulation strategies and environmental/energy applications

Progress in the design, synthesis, and modification of metal-organic frameworks (MOFs) has immensely helped expand their applications in a wide variety of research fields. Such developments offered great opportunities for upgrading their efficiencies in diverse photocatalytic applications (e.g., N₂/CO₂ reduction, H₂ generation, organic synthesis, and environmental remediation) through enhanced conversion/storage of solar energy. The MOF-based photocatalytic platforms are, nonetheless, subject to many practical problems (e.g., inapplicability for industrial upscaling and thermodynamic instability under environmental conditions). In this review, the effects of synthesis/modification strategies on MOF photocatalysis have been discussed with respect to the type of inorganic nodes, the modulation of organic ligands, and the pre-/post-synthesis modification in MOF networks (i.e., MOF-based composite). Particular emphasis was placed on the technical advances achieved in the photoelectronic/catalytic performances of MOFs in multiple energy/environmental (redox) reactions based on both experimental and theoritical analyses. Further, the technical merits/disadvantages of MOF photocatalysts (in terms of structural defects, light absorption, active sites, and kinetic/thermodynamic stability) have been evaluated in relation to quantum efficiency and charge transfer mechanisms in various photo-redox reactions. The pursuit of strategies for enhanced kinetic stability of MOFs have also been highlighted based on the nature/strength of coordination modes, the inertness of metal centers, and the functionality of ligand types. Lastly, the current limitations of MOF-based photocatalysts are addressed with respect to their practical applications at industrial scales along with a discussion on their future use.     

Metal-organic frameworks for CO2 photoreduction

Metal-organic frameworks (MOFs) have attracted much attention because of their large surface areas, tunable structures, and potential applications in many areas. In recent years, MOFs have shown much promise in CO₂ photoreduction. This review summarized recent research progresses in MOF-based photocatalysts for photocatalytic reduction of CO₂. Besides, it discussed strategies in rational design of MOF-based photocatalysts (functionalized pristine MOFs, MOF-photosensitizer, MOF-semiconductor, MOF-metal, and MOF-carbon materials composites) with enhanced performance on CO₂ reduction. Moreover, it explored challenges and outlook on using MOF-based photocatalysts for CO₂ reduction.     

Three-dimensional flower-like Co-based metal organic frameworks as efficient multifunctional catalysts towards oxygen reduction,oxygen evolution and hydrogen evolution reactions

Design and development of cost-efficient multifunctional three-dimensional (3D) metal organic frameworks (MOFs) towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are very significant for green energy devices. Herein, a scalable one-pot solvothermal method is developed to obtain a series of multifunctional 3D flower-like MOFs. In addition, systematic studies are also conducted on the effects of various metal cations and N-containing ligands on the structures, compositions, and multifunctional performance of the obtained MOFs. As a result, 3D flower-like Co-MOFs using Co²⁺ as a metal cation and 2,2’:6′,2″-terpyridine as a N-containing ligand exhibit the highest multifunctional performance towards ORR, OER and HER. The scalable method provides a new prospect to design and develop other MOFs-based multifunctional catalysts.     

Recent progress in metal-doped TiO2, non-metal doped/codoped TiO2 and TiO2 nanostructured hybrids for enhanced photocatalysis

Titanium dioxide remains a benchmark photocatalyst with high stability, low cost, and less toxicity, but it is active only under UV light; thus, in practical applications using visible light, its catalytic reactions are stalled. To enhance its catalytic activity under visible light, non-metal/codoped TiO₂ structures are being studied. These structures improve the photocatalytic activity of TiO₂ in visible light by reducing its energy bandgap. This might be useful in wastewater treatment for the photocatalytic degradation of organic contaminants under visible and UV light irradiation. In this intensive review, we describe recent developments in TiO₂ nanostructured materials for visible-light driven photocatalysis, such as (i) mechanistic studies on photo-induced charge separation to understand the photocatalytic activity and (ii) synthesis of non-metal doped/codoped TiO₂ and TiO₂ nanostructured hybrid photocatalysts. Furthermore, the effects of various parameters on their photocatalytic efficiency, photodegradation of various organic contaminants present in wastewater, and photocatalytic disinfection are delineated.     

A review on graphitic carbon nitride (g-C3N4) – metal organic framework (MOF) heterostructured photocatalyst materials for photo(electro)chemical hydrogen evolution

Graphitic carbon nitride (g-C₃N₄)-based heterostructured photocatalysts have recently attracted significant attention for solar water splitting and photocatalytic hydrogen (H₂) evolution, because of their alterable physicochemical, optical and electrical properties, such as tunable band structure, ultrahigh specific surface area and controllable pore size, defect formation and active sites. On the other hand, metal-organic frameworks (MOFs) possess a favorable surface area, permanent porosity and adjustable structures that allow them to be suitable candidates for diverse applications. In this review, we therefore comprehensively discuss the structural properties of heterogeneous g-C₃N₄/MOF-based photocatalysts with a special emphasis on their photocatalytic performance regarding the mechanism of heterogeneous photocatalysis, including advantages, challenges and design considerations.     

Review of surface photovoltage spectra of nano-sized semiconductor and its applications in heterogeneous photocatalysis

Heterogeneous photocatalysis is a promising technique valuable for environmental purification. Nano-sized semiconductors such as ZnO and TiO₂, which is one of the most basic functional materials, have emerged as effective photocatalyst materials. The surface photovoltage spectra (SPS) can be an effective method for quickly evaluating the photocatalytic activity of semiconductor materials since it can provide a rapid, non-destructive monitor of the semiconductor surface properties such as surface band bending, surface and bulk carrier recombination and surface states, mainly showing the carrier separation and transfer behavior with the aid of light, especially the electric-field-induced surface photovoltage spectra (EFISPS), in which SPS is combined with the electric-field-modified technique. In this review, the basic principles, measurement and applications of the SPS and EFISPS are mainly discussed together with some fundamental aspects like the electric properties of semiconductor surface and the principle of electric field effect. In particular, the applications of SPS to nano-sized semiconductors such as ZnO and TiO₂ in heterogeneous photocatalysis are emphasized, which involve mainly evaluating the photocatalytic activity by analyzing semiconductor surface properties such as the separation efficiency of photoinduced carriers under illumination by the SPS measurement, highlighting our own contributions. The results show that the weaker the surface photovoltage signal is, the higher the photocatalytic activity is in the case of nano-sized semiconductor photocatalysts.     

A critical review in strategies to improve photocatalytic water splitting towards hydrogen production

Water splitting for hydrogen production under light irradiation is an ideal system to provide renewable energy sources and to reduce global warming effects. Even though significant efforts have been devoted to fabricate advanced nanocomposite materials, the main challenge persists, which is lower efficiency and selectivity towards H₂ evolution under solar energy. In this review, recent developments in photo-catalysts, fabrication of novel heterojunction constructions and factors influencing the photocatalytic process for dynamic H₂ production have been discussed. In the mainstream, recent developments in TiO₂ and g-C₃N₄ based photo-catalysts and their potential for H₂ production are extensively studied. The improvements have been classified as strategies to improve different factors of photocatalytic water splitting such as Z-scheme systems and influence of operating parameters such as band gap, morphology, temperature, light intensity, oxygen vacancies, pH, and sacrificial reagents. Moreover, thermodynamics for selective photocatalytic H₂ production are critically discussed. The advances in photo-reactors and their role to provide more light distribution and surface area contact between catalyst and light were systematically described. By applying the optimum operating parameters and new engineering approach on photoreactor, the efficiency of semiconductor photocatalysts for H₂ production can be enhanced. The future research and perspectives for photocatalytic water splitting were also suggested.     

Nanoporous metal organic framework materials for smart applications

Abstract

This review is concerned with the recent advances in metal organic framework (MOF) materials. We highlight the unique combination of physicochemical and thermomechanical characteristics associated with MOF-type materials and illustrate emergent applications in three challenging technological sectors: energy, environmental remediation and biomedicine. MOFs represent an exciting new class of nanoporous crystalline solids constituting metal ions/clusters and multifunctional organic linkages, which self-assemble at molecular level to generate a plethora of ordered 3D framework materials. The most intriguing feature of a MOF lies in its exceptionally large surface area, far surpassing those of the best activated carbons and zeolites. Next generation multifunctional materials encompassing MOF based thin films, coatings, membranes and nanocomposites have potential for exploitation in an immense array of unconventional applications and smart devices. We pinpoint the key technological challenges and basic scientific questions to be addressed, so as to fulfil the translational potential for bringing MOFs from the laboratory into commercial applications.     

A critical review on core/shell-based nanostructured photocatalysts for improved hydrogen generation

Photocatalytic water splitting into gaseous hydrogen and oxygen in the presence of semiconductor photocatalysts under a visible spectrum of solar irradiation is one of the most promising processes for plummeting energy demands and environmental pollution. Among the successful photocatalytic materials, the core/shell nanostructures show promising results owing to their fascinating morphology that protects the surface features of the core besides the effective separation of photo-excitons resulting in an enhanced rate of hydrogen production up to 162 mmol h⁻¹g⁻¹_cat, which is a notable highest value reported in the literature. In this review, we have focused on the basic characteristics of the core-shell structure-based semiconductor photocatalytic systems and their efficient water-splitting reactions under light irradiation. Comprehensive detail on various synthesis methods of core-shell nanostructures, shell thickness-dependent properties, charge-transfer reaction mechanisms, and photocatalytic stability are highlighted in this review. Core-shell nanostructured materials have been extensively used as a photocatalyst, co-catalyst, and by coupling with supporting materials to improve the apparent quantum efficiency up to 45.6%. Besides, important photocatalytic properties that influence the redox reactions i.e., effective exciton separation, the effect of different light sources/wavelengths, surface charge modeling, photocatalytic active sites, and turnover frequency (TOF) have also been focused on and extensively described. Finally, the present and future prospects of the core-shell nanostructured photocatalysts for solar energy conversion into green hydrogen production have been expounded.     

0D, 1D and 2D nanomaterials for visible photoelectrochemical water splitting. A Review

Global energy problems of the 21st century have led to the search for alternative energy sources, among which is hydrogen produced via photoelectrochemical solar water splitting. Photo-electrochemical water splitting using semiconductor nanostructured materials is a progressive method for producing hydrogen. The unique electronic, mechanical, surface and optical properties of nanomaterials make it possible to create photocatalysts with complex structures of energy zones, allowing the use of a wide range of sunlight and exerting a positive effect on absorption and scattering of sunlight. This review contains a detailed analysis of current studies aimed at improving the efficiency of photocatalytic systems by using 0D, 1D and 2D nanostructures. Special attention is paid to the mechanisms of photocatalytic water splitting to produce hydrogen with the help of various nanostructures.     

Recent advances in non-metals-doped TiO2 nanostructured photocatalysts for visible-light driven hydrogen production,CO2 reduction and air purification

The generation of hydrogen and oxygen from the photocatalytic water splitting reaction under visible light is a promisingly renewable and clean source for H₂ fuel. The transition metal oxide semiconductors (e.g. TiO₂, WO_3, ZnO, and ZrO₂) are have been widely used as photocatalysts for the hydrogen generation. Because of safety, low cost, chemical inertness, photostability and other characteristics (bandgap, corrosion resistance, thermal and environmental stability), TiO₂ is considered as a most potential catalyst of the semiconductors being investigated and developed. However, the extensive applications of TiO₂ are hampered by its inability to exploit the solar energy of visible region. Other demerits are lesser absorbance under visible light, and recombination of photogenerated electron-hole pairs. In this review, we focus on the all the possible reactions taking place at the catalyst during photo-induced H₂ from water splitting reaction, which is green and promising technology. Various parameter affecting the photocatalytic water splitting reactions are also studied. Predominantly, this review is focussed on bandgap engineering of TiO₂ such as the upward shift of valence band and downward shift of conduction bands by doping process to extend its light absorption property into the visible region. Furthermore, the recent advances in this direction including various new strategies of synthesis, multiple doping, hetero-junction, functionalization, perspective and future opportunities of non-metals-doped TiO₂-based nanostructured photocatalysts for various photocatalytic applications such as efficient hydrogen production, air purification and CO₂ reduction to valuable chemicals have been discussed.     

Research progress of defect-engineered UiO-66(Zr) MOFs for photocatalytic hydrogen production

In recent years, defect-engineered Zr-based UiO-66 metal-organic frameworks (UiO-66(Zr) metal-organic frameworks (MOFs)) have shown huge advantages in catalytic, functional materials, adsorption, and other fields due to their large surface areas, well-ordered porous structures, and flexible tailorability. It is extremely challenging to introduce defect sites in the synthesis of MOFs to regulate the physicochemical properties of materials such as (energy band structure, pore structure, etc.) to obtain an excellent performance. This paper reviews the recent research results of synthesis methods, characterization technologies, and application fields of defect-engineered UiO-66(Zr) MOFs materials in order to provide new insights to synthesize high-performance UiO-66(Zr) MOFs materials and promote the development of UiO-66(Zr) in various fields.     

Synthesis of Au/UiO-66-NH2/Graphene composites as efficient visible-light photocatalysts to convert CO2

The production of new solar fuel through CO₂ photocatalytic reduction has aroused tremendous attention in recent years because of the increased demand of global energy sources and global warming caused by the mass concentration of CO₂ in the earth's atmosphere. In this work, UiO-66-NH₂ was co-modified by the Au nanoparticles (Au-NPs) and Graphene (GR). The resultant nanocomposite exhibits a strong absorption edge in visible light owing to the surface plasmon resonance (SPR) of Au-NPs. More attractively, Au/UiO-66-NH₂/GR displays much higher photocatalytic activity (49.9 μmol) and selectivity (80.9%) than that of UiO-66-NH₂/GR (selectivity: 71.6%) and pure UiO-66-NH₂ (selectivity: 38.3%) for the CO₂ reduction under visible light. The enhanced photocatalytic performance is primarily dued to the surface plasmon resonance (SPR) of Au-NPs, which could enhance the visible light absorption. The GR sheets could play as an electron acceptor with superior conductivity and thus suppress the recombination of electrons and holes. Besides, the GR could also improve the dispersibility of UiO-66-NH₂ so as to expose more active sites and strengthen the capture of CO₂. The contact effect and synergy effect among different samples are strengthened in the ternary composites and the photocatalytic performance is therefore improved. This study demonstrates a MOF based hybrid composite for efficient photocatalytic CO₂ reduction, the findings not only prove great potential for the design and application of MOFs-based materials but also bring light to novel chances in the development of new high performance photocatalysts.     

State of the art advancement in rational design of g-C3N4 photocatalyst for efficient solar fuel transformation,environmental decontamination and future perspectives

Recently, the graphite based heterogeneous photocatalysts has attained tremendous research attention in various environmental applications. Among them, the graphitic carbon nitride (g-C₃N₄) is categorized as a unique solar active particle with its outstanding intrinsic properties i.e., adequate band configuration, excellent light absorptivity and thermo-physical durability, which make it highly useful and reliable for revenue transformation and ecological concerns. Considering the intrinsic potential of g-C₃N₄ in photocatalysis, so far, no report has been done in literature for its extraordinary configuration, morphological characteristics and perspective tuning for said applications. To overcome this research gap, our primary emphasis of this review regarding photocatalysis is to provide layout as well as the advancement of visible-light-fueled materials as highly stabilized and extremely effective ones for pragmatic implementation. Thus, this existing comprehensive assessment conducts a systematic survey over visible light driven non-metal novel g-C₃N₄. The major advancement of this evaluation is the fabrication of well-designed nanosized g-C₃N₄ photocatalysts with unique configurable frameworks and compositions. Furthermore, alternative techniques in order to customize the analogue band configuration and noticeable cultivation such as metal (cation), nonmetal (anion) doping, worthy metal activating, and alloy initiation with certain semiconductors are discussed in detail. In addition to this, g-C₃N₄ photocatalytic functionalities towards photocatalytic hydrogen evolution, CO₂ photoreduction, biological metal ions deterioration as well as bacterial sanitization are also presented and discussed in detail. Therefore, we believe that such a pivotal compact assessment can provide a roadmap in several perspectives on the currently underway obstacles in the innovation of effective g-C₃N₄ catalytic design processes. Moreover, this critical assessment will ultimately serve as a useful supplement in the research area of g-C₃N₄ nanosized photocatalysts and for the researchers working on its key aspects in diverse range of natural, chemistry, engineering and environmental applications.     

Recent advances in the design of semiconductor hollow microspheres for enhanced photocatalyticv water splitting

Photocatalytic water splitting is a promising method to produce clean and renewable energy, which provides an alternative solution to solve environmental and resource problems. New catalysts based on semiconductor nanoparticles have received increasing attention since they facilitate all the reactions needed for “artificial photosynthesis”. In recent decades, hollow microspheres have provided an ideal platform for efficient utilization. Scientists are working to understand the basic principles, band structures, and modification strategies of hollow microspheres to enhance photocatalytic performance. In this paper, the research progress of hollow microsphere photocatalysts in the field of water splitting is reviewed. In particular, the photocatalytic principles of hollow microspheres and the methods to improve the performance of semiconductor photocatalysts are discussed in depth. The structural advantages and defects of hollow microspheres and modification methods of semiconductor band structure are introduced. Finally, the remaining challenges are summarized, and some insights into new trends and improvement directions for hollow materials are provided. This review will provide new insights for understanding hollow microspheres and help researchers in related fields to have a deeper and more comprehensive understanding of hollow microspheres in photocatalytic water splitting.     

Review of photoluminescence performance of nano-sized semiconductor materials and its relationships with photocatalytic activity

In this review, the photoluminescence (PL) performance and mechanism of nano-sized semiconductor materials, such as TiO₂ and ZnO, are introduced, together with their attributes and affecting factors. Moreover, the applications of PL spectra in environmental photocatalysis are discussed in detail, viz. the inherent relationships between the PL intensity and photocatalytic activity are revealed on the basis of PL attributes, demonstrating that the PL spectra can reflect some important information such as surface defects and oxygen vacancies, surface states, photo-induced charge carrier separation and recombination processes in nano-sized semiconductor materials. Thus, the PL spectrum can provide a firm foundation in theory for designing and synthesizing new semiconductor photocatalysts with high activity, as well as quickly evaluating the photocatalytic activity of semiconductor samples.     

Co-application of liquid phase plasma process for hydrogen production and degradation of acetaldehyde over NiTiO2 supported on porous materials

Photocatalytic decomposition of acetaldehyde-contained wastewater was assessed for the degradation of pollutants and the production of hydrogen. Liquid phase plasma was applied in the photoreaction as a light source. The evolution of hydrogen and acetaldehyde degradation were characterized by the photocatalytic decomposition system. Ni-loaded TiO₂ photocatalysts and various porous materials were introduced to the photocatalytic reaction. The photochemical decomposition by irradiation of the liquid phase plasma without photocatalysts produced some hydrogen evolution with the degradation of acetaldehyde, which was attributed to the decomposition of the reactant by active species generated by the irradiation of liquid phase plasma. The Ni loading on TiO₂ brought out an enhancement of acetaldehyde degradation and hydrogen evolution. In the photocatalysis of acetaldehyde-contained wastewater using the liquid phase plasma, hydrogen evolution was accelerated due to the additional hydrogen production by the photocatalytic decomposition of acetaldehyde. The porous materials could be used as an effective photocatalytic support. MCM-41 mesoporous material has acted as a highly efficient photocatalytic support to the TiO₂ photocatalyst.     

Photocatalysis of TiO2 nanoparticles supported on natural zeolite

Abstract

In order to achieve rapid and efficient decomposition of organic pollutants and put it to wastewater treatment, the composite materials of nanoTiO₂ powder immobilised on zeolite were synthesised. Moreover, the effects of technology parameters, such as TiO₂ loading content, calcining temperature and ultrasonic treatment, on photocatalytic reactivity were examined. The proposed research investigates the following aspects, which are important in understanding the preparation and application of TiO₂/zeolite composite photocatalysts: nanosize TiO₂ particles were supported on natural zeolite by a simple sol–gel method in order to maximise the photocatalytic performance of the nanosize TiO₂ as well as reduce the preparation cost; and the effects of TiO₂ loading content, calcining temperature and ultrasonic treatment on photocatalytic reactivity were researched. The novel aspect of the proposed photocatalysts is the combination of nanosize TiO₂ particles and natural zeolite by a simple sol–gel method. The product of the research can be used in wastewater treatment resolving the difficulties of TiO₂ recovery and surface contact based photocatalytic reaction.