A Visible Light-Driven α-MnO2/UiO-66-NH2 S-Scheme Photocatalyst toward Ameliorated Oxy-TCH Degradation and H2 Evolution.

Photocatalytic hydrogen production and pollutant degradation using a heterogeneous photocatalyst remains an alternative route for mitigating the impending pollution and energy crisis. Hence, the development of cost-effective and environmentally friendly semiconducting materials with high solar light captivation nature is imperative. To overcome this challenge, α-MnO2 nanorod (NR)-modified MOF UiO-66-NH2 (UNH) was prepared via a facile solvothermal method, which is efficient toward H2 evolution and oxy-tetracycline hydrochloride (O-TCH) degradation. The field-emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HR-TEM) results of the α-MnO2@UNH (MnU) hybrid reveals its nanorod embedded in MOF matrix, and the X-ray photoelectron spectroscopy (XPS) result confirms the interaction of UNH moiety with α-MnO2 NRs. Additionally, the outstanding separation of photogenerated excitons and the charge-transfer efficacy are further validated by photoluminescence (PL), time-resolved photoluminescence (TRPL), electrochemical impedance spectroscopy (EIS), and transient photocurrent analysis, which are the key causes for photoactivity augmentation in the MnU composites. The MnU-2 composite shows a superior O-TCH degradation efficiency of 93.23% and an excellent H2 production rate of about 410.6 µmol h-1 upon light irradiation. This study provides significant evidence in favor of the suggested mediator-free S-scheme-adapted charge migration path, and it effectively explains the enhanced exciton separation leading to extraordinary catalytic efficiency of the proposed composite.

MgIn2S4/UiO-66-NH2 MOF-Based Heterostructure: Visible-Light-Responsive Z-Scheme-Mediated Synergistically Enhanced Photocatalytic Performance toward Hydrogen and Oxygen Evolution.

Hydrogen and oxygen evolution via photocatalytic water splitting remains the quintessential alternative to fossil fuels. Photocatalysts must be sufficiently robust, competent, and productive toward harnessing sunlight in order to utilize the solar spectrum for maximal photocatalytic output. Herein, we have fabricated the MgIn2S4/UiO-66-NH2 composite via a facile solvothermal route and have determined its efficacy toward light-induced H2 and O2 generation reactions through water splitting with the aid of different sacrificial agents. Initially, the formation of pristine and composite materials was ascertained by PXRD, FTIR, etc. Moreover, with the aid of sophisticated morphological characterization techniques (FESEM and HRTEM), the intricate interaction between MgIn2S4 and UiO-66-NH2 was revealed. Additionally, the XPS studies suggested the effective interaction between the individual components with binding energy shifting suggesting the transfer of electrons from Zr-MOF to MgIn2S4. The PL and electrochemical aspects supported the effective photogenerated charge segregation in the prepared composite leading to superior photocatalytic outputs. Amidst the prepared composites of (3, 5, and 7 wt %) MgIn2S4/UiO-66-NH2, the 5 wt % or UM-2 composite displays optimal H2 and O2 evolution performances of 493.8 and 258.6 µmol h-1 (4-fold greater than for pristine MgIn2S4 and UiO-66-NH2), respectively. The nanocomposite's enhanced performance is indeed a consequence of the coadjuvant interaction among pristine UiO-66-NH2 and MgIn2S4 components that transpires via the Z-scheme-mediated charge transfer by enabling facile exciton segregation and channelization. Moreover, the composite inherited the remarkable framework stability of parent Zr-MOF, and the MgIn2S4 insertion had a negligible impact on the framework integrity. This work will offer a valuable model for developing robust Zr-MOF-based nanocomposite photocatalysts and evaluating their superior performance toward photocatalytic water redox reactions.

Inner transition metal-modulated metal organic frameworks (IT-MOFs) and their derived nanomaterials: a strategic approach towards stupendous photocatalysis.

Photocatalysis, as an amenable and effective process, can be adopted for pollution remediation and to alleviate the ongoing energy crisis. In this case, recently, metal organic frameworks (MOFs) have attracted increasing attention in the field of photocatalysis owning to their unique characteristics including large specific surface area, tuneable pore architecture, mouldable framework composition, tuneable band structure, and exceptional photon absorption tendency complimented with superior anti-recombination of excitons. Among the plethora of frameworks, inner transition metal based-MOFs (IT-MOFs) have started to garner significant traction as photocatalysts due to their distinct characteristics compared to conventional transition metal-based frameworks. Typically, IT-MOFs have the tendency to generate high nuclearity clusters and possess abundant Lewis acidic sites, together with mixed valency, which aids in easily converting redox couples, thereby making them a suitable candidate for various photocatalytic reactions. Therefore, in this contribution, we aim to summarise the excellent photocatalytic performance of IT-MOFs and their composites accompanied by a thorough discussion of their topological changes with a variation in the structure of the metal cluster, fabrication routes, morphological features, and physico-chemical properties together with a brief discussion of computational findings. Moreover, we attempt to explore the scientific understanding of the functionalities of IT-MOFs and their composites with detailed mechanistic pathways for in-depth clarity towards photocatalysis. Furthermore, we present a comprehensive analysis of IT-MOFs for various crucial photocatalytic applications such as H2/O2 evolution, organic pollutant degradation, organic transformation, and N2 and CO2 reduction. In addition, we discuss the measures employed to enhance their performance with some future directions to address the challenges with IT-MOF-based nanomaterials.

Hydrolytically stable mixed ditopic linker based zirconium metal organic framework as a robust photocatalyst towards Tetracycline Hydrochloride degradation and hydrogen evolution.

In the existing eco-crisis, designing and engineering an efficient as well as water stable photocatalyst for energy conversion and pollutant abatement remains crucial. In this regard, a mixed linker type zirconium metal organic framework (Zr-MOF) with terepthalic acid based ditopic linkers were utilized to design a single component photocatalyst through single step solvothermal method to utilize photons from visible light illumination towards hydrogen energy (H2) production and Tetracycline Hydrochloride (TCH) degradation. The one pot synthesized mixed linker based Zr-MOF displays visible light absorption through band gap tuning, superior exciton segregation and oxygen vacancy that cumulatively supports the enhancement in the photocatalytic output with respect to their pristine counterparts. Additionally, the X-ray photoelectron spectroscopy, optical and electrochemical studies strongly reinforces the above claims. The prepared mixed linker Zr-MOF showed superior photocatalytic H2 evolution performance of 247.88 µmol h-1 (apparent conversion efficiency; ACE = 1.9%) that is twice than its pristine Zr-MOFs. Moreover, in TCH degradation, the mixed linker MOF displays an enhanced efficacy of 91.8 % and adopts pseudo-first order type kinetics with a rate constant value of 0.032. Typically, the active species participating for the TCH photo-degradation follows the order of hydroxyl (OH.) < superoxide (O2.-) radicals. Consequently, the mixed linker Zr-MOF could be effectively used as a robust photocatalyst exhibiting boosted TCH degradation and H2 production.

Metal organic framework-based Janus nanomaterials: rational design, strategic fabrication and emerging applications.

Janus nanoparticles (JNPs) with dual segments comprising chemically distinct compositions have garnered the attention of researchers in the past few years. The combination of different materials with diversified morphology, topology, and distinct physico-chemical characteristics into the single Janus nanocrystal has yielded multifarious capabilities for a myriad of emerging applications involving catalysis, gas separation, electro-catalysis, adsorption and energy storage. However, the traditional Janus entities significantly lack the need for populous active sites and high surface area. To overcome the textural hurdles and improve the functionalities of JNPs, porous MOFs were eventually introduced into Janus particles. MOFs are well endowed with varied pore apertures, structures, large surface areas and tailored characteristics, making them potentially invaluable for Janus fabrication. Depending upon the usage, MOFs can be explored to design Metal@MOF, polymetalic@MOF, MOF@MOF and MOF-derived JNPs. In this regard, we have represented a holistic summarization of the design, synthesis and emerging applications of a rising class of multi-functionalized MOF-based Janus nanomaterials. Moreover, this article will significantly aid researchers with a vision of creating dual-composition porous nanomaterials as the MOF-based Janus nanoparticles is at infancy.

Mixed-Valence Bimetallic Ce/Zr MOF-Based Nanoarchitecture: A Visible-Light-Active Photocatalyst for Ciprofloxacin Degradation and Hydrogen Evolution.

A mixed-valency bimetallic Ce/Zr MOF with Ce3+/Ce4+ ions incorporated and an oxygen vacancy-rich single-component photocatalyst have been designed through the one-step solvothermal route to harness photons from the visible-light spectrum for green energy (H2) generation and ciprofloxacin (CIP) degradation. The one-pot-engineered bimetallic Ce/Zr MOF shows visible-light-active characteristics accompanied by a narrower band gap, along with enhanced exciton separation and superior ligand-to-metal charge transfer (LMCT), due to the presence of an interconvertible Ce3+/Ce4+ ions pair in comparison to its pristine MOF counterpart. The Ce ion insertion led to increase in electron density around the Zr4+ ion, along with generation of some oxygen vacancies (OV), which cumulatively led to the rise in the photo-reaction output. The synthesized UNH (Ce/Zr 1:1) MOF displayed a boosted photocatalytic H2 production rate of 468.30 µmol h-1 (ACE = 3.51%), which is around fourfolds higher than that of pristine MOFs. Moreover, for CIP photodegradation, the UNH (Ce/Zr 1:1) shows an enhanced efficiency of 90.8% and follows pseudo-first-order kinetics with a rate constant of 0.0363. Typically, the active species involved in the photo-redox reaction of the CIP photodegradation follows the order hydroxyl radical (OH•) < superoxide radical (O2•-), as confirmed by the TA and NBT tests. Consequently, the bimetallic Ce/Zr MOF can be readily employed as a robust photocatalyst with enhanced tendencies towards CIP degradation and H2 evolution.

Hydrolytically stable citrate capped Fe3O4@UiO-66-NH2 MOF: A hetero-structure composite with enhanced activity towards Cr (VI) adsorption and photocatalytic H2 evolution.

Design and facile fabrication of a magnetically separable hetero-structure photocatalyst as well as an adsorbent having dual green benefits towards energy conversion and pollutant remediation are quite indispensable in the current scenario. In this regard, a composite of citrate capped Fe3O4 and UiO-66-NH2 has been designed to remediate Cr (VI) by adsorption and harvest photons from visible light for clean energy (H2) conversion. The material was prepared by the union of citrate capped Fe3O4 (CCM) and versatile aqueous stable Zr-based MOF (UiO-66-NH2) through in-situ solvothermal method. The composite of CCM with MOF (MU-2) was studied through sophisticated analysis techniques; PXRD, FT-IR, BET, UV-Visible DRS, PL, TG, HRTEM and XPS etc. to reveal the inherent characteristics of the material. BET surface analysis revealed high specific surface area (572.13 m2 g-1) of MU-2 in comparison to its pristine MOF. Furthermore, the dual function composite MU-2's VSM studies showed that its magnetic saturation is 3.07 emu g-1 that is suitable for magnetic separation after desired reaction from aqueous media. The Cr (VI) sorption studies revealed that the composite adsorbent (MU-2) showed maximum monolayer adsorption capacity (Qm) of 743 mg g-1 which followed pseudo second order kinetics. Moreover, the sorption thermodynamics revealed that the process was spontaneous and endothermic in nature. In addition to it, the synthesized composite material displayed enhanced activity towards photocatalytic H2 evolution with a maximum evolution rate of 417 µmole h-1 with an apparent conversion efficiency (ACE) of 3.12 %. Typically, MU-2 displays high adsorptions of Cr (VI) as well as some extent of Cr (VI) reduction owning to its populous active sites and free carboxylate groups respectively. Moreover, the synergistic effect of CCM and UNH in the composite resulted in Z scheme mediated charge transfer mechanism that showed enhanced H2 photo-evolution rates. Hence, MU-2 can be readily utilized as magnetically retrievable dual function composite for Cr (VI) adsorption and photocatalytic H2 evolution.

UiO-66-NH2 Metal-Organic Frameworks with Embedded MoS2 Nanoflakes for Visible-Light-Mediated H2 and O2 Evolution.

Hydrogen evolution from water splitting by means of a photocatalytic approach is an ideal future energy source and free of fossil reserves, in contrary photocatalytic O2 evolution remains a bottleneck due to high over potential and low efficiency. For reasonable use of solar light, photocatalysts must be sufficiently stable and efficient toward harvesting of sunlight from both theoretical and practical viewpoints. In this regard, here we have prepared MoS2-modified UiO-66-NH2 MOF through a facile hydrothermal technique and evaluated its efficiency toward photocatalytic H2 and O2 evolution by water splitting in the presence of sacrificial agents. A couple of similar type of analyses have been studied previously; however, this analysis represents a diverse scientific approach on the basis of interfacial contact toward reveal the actual potential of nanoflakes MoS2 as well as UiO-66-NH2. In this regard the as-synthesized photocatalyst was well-characterized by XRD, FTIR, UV-vis diffuse reflectance spectra, FESEM, HRTEM, XPS, and BET analysis techniques, which provide sufficient evidence toward successful synthesis of the pristine materials and efficacious anchorage of MoS2 on the active surface of UiO-66-NH2 by the ionic interaction between Zr-O and S/Mo. Among the synthesized photocatalysts (3 wt %) MoS2/UiO-66-NH2 shows the optimum outcome toward H2 and O2 evolution, i.e., 512.9 µmol/h (4.37 times greater than bare UiO-66-NH2) and 263.6 µmol/h (4.25 and 11.32 times greater than bare UiO-66-NH2 and MoS2, respectively). The superior performance obtained by the composite is due to the synergistic effect of pristine UiO-66-NH2 and MoS2 which proceeds through a type-II interband alignment for the facile channelization of excitons. This investigation will bestow a beneficial blue-print to construct challenging photocatalysts and to find out the paramount performance toward photocatalytic water redox reaction.

A type-II interband alignment heterojunction architecture of cobalt titanate integrated UiO-66-NH2: A visible light mediated photocatalytic approach directed towards Norfloxacin degradation and green energy (Hydrogen) evolution.

Environmental pollution and energy scarcity is a major issue of the current scenario which forbear the progress of developing world. To overcome these problems towards a sustainable future, the utilization of sunlight by means of photocatalysis can be regarded as a best and suitable pathway. To validate this purpose, design and development of efficient heterogeneous photocatalyst for harvesting solar energy should be the major research concern for scientific community. In this regard herein, we have prepared a series of stable and efficient CoTiO3/UiO-66-NH2 p-n junction mediated heterogeneous photocatalyst by hydrothermal method. The functionalised linker of UiO-66-NH2 provided an intimate interfacial contact with CoTiO3 by Co/TiON ionic interaction, as proved by HRTEM and XPS analysis. Moreover the inverted V-shaped Mott-Schottky plot confirmed the junction formation in the optimised CoTiO3/UiO-66-NH2 material. In addition, EIS and PL analysis also provides sufficient evidence about the hindrance of active species recombination in composite as a result of p-n hetero junction. LC-MS characterization technique traces the assorted intermediate species produced in the course of photodegradation of Norfloxacin and confirms its complete degradation to corresponding CO2, H2O and NH4+ by the optimised CoTiO3/UiO-66-NH2. The highest photo-catalytic activity obtained towards Norfloxacin degradation is 90.13% and H2 production is 530.87 µmol in 1 h. The enhanced photo-catalytic reaction follows Type-II p-n hetero junction charge transfer mechanism and thus, paves a new way to design MOF based heterojunction photocatalyst for diverse photo catalytic performance.

Bandgap engineering via boron and sulphur doped carbon modified anatase TiO2: a visible light stimulated photocatalyst for photo-fixation of N2 and TCH degradation.

The present research reports the synthesis of two-dimensional (2D) sheet/flake-like nanostructures of crystalline carbon modified TiO2 (CT), B-TiO2 (B-CT), and S-TiO2 (S-CT) using a facile one-pot synthesis method. The crystallinity and phase purity (anatase) of the prepared nano-photocatalyst were characterised using X-ray diffraction, selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM) analysis. Furthermore, the morphological details and elemental content of the sample were studied via scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), respectively. Additionally, the optoelectronic features of all of the prepared specimens were measured via UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence (PL), impedance and Mott-Schottky studies. After successful characterisation, their photocatalytic performance was tested towards dinitrogen photo-fixation and tetracycline hydrochloride (TCH) degradation under visible light illumination. Moreover, the effective charge separation and greater availability of the active surface area led to the robust photocatalytic activity of the fabricated B-CT compared to the CT and S-CT samples, which correlates well with the PL, impedance and surface area analysis. B-CT displays the highest photocatalytic activity, i.e. 32.38 µmol L-1 (conversion efficiency = 0.076%) of ammonia production, and 95% tetracycline hydrochloride (10 ppm) degradation. Here, we have effectively designed a novel and productive pathway towards the enhancement of the photocatalytic performance of visible photon active TiO2-based materials for energy and environmental sustainability.

HPW-Anchored UiO-66 Metal-Organic Framework: A Promising Photocatalyst Effective toward Tetracycline Hydrochloride Degradation and H2 Evolution via Z-Scheme Charge Dynamics.

The abolition of environmental pollutants and production of hydrogen (H2) from water using a heterogeneous photocatalyst is a demanding science of the current scenario to solve the increasing environmental pollution and worldwide energy catastrophe in modern life. To validate this purpose, the design of low-cost and durable semiconductor-based photocatalysts with great light absorption capacity becomes the most challenging issue for researchers. Regarding this, herein the phosphotungstic acid (HPW)-anchored Zr6O4(OH)4(BDC)6 (UiO-66) metal-organic framework (MOF), i.e., HPW@UiO-66, has been prepared by a hydrothermal method and is efficient, stable, and capable of harvesting solar energy toward the degradation of tetracycline hydrochloride (TCH) and H2 production in the presence of a sacrificial donor. The ionic interaction between HPW and UiO-66 plays a key role toward the photostability and charge-transfer mechanism of the composite and is well characterized with X-ray diffraction, UV diffuse-reflectance spectroscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy. A total of 30 wt % HPW@UiO-66 shows a maximum degradation of about 87.24% of a 20 ppm TCH solution in 60 min of solar-light irradiation and about 353.89 µmol/h of H2 production. The conduction- and valence-band potentials are well characterized with Mott-Schottky measurement and a delay charge recombination process through electrochemical impedance spectroscopy. The proposed mediator-free Z-scheme-oriented electron-hole migration route is well supported by photoluminescence, and the scavenger test well explains the better charge-carrier separation and high catalytic performance of the prepared composite. This research will bestow an advantageous blueprint to fabricate novel and challenging photocatalysts toward the photocatalytic treatment of environmental pollutants and H2 evolution.