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The self-assembled metal-organic cages (MOCs) have been evolved as a paradigm of enzyme-mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components and constitute microenvironments characteristic of enzymatic spatial confinement and versatile host-guest interactions, thus facilitating unconventional organic transformations via unique driving-forces such as weak noncovalent binding and electron/energy transfer. Recently, MOC-based photoreactors emerged as a burgeoning platform of supramolecular photocatalysis, displaying anomalous reactivities and selectivities distinct from bulk solution. This perspective recaps two decades journey of the photoinduced radical reactions by using photoactive metal-organic cages (PMOCs) as artificial reactors, outlining how the cage-confined photocatalysis was evolved from stoichiometric photoreactions to photocatalytic turnover, from high-energy UV-irradiation to sustainable visible-light photoactivation, and from simple radical reactions to multi-level chemo- and stereoselectivities. We will focus on PMOCs that merge structural and functional biomimicry into a single-cage to behave as multi-role photoreactors, emphasizing their potentials in tackling current challenges in organic transformations through single-electron transfer (SET) or energy transfer (EnT) pathways in a simple, green while feasible manner., (© 2024 Wiley‐VCH GmbH.)

The production of renewable feedstocks through the coupled oxygen evolution reaction (OER) with selective organic oxidation requires a perfect balance in the choice of a catalyst and its synthesis access, morphology, and catalytic activity. Herein we report a rapid in-liquid plasma approach to produce a hierarchical amorphous birnessite-type manganese oxide layer on 3D nickel foam. The as-prepared anode exhibits an OER activity with overpotentials of 220, 250, and 270 mV for 100, 500, and 1000 mA·cm -2 , respectively, and can spontaneously be paired with chemoselective dehydrogenation of benzylamine under both ambient and industrial (6 M KOH, 65 °C) alkaline conditions. The in-depth ex-situ and in-situ characterization unequivocally demonstrate the intercalation of potassium in the birnessite-type phase with prevalent Mn III states as an active structure, which displays a trade-off between porous morphology and bulk volume catalytic activity. Further, a structure-activity relationship is realized based on the cation size and structurally similar manganese oxide polymorphs. The presented method is a substantial step forward in developing a robust MnO x catalyst for combining effective industrial OER and value-added organic oxidation.

In this study, we are reporting biogenic synthesis of silver nanoparticles and hydrothermal synthesis of zinc oxide nanoparticles. Using convenient mechanical milling methods, nanocomposites with superior photocatalytic and catalytic properties are synthesized. Herein, we have adopted a green, eco-friendly, and economical route for the synthesis of Ag nanoparticles using Zingiber officinalae rhizome extract in an aqueous solution. The synthesized materials were characterized using UV-Vis spectroscopy, XRD, SEM & FE-SEM, FT-IR, Raman, and a particle size analyzer with zeta potential analysis. The photocatalytic activities of Ag, ZnO and their composites were studied by observing the degradation of methylene blue and crystal violet dyes under natural sunlight. Then the catalytic efficacies of synthesized nanoparticles for various organic transformation reactions were studied. Ag-ZnO nanocomposites were predicted to have improved photocatalytic activity and organic transformation reactions, allowing them to be used in environmental remediation applications., Competing Interests: Conflict of interestThere is no conflict of interest for the publication of article., (© King Abdulaziz City for Science and Technology 2022.)

The biofouling potential of three isolated dissolved organic fractions from seawater according to their molecular weights (MWs), namely, fractions of biopolymers (F.BP, MW > 1000 Da), humic substances and building blocks (F.HS&BB, MW 350-1000 Da), and low molecular weight compounds (F.LMW, MW < 350 Da) were characterized by assimilable organic carbon (AOC) content. The AOC/DOC ratio was in the order of F.LMW (∼35%) > F.BP (∼19%) > F.HS&BB (∼8%); AOC/DOC of seawater was ∼20%; organic compositions of seawater were BP ∼6%, HS&BB ∼52% and LMW ∼42%; LMW accounted for >70% of AOC in seawater. Their impact on SWRO biofouling in term of flux decline rate was in the order of F. LMW (∼30%) > F.BP (∼20%) > F.HS&BB (<10%). Despite being the major organic compound in seawater, HS&BB showed marginal effect on biofouling. The role of indigenous BP was less critical owing to its relatively low concentration. LMW, which was the major AOC contributor, played a significant role in biofouling by promoting microbial growth that contributed to the build-up of soluble microbial products and exopolymeric substances (i.e., in particular BP). Therefore, seawater pretreatment shall focus on the removal of AOC (i.e., LMW) rather than the removal of biopolymer., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Constructing Z-scheme photocatalysts is an effective approach to enhance the conversion efficiency of solar to chemical energy. Herein, W 18 O 49 /g-C 3 N 4 heterostructures have been synthesized by growing W 18 O 49 ultrathin nanowires on g-C 3 N 4 nanosheets via a convenient solvothermal process. Various characterizations were performed on the materials to understand the structure-performance relationship. The photocatalytic properties of the W 18 O 49 /g-C 3 N 4 heterostructures were evaluated by the two oxidation reactions, phenol degradation and oxidative NC coupling of benzylamines, under a simulated sunlight (360 ≤  λ  ≤ 780 nm). With tuning the W 18 O 49 /g-C 3 N 4 mass ratio, the optimal photocatalyst of W 18 O 49 (30)/g-C 3 N 4 containing 30 wt% W 18 O 49 nanowires exhibited the highest activity in both the photocatalytic reactions. The generations and contributions of the active species in the photocatalytic reactions were identified by electron spin resonance (ESR) spectra and active-species-eliminating experiments. Accordingly, the photocatalytic mechanism of W 18 O 49 /g-C 3 N 4 heterostructures has been expounded based on the direct Z-scheme electron transfer between the two semiconductors as well as the synergistic actions of active sites on W 18 O 49 nanowires and g-C 3 N 4 nanosheets. This work demonstrates a rational paradigm to construct 1D/2D semiconductor heterostructures and provides further insights into Z-scheme photocatalytic mechanism for boosting solar-driven pollutant degradation and organic transformation., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Heteroatom-doped porous carbon derived from biomass have recently received increasing attention due to their unique properties such as high electrical conductivity, large specific surface area, high porosity, and easy availability, which are appealing materials for versatile applications in catalysis, energy, separation and adsorption, and life sciences as well. On the basis of our previous work in this field, we summarized in this account our recent progress on design, synthesis of metal (e. g., Pd, Co) nanoparticles supported heteroatom-doped hierarchical porous carbon material derived from bamboo shoots and their applications for important organic transformations, including chemoselective semihydrogenation of alkynes, hydrosilylation of alkynes, cascade synthesis of benzofurans from terminal alkynes and iodophenols, selective hydrogenation of functionalized nitroarenes to form anilines, imines, and formamides. Finally, the current state and future challenges in this field are discussed. We hope this account could shed light on the rational design of novel non-noble metal based heterogeneous catalysts derived from biomass for efficient and sustainable organic transformations., (© 2019 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The deterioration in its strength from long-term degradation of organic matter and release of pharmaceutically active compounds (PhACs) have caused adverse environmental effects in municipal sewage sludge (MSS) landfill. Lime and a mixture of lime and mussel shell were employed as potential stabilization agents for MSS in this work. Their efficacy was assessed by investigating the effects on transformation of organic matter, as well as the occurrence and fate of four PhACs (fluoxetine, gemfibrozil, triclosan and carbamazepine) over 42 days. The addition of the selected agents: (i) prevented the microbial degradation of organic matter; (ii) modified the predominant functional groups of amide groups (amide I and II) and polysaccharides to deprotonated carboxylic groups and destruction of amide groups; and (iii) shifted the abundance of organic constituents from microbial by-products to humic acid-like organics with conformational changes. The measurement method provided reliable and precise results for determining PhAC concentrations in MSS with and without amendment, although matrix effects and process effects were found to affect measurement sensitivity. Available fractions of the PhACs increased in MSS with lime addition, but decreased in the presence of the mixture of lime and mussel shell due to the strong adsorption effects of the shells. The mixture of lime and mussel shell would be recommended for stabilizing MSS prior to being landfilled. However, longer term and larger scale investigation may be needed to better evaluate the applicability of lime and mussel shell for reducing the hazards and facilitating the management of MSS., (Copyright © 2018. Published by Elsevier Ltd.)

Metal-organic frameworks (MOFs) have attracted significant research attention in diverse areas due to their unique physical and chemical characteristics that allow their innovative application in various research fields. Recently, the application of MOFs in heterogeneous photocatalysis for water splitting, CO2 reduction, and organic transformation have emerged, aiming at providing alternative solutions to address the world-wide energy and environmental problems by taking advantage of the unique porous structure together with ample physicochemical properties of the metal centers and organic ligands in MOFs. In this review, the latest progress in MOF-involved solar-to-chemical energy conversion reactions are summarized according to their different roles in the photoredox chemical systems, e.g., photocatalysts, co-catalysts, and hosts. The achieved progress and existing problems are evaluated and proposed, and the opportunities and challenges of MOFs and their related materials for their advanced development in photocatalysis are discussed and anticipated., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)