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High-performing catalysts for the hydrogen evolution reaction (HER) via water electrolysis are of great importance for producing carbon-free green fuels. Compared to the routinely used metal-based systems under acidic conditions, metal-free pH-universal HER catalysts are smarter options taking into account the practical usability, sustainability, biocompatibility, and nominal cytotoxicity. Herein, we present an indigo-based organic conjugated porous polymer featuring a pronounced 2D few-layered morphology with surface-decorated hydrogen bonding sites for a deep catalyst–water contact and promising electrochemical HER activity. Indigo, being a vat dye, reduces in situ to its anionic leuco analogue and further promotes catalytic activity. The material manifested equipotent activity in acidic, alkaline, and neutral media superior to the contemporary metal-free carbonaceous electrocatalysts and comparable to the state-of-the-art metal-based catalytic systems. Under appropriate conditions, the material showed an overpotential of only 28 mV at 10 mA cm−2 current density. [ABSTRACT FROM AUTHOR]

Going down the particle size to nanodomain opens up innovative allies to expedite the physical and chemical properties of materials, and in turn, facilitates the manipulation of their catalytic propensity. Herein, we provide a succinct perspective of the wide spectrum of nanoparticles (NPs) in catalysis highlighting the underlying chemistry of different aspects, the introspective thread connecting them, and the ways to devise operando algorithms for exploiting such inter-connected systems. Following an introductory section discussing the generic miens of NPs, we went on to discuss the role of nanocrystals, especially various crystal facets and morphological anomalies in catalysis. The electronic shuttling involved in these catalysis vis-à-vis surface plasmon effect, Mott–Schottky contact, and Z-scheme systems, all in the nanodomain, was then explained. Following this, we introduced the concept of "Soft Matter" and "Active Matter", essentially the ones exploiting previously discussed chemistry, and explained the role of their in situ morphological precedence and stimuli-induced motility in catalysis. Finally, the emerging concept of Operando Systems Chemistry Algorithm (OSCA) was instituted discussing the devising strategies of tandem compartmentalized chemical arrays as individual algorithm analogs to sequentially impact the properties of aforementioned soft and active matters for targeted catalytic assays. [ABSTRACT FROM AUTHOR]

Over the past decade, porous organic polymers (POPs) have emerged as powerful photocatalysts for organic transformations and wastewater decontamination. The surface properties and pore space of POPs have been tailored to find optimal physical dimensions for adsorption and catalysis, whereas playing with the donor–acceptor building units lends them unique prospects for bandgap engineering, beneficial for customized applications including the degradation of simple as well as persistent pollutants. Here in this critical perspective, we focused beyond these generic scenarios and provided a detailed physicochemical explanation for the experimental observations. Considering the invaluable role of excitons, along with mobile electrons and holes, we fundamentally justified the reactivities of POPs with regard to water treatment. Both semiconducting and molecular catalyst approaches have been considered for different types of POPs. Depending on the porosity, structural formation and defects in the POP backbone, the exciton formation, charge separation, charge diffusion, etc. are critically explained, highlighting the influence of the dielectric constant and skeletal polarizability of the material. The translation of this fundamental understanding to various reactive oxygen species generation through charge transfer (e.g., O2˙−) and exciton–exciton annihilation (e.g., 1O2) by proximity-induced FRET or Dexter pathways is discussed. The role of the hydrophilic POP skeleton in overall in-water photochemical applications is also discussed. Finally, the gaps in the current state-of-the-art are considered and the future prospects to mitigate these issues are argued. [ABSTRACT FROM AUTHOR]

A facile, single-step development strategy of a sub-nanoscopic Lewis acidic Co and basic imidazole grafted porous organic polymer is reported. The synergistic activation of an epoxide and CO2 by the Lewis pairs present in the material manifested their rapid conversion to cyclic carbonates under ambient pressure with high yield, selectivity, and TOF. [ABSTRACT FROM AUTHOR]

In this review, we have portrayed the structure, synthesis and applications of a variety of biomimetic MOFs from an unprecedented angle. Synthetic MOF analogues of five distinct enzymes: phosphotriesterase, hydrogenase, cytochrome P450, chymotrypsin and carbonic anhydrase, have been discussed with their skeletal comparison to actual enzymatic active sites as reference, and an explanation of catalytic pathways from the mechanistic cycle of the corresponding enzymes is depicted. We demonstrated critically each of the five discrete situations by assimilating available benchmark researches in an attempt to provide a concise literature source on the ingenious design strategies and versatile biomimetic applications of this domain of materials. [ABSTRACT FROM AUTHOR]

A heterogeneous photocatalyst amenable to catalyze different chemical reactions is a highly enabling and sustainable material for organic synthesis. Herein we report the synthesis and characterization of an azobenzene-based organic π–conjugated porous polymer (AzoCPP) as heterogeneous dual photocatalyst manifesting net-oxidative bromination of arenes and dehydroxylation of boronic acids to corresponding phenols. Hierarchical porosity and high surface area of the nano-sized AzoCPP allowed superior catalyst-substrate contact during catalyses, whereas the inherent structural defect present in the CPP backbone resulted in low-energy sinks functioning as de facto catalytic sites. A combination of these two structure-property aspects of AzoCPP, in addition to the dielectric constant manipulation of the system, led to excellent catalytic performance. The protocols remained valid for a wide substrate scope and the catalyst was recycled multiple times without substantial loss in catalytic activity. With the aid of subsequent control experiments and analytical characterizations, mechanisms for each catalysis are proposed and duly corroborated. [ABSTRACT FROM AUTHOR]