Selective electrochemical nitrogen fixation to ammonia catalyzed by a novel microporous vanadium phosphonate via the distal pathway.

Herein, a microporous organic-inorganic hybrid, vanadium phosphonate (VPn) material has been developed. With the combined advantages of the periodic organic-inorganic skeleton, a regular microporous channel with a crystalline pore wall, and good surface area, VPn displays electrocatalytic NRR activity with a selective NH3 yield (11.84 µg h-1 mgcat-1), faradaic efficiency of 26.29% at -0.6 V and high stability up to 15 h. The isotopic labeling experiment also verifies the electrosynthesis of NH3 both qualitatively and quantitatively. The theoretical simulation reveals that the associative distal route serves as the most favourable pathway during the NRR, with the first protonation step of *N2 leading to *NNH as the potential determining step.

Mitigating Interfacial Capacity Fading in Vanadium Pentoxide by Sacrificial Vanadium Sulfide Encapsulation for Rechargeable Mg-Ion Batteries.

Rechargeable Mg-ion Batteries (RMB) containing a Mg metal anode offer the promise of higher specific volumetric capacity, energy density, safety, and economic viability than lithium-ion battery technology, but their realization is challenging. The limited availability of suitable inorganic cathodes compatible with electrolytes relevant to Mg metal anode restricts the development of RMBs. Despite the promising capability of some oxides to reversibly intercalate Mg+2 ions at high potential, its lack of stability in chloride-containing ethereal electrolytes, relevant to Mg metal anode hinders the realization of a full practical RMB. Here the successful in situ encapsulation of monodispersed spherical V2O5 (≈200 nm) is demonstrated by a thin layer of VS2 (≈12 nm) through a facile surface reduction route. The VS2 layer protects the surface of V2O5 particles in RMB electrolyte solution (MgCl2 + MgTFSI in DME). Both V2O5 and V2O5@VS2 particles demonstrate high initial discharge capacity. However, only the V2O5@VS2 material demonstrates superior rate performance, Coulombic efficiency (100%), and stability (138 mA h g-1 discharge capacity after 100 cycles), signifying the ability of the thin VS2 layer to protect the V2O5 cathode and facilitate the Mg+2 ion intercalation/deintercalation into V2O5.

Porous organic-inorganic hybrid materials for catalysis, energy and environmental applications.

The introduction of organic functionalities into porous inorganic materials not only makes the resulting hybrid porous framework to be more flexible and hydrophobic, but also provides additional scope for anchoring metal binding sites, which is beneficial for different frontline applications. Furthermore, the nanoscale porosity and high surface area of these organic-inorganic hybrid materials offer a better dispersion of active sites, which greatly enhances their application potential in adsorption, sensing, drug-delivery, energy storage, optoelectronics, light harvesting and catalysis. Easy post-synthetic functionalization of these hybrid materials has widened their application potential. Herein, we highlight several important synthetic strategies to design a wide range of organic-inorganic hybrid porous materials starting from the respective molecular precursors and their task-specific applications in energy and environmental research. We also outline the recent developments in their respective application areas together with various challenges that need to be overcome.

Metal-Free Triazine-Based 2D Covalent Organic Framework for Efficient H2 Evolution by Electrochemical Water Splitting.

Hydrogen evolution reaction (HER) by electrochemical water splitting is one of the most active areas of energy research, yet the benchmark electrocatalysts used for this reaction are based on expensive noble metals. This is a major bottleneck for their large-scale operation. Thus, development of efficient metal-free electrocatalysts is of paramount importance for sustainable and economical production of the renewable fuel hydrogen by water splitting. Covalent organic frameworks (COFs) show much promise for this application by virtue of their architectural stability, nanoporosity, abundant active sites located periodically throughout the framework, and high electronic conductivity due to extended π-delocalization. This study concerns a new COF material, C6 -TRZ-TFP, which is synthesized by solvothermal polycondensation of 2-hydroxybenzene-1,3,5-tricarbaldehyde (TFP) and 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris[(1,1'-biphenyl)-4-amine]. C6 -TRZ-TFP displayed excellent HER activity in electrochemical water splitting, with a very low overpotential of 200 mV and specific activity of 0.2831 mA cm-2 together with high retention of catalytic activity after a long duration of electrocatalysis in 0.5 m aqueous H2 SO4 . Density functional theory calculations suggest that the electron-deficient carbon sites near the π electron-donating nitrogen atoms are more active towards HER than those near the electron-withdrawing nitrogen and oxygen atoms.

Influence of Indium as a Promoter on the Stability and Selectivity of the Nanocrystalline Cu/CeO2 Catalyst for CO2 Hydrogenation to Methanol.

Stable catalyst development for CO2 hydrogenation to methanol is a challenge in catalysis. In this study, indium (In)-promoted Cu nanoparticles supported on nanocrystalline CeO2 catalysts were prepared and explored for methanol production from CO2. In-promoted Cu catalysts with ∼1 wt % In loading showed a methanol production rate of 0.016 mol gCu-1 h-1 with 95% methanol selectivity and no loss of activity for 100 h. It is found that the addition of indium remarkably increases Cu dispersion and decreases Cu particle size. In addition led to an increased metal-support interaction, which stabilizes Cu particles against sintering during the reaction, leading to high stability and activity. In addition, density functional theory calculations suggested that the reaction is proceeding via reverse water gas shift (RWGS) mechanism where the presence of In stabilized intermediate species and lowered CO2 activation energy barriers.

The design and synthesis of heterogeneous catalysts for environmental applications.

With the rapid advancements in synthetic strategies, the field of heterogeneous catalysis has expanded enormously over the last few decades, and today it is one of the foremost areas in energy and environmental research. Various templating and non-templating routes for designing porous nanomaterial-based catalysts starting from precursor building blocks are highlighted here. CO2 and biomass are two major abundant resources that can be utilized as feedstocks for various heterogeneous catalytic processes. These are described in brief, together with environmental clean-up applications and future perspectives for addressing environmental issues.

Metformin-Templated Nanoporous ZnO and Covalent Organic Framework Heterojunction Photoanode for Photoelectrochemical Water Oxidation.

Photoelectrochemical water-splitting offers unique opportunity in the utilization of abundant solar light energy and water resources to produce hydrogen (renewable energy) and oxygen (clean environment) in the presence of a semiconductor photoanode. Zinc oxide (ZnO), a wide bandgap semiconductor is found to crystallize predominantly in the hexagonal wurtzite phase. Herein, we first report a new crystalline triclinic phase of ZnO by using N-rich antidiabetic drug metformin as a template via hydrothermal synthesis with self-assembled nanorod-like particle morphology. We have fabricated a heterojunction nanocomposite charge carrier photoanode by coupling this porous ZnO with a covalent organic framework, which displayed highly enhanced photocurrent density of 0.62 mA/cm2 at 0.2 V vs. RHE in photoelectrochemical water oxidation and excellent photon-to-current conversion efficiency at near-neutral pH vis-à-vis bulk ZnO. This enhancement of the photocurrent for the porous ZnO/COF nanocomposite material over the corresponding bulk ZnO could be attributed to the visible light energy absorption by COF and subsequent efficient charge-carrier mobility via porous ZnO surface.

Morphologically controlled cobalt oxide nanoparticles for efficient oxygen evolution reaction.

Electrochemical water oxidation is one of the thrust areas of research today in solving energy and environmental issues. The morphological control in the synthesis of nanomaterials plays a crucial role in designing efficient electrocatalyst. In general, various synthetic parameters can direct the morphology of nanomaterials and often this is the main driving force for the electrocatalyst in tuning the rate of the oxygen evolution reaction (OER) for the electrochemical water-splitting. Here, a facile and cost-effective synthesis of spinel cobalt oxides (Co3O4) via a one-pot hydrothermal pathway with tunable morphology has been demonstrated. Different kinds of morphologies have been obtained by systematically varying the reaction time i.e. nanospheres, hexagon and nanocubes. Their catalytic activity has been explored towards OER in 1.0 M alkaline KOH solution. The catalyst Co3O4-24 h nanoparticles synthesized in 24 h reaction time shows the lowest overpotential (η) value of 296 mV at 10 mA cm-2 current density, in comparison to that of other as-prepared catalysts i.e. Co3O4-pH9 (311 mV), Co3O4-12 h (337 mV), and Co3O4-6 h (342 mV) with reference to commercially available IrO2 (415 mV). Moreover, Co3O4-24 h sample shows the outstanding electrochemical stability up to 25 h time.

Ag nanoparticle-decorated, ordered mesoporous silica as an efficient electrocatalyst for alkaline water oxidation reaction.

In recent years, several novel strategies for speeding up the slow kinetics of the water oxidation reaction have attracted considerable attention for generation of O2. This is particularly important from the environmental perspective. Here we report a SBA-15 type, 2D-hexagonal functionalized mesoporous organosilica material as support for small Ag nanoparticles (NPs) by grafting the silica surface with 3-aminopropyltriethoxysilane, followed by chemical impregnation of Ag NPs at its surface, to obtain a AgNPs@SBA-NH2 material. The AgNPs@SBA-NH2 has been thoroughly characterized using several instrumental tools, such as powder X-ray diffraction, ultra-high resolution transition electron microscopy, N2 sorption, FT-IR spectroscopy, thermogravimetric and differential thermal analysis and X-ray photoelectron spectroscopy. High Brunauer-Emmett-Teller (BET) surface area and fine dispersion of Ag NPs throughout the surface of the amine-functionalized mesoporous material could enhance the rate of oxygen evolution reaction (OER) activity for AgNPs@SBA-NH2 in the electrochemical water splitting reaction.

Iron phosphide anchored nanoporous carbon as an efficient electrode for supercapacitors and the oxygen reduction reaction.

Inspired by their distinctive properties, transition metal phosphides have gained immense attention as promising electrode materials for energy storage and conversion applications. The introduction of a safe and large-scale method of synthesizing a composite of these materials with carbon is of great significance in the fields of electrochemical and materials sciences. In the current effort, we successfully synthesize an iron phosphide/carbon (FeP/C) with a high specific surface area by the pyrolysis of the gel resulting from the hydrothermal treatment of an iron nitrate-phytic acid mixed solution. In comparison with the blank (P/C), the as-synthesized FeP/C appears to be an efficient electrode material for supercapacitor as well as oxygen reduction reaction (ORR) applications in an alkaline medium in a three-electrode system. In the study of supercapacitors, FeP/C shows areal capacitance of 313 mF cm-2 at 1.2 mA cm-2 while retaining 95% of its initial capacitance value after 10 000 cycles, while in the ORR, the synthesized material exhibits high electrocatalytic activity with an onset potential of ca. 0.86 V vs. RHE through the preferred four-electron pathway and less than 6% H2O2 production calculated in the potential range of 0.0-0.7 V vs. RHE. The stability is found to be better than those of the benchmark Pt/C (20 wt%) catalyst.

Materials with Nanoscale Porosity: Energy and Environmental Applications.

In this personal account, several key inventions on designing novel microporous and mesoporous materials, and their applications in energy and environmental research are reviewed. Although, crystalline materials with sub-nanometer pore size regime like zeolites, AlPOs, MOFs, ZIFs etc. are known over the years, silicious and non-silicious mesoporous materials have revolutionized the research on the materials with nanoscale porosity in last two and half decades. A wide range of inorganic, organic-inorganic hybrid as well as purely organic mesoporous materials with either periodic or disordered mesopores are known. Apart from conventional hydrothermal syntheses involving soft templating route, hard templating, evaporation induced self-assembly (EISA), electrochemical or solvothermal (using hydrophilic solvents) synthetic routes are often employed in designing a large spectrum of mesoporous materials. Ease of synthesis using available cheap raw chemicals and versatility in the framework compositions together with the unique surface properties like exceptionally high surface area, pore volume and tunability in pore dimensions have made these materials very exciting to a wide range of researchers working on materials chemistry. Nanoscale porosity in the semiconductor nanomaterials is highly beneficial for the photocatalytic, optoelectronic and related light-harvesting applications. Their high chemical stability has been explored intensively in designing novel heterogeneous catalysts for the synthesis of biofuels from biomass or CO2 fixation to reactive organic molecules for the synthesis of fine chemicals and fuels, which has a large impact on energy and environmental research for the years to come. Diversity in mesoporous frameworks and their potential applications related to light harvesting, generation of renewable energy and synthesis of value added fine chemicals and fuels through environment friendly routes are mostly focused in this review.

Microporous Nanotubes and Nanospheres with Iron-Catechol Sites: Efficient Lewis Acid Catalyst and Support for Ag Nanoparticles in CO2 Fixation Reaction.

FeIII -containing hyper-crosslinked microporous nanotubes (FeNTs) and nanospheres (FeNSs) are synthesized through the reaction of catechol and dimethoxymethane in the presence of FeCl3 or CF3 SO3 H. Both FeNTs and FeNSs demonstrate excellent catalytic activity in Lewis acid catalysis (hydrolysis and regioselective methanolysis of styrene oxide) and tandem catalysis involving a sequential oxidation-cyclization process, which selectively converts benzyl alcohol to 2-phenyl benzimidazole. Apart from Lewis acidity, the FeNTs and FeNSs also showed CO2 uptake capacities of 2.6 and 2.2 mmol g-1 , respectively, at a pressure of 1 atm and temperature of 273 K. Furthermore, Ag nanoparticles are immobilized successfully on the surfaces of FeNTs and FeNSs by the liquid-phase impregnation method to prepare Ag@FeNT and Ag@FeNS nanocomposites, which show high catalytic activity for the selective fixation of CO2 to phenylacetylene to yield phenylpropiolic acid at 60 °C and 1 atm CO2 pressure. Hence, FeIII -catechol-containing hyper-crosslinked nanotubes and nanospheres have huge potential not only as Lewis acid catalysts, but also as excellent supports for immobilizing Ag nanoparticles in the design of a robust catalyst for the carboxylation of terminal alkynes, which has wide scope in catalysis and environmental research.

Porous Polymer Bearing Polyphenolic Organic Building Units as a Chemotherapeutic Agent for Cancer Treatment.

Cancer is one of the most deadly diseases worldwide. Although several chemotherapeutic agents are available at present for its treatment, they have their own limitations. The main problems of these chemotherapeutic agents are cost involvement and severe life-threatening antagonistic effects. Here, we report a new biodegradable N-rich porous organic polymer methylenedianiline-triformyl phloroglucinol (MDTFP-1) synthesized via a Schiff base condensation reaction between two reactive monomers, that is, 4,4'-methylenedianiline and 2,4,6-triformyl phloroglucinol under inert atmosphere. Because this porous polymer contains polyphenolic building units and has a high Brunauer-Emmett-Teller surface area (283 m2 g-1), it has been explored in the anticancer activity using HCT 116, A549, and MIA PaCa-2 cell lines. We have carried out the flow cytometric assessment using Annexin-V-FITC/PI staining through the exposed level of phosphatidylserine in the outer membrane of cells with MDTFP-1-induced apoptosis. Our results suggested that apoptosis of cells have been enhanced in a time-dependent manner in the presence of this novel porous polymer.

Role of Surface Phenolic-OH Groups in N-Rich Porous Organic Polymers for Enhancing the CO2 Uptake and CO2/N2 Selectivity: Experimental and Computational Studies.

Design and successful synthesis of phenolic-OH and amine-functionalized porous organic polymers as adsorbent for postcombustion CO2 uptake from flue gas mixtures along with high CO2/N2 selectivity is a very demanding research area in the context of developing a suitable adsorbent to mitigate greenhouse gases. Herein, we report three triazine-based porous organic polymers TrzPOP-1, -2, and -3 through the polycondensation of two triazine rings containing tetraamine and three dialdehydes. These porous organic polymers possess high Brunauer-Emmett-Teller (BET) surface areas of 995, 868, and 772 m2 g-1, respectively. Out of the three materials, TrzPOP-2 and TrzPOP-3 contain additional phenolic-OH groups along with triazine moiety and secondary amine linkages. At 273 K, TrzPOP-1, -2, and -3 displayed CO2 uptake capacities of 6.19, 7.51, and 8.54 mmol g-1, respectively, up to 1 bar pressure, which are considerably high among all porous polymers reported till date. Despite the lower BET surface area, TrzPOP-2 and TrzPOP-3 containing phenolic-OH groups showed higher CO2 uptakes. To understand the CO2 adsorption mechanism, we have further performed the quantum chemical studies to analyze noncovalent interactions between CO2 molecules and different polar functionalities present in these porous polymers. TrzPOP-1, -2, and -3 have the capability of selective CO2 uptake over that of N2 at 273 K with the selectivity of 61:1, 117:1, and 142:1 by using the initial slope comparing method, along with 108.4, 140.6, and 167.4 by using ideal adsorbed solution theory (IAST) method, respectively. On the other hand, at 298 K, the calculated CO2/N2 selectivities in the initial slope comparing method for TrzPOP-1, -2, and -3 are 27:1, 72:1, and 96:1, whereas those using IAST method are 42.1, 75.7, and 94.5, respectively. Cost effective and scalable synthesis of these porous polymeric materials reported herein for selective CO2 capture has a very promising future for environmental clean-up.

Supported Porous Nanomaterials as Efficient Heterogeneous Catalysts for CO2 Fixation Reactions.

CO2 is a major greenhouse gas responsible for global warming and can act as an abundant and inexpensive C1 source for enhancing the chain length/functionalization of a wide range of reactive organic molecules. It is moderately reactive, nontoxic and renewable. Thus, CO2 fixation reactions are important to meet the global challenges, that is, to mitigate the concentration of CO2 in the atmosphere through its fruitful utilization, which is of great interest from economic and environmental perspectives. Various metallic nanoparticles as well as metal oxides can be supported over high surface area porous materials and the resulting nanomaterial can act as heterogeneous and reusable solid catalyst for CO2 fixation reactions for the synthesis of a large number of fuels, natural products agrochemicals, and pharmaceutical compounds. Here we present an overview of the recent progress as well as promising future of metal/metal oxide nanoparticles supported over porous nanomaterials as heterogeneous catalysts for a wide spectrum of these CO2 fixation reactions.

Pd NP-Decorated N-Rich Porous Organic Polymer as an Efficient Catalyst for Upgradation of Biofuels.

Hydrodeoxygenation process is a potential route for upgrading biofuel intermediates, like vanillin, which is obtained in huge quantities through the chemical treatment of the abundant lignocellulosic biomass resources of nature, and this is attracting increasing attentions over the years. Herein, we report the grafting of palladium nanoparticles at the surface of porous organic polymer Pd-PDVTTT-1 synthesized through the co-condensation of 1,3,5-triallyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and divinylbenzene in the presence of radical initiator under solvothermal reaction conditions. The Pd-PDVTTT-1 material has been characterized thoroughly by powder X-ray diffraction, nitrogen sorption, ultra-high-resolution transmission electron Microscopy, Fourier-transform infrared spectroscopy, 13C MAS NMR, and X-ray photoelectron spectroscopy analyses. High surface area together with good thermal stability of the Pd-PDVTTT-1 material has motivated us to explore its potential as heterogeneous catalyst in the hydrodeoxygenation of vanillin for the production of upgraded biofuel 2-methoxy-4-methylphenol in almost quantitative yield and high selectivity (94%).

A new microporous oxyfluorinated titanium(IV) phosphate as an efficient heterogeneous catalyst for the selective oxidation of cyclohexanone.

Designing a new porous nanomaterial for eco-friendly catalytic reactions is very challenging. Here, a new crystalline microporous oxyfluorinated titanium phosphate material (TIPO-1) has been synthesized under hydrothermal conditions in the absence of any structure directing agent. The triclinic crystalline phase with the unit cell parameters a=7.962Å, b=10.006Å, c=13.979Å, α=96.921°, ß=95.851° and γ=93.760° has been indexed for TIPO-1 and it has been characterized through powder X-ray diffraction, nitrogen adsorption/desorption, XPS, FT-IR, 31P MAS NMR spectroscopy, UHR-TEM, FE-SEM and TGA/DTA analysis. The material exhibited excellent catalytic activity in liquid phase partial oxidation of cyclohexanone to adipic acid (up to 92% conversion) in the presence of aqueous H2O2 as oxidant together with value added side products like 1,6-hexandial and ε-caprolactone for reactions in different solvents. The material showed excellent recycling efficiency for six consecutive reaction cycles without any significant loss in catalytic activity.

MnAPO-5 as an efficient heterogeneous catalyst for selective liquid phase partial oxidation reactions.

Heterogeneous catalysts play a key role in addressing the economic and environmental issues of the chemical industry due to their several advantages, like ease of product separation, work-up and high recycling efficiency. Herein, we report the synthesis of a robust manganese(iv)-containing aluminophosphate material (MnAPO-5), with an AFI framework topology. This material has been characterized thoroughly by powder XRD, XPS, UHR TEM, FE SEM, 31P CP MAS NMR, atomic absorption spectroscopy, UV-visible spectroscopy and TGA. The Mn-containing microporous material has been employed as a heterogeneous catalyst for the oxidation of styrene and the synthesis of adipic acid from cyclohexanone in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant in air and it displayed very high recycling efficiency.

Covalent Organic Framework Material Bearing Phloroglucinol Building Units as a Potent Anticancer Agent.

Covalent organic frameworks (COFs) having periodicity in pores of nanoscale dimensions can be suitably designed for the organic building units bearing reactive functional groups at their surfaces. Thus, they are an attractive option as an anticancer agent to overcome the limitations of chemotherapy. Herein, we first report a new porous biodegradable nitrogen containing COF material, EDTFP-1 (ethylenedianiline-triformyl phloroglucinol), synthesized using 4,4'-ethylenedianiline and 2,4,6-triformylphloroglucinol via Schiff base condensation reaction. EDTFP-1 exhibited 3D-hexagonal porous structure with average pores of ca. 1.5 nm dimension. Here, we have explored the anticancer potentiality of EDTFP-1. Result demonstrated an enhanced cytotoxicity was observed against four cancer cells HCT 116, HepG2, A549, and MIA-Paca2 with significant lower IC50 on HCT116 cells. Additionally, EDTFP-1-induced cell death was associated with the characteristic apoptotic changes like cell membrane blebbing, nuclear DNA fragmentation, externalization of phosphatidylserine from the cell membrane followed by a loss of mitochondrial membrane potential as well as modulation of pro and antiapoptotic proteins. Further, the result depicted a direct correlation between the generations of ROS with mitochondrial-dependent apoptosis through the involvement of p53 phosphorylation upon EDTFP-1 induction, suggesting this COF material is a novel chemotherapeutic agent for cancer treatment.

Palladium nanoparticles embedded on mesoporous TiO2 material (Pd@MTiO2) as an efficient heterogeneous catalyst for Suzuki-Coupling reactions in water medium.

An efficient and recyclable catalytic system composed of palladium nanoparticles embedded over mesoporous TiO2 material (Pd@MTiO2) has been synthesized and its catalytic activity has been explored in Suzuki-Miyaura cross-coupling reaction of aryl halides in water medium. This catalytic system is a very simple and highly active protocol for carrying out the Suzuki coupling of aryl bromide and aryl chloride with boronic acids, which proceed smoothly in excellent yields under mild reaction conditions. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FT-IR), and N2 sorption studies are used to characterize the Pd@MTiO2 material. Environmentally friendly reaction conditions, high product yield, tolerance of variety of functionalities in the reactants and reusability suggested future potential of Pd@MTiO2 for the synthesis of a wide range of biaryl compounds.