Facile Hydrogenolysis of Sugars to 1,2-Glycols by Ru@PPh3/OPPh3 Confined Large-Pore Mesoporous Silica.

Tandem hydrogenation vis-à-vis hydrogenolysis of xylose to 1,2-glycols remains a major challenge. Although one-pot conversion of xylose to 1,2-glycols requires stringent conditions, a sustainable approach would be quite noteworthy. We have developed a microwave route for the one-pot conversion of pentose (C5) and hexose (C6) sugars into glycol and hexitol, without pressurized hydrogen reactors. A pronounced hydrogenolysis of sugars to glycols is observed by Ru single atom (SA) on triphenylphosphine/phosphine oxide-modified silica (Ru@SiP), in contrast to Ru SA on pristine (Ru@SiC) and 3-aminopropyl-modified silica (Ru@SiN). A promising "ligand effect" was observed through phosphine modification of silica that presents a 70% overall yield of all reduced sugars (xylitol + glycols) from a 99% conversion of xylose with Ru@SiP. A theoretical study by DFT depicts an electronic effect on Ru-SA by triphenylphosphine that promotes the catalytic hydrogenolysis of sugars under mild conditions. Hence, this research represents an important step for glycols from biomass-derived sources.

Recent Progress and Opportunity of Metal Single-Atom Catalysts for Biomass Conversion Reactions.

The conversion of lignocellulosic biomass into platform chemicals and fuels by metal single atoms is a new domain in solid catalysis research. Unlike the conventional catalysis route, single-atom catalysts (SACs) proliferate maximum utilization efficiency, high catalytic activity, and good selectivity to the desired product with an ultralow loading of the active sites. More strikingly, SACs show a unique cost-effective pathway for the conversion of complex sugar molecules to value-added chemicals in high yield and selectivity, which may be hindered by conventional metal nanoparticles. Primarily, SACs having adjustable active sites could be easily modified using sophisticated synthetic techniques based on their intended reactions. This review covers current research on the use of SACs with a strong emphasis on the fundamentals of catalyst design, and their distinctive activities in each type of reaction (hydrogenation, hydrogenolysis, hydrodeoxygenation, oxidation, and dehydrogenation). Furthermore, the fundamental insights into the superior actions of SACs within the opportunity and prospects for the industrial-scale synthesis of value-added products from the lignocelluloses are covered.

Covalent Organic Framework as a Metal-Free Photocatalyst for Dye Degradation and Radioactive Iodine Adsorption.

Exploring a covalent organic framework (COF) material as an efficient metal-free photocatalyst and as an adsorbent for the removal of pollutants from contaminated water is very challenging in the context of sustainable chemistry. Herein, we report a new porous crystalline COF, C6-TRZ-TPA COF, via segregation of donor-acceptor moieties through the extended Schiff base condensation between tris(4-formylphenyl)amine and 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline. This COF displayed a Brunauer-Emmett-Teller (BET) surface area of 1058 m2 g-1 with a pore volume of 0.73 cc g-1. Again, extended π-conjugation, the presence of heteroatoms throughout the framework, and a narrow band gap of 2.2 eV, all these features collectively work for the environmental remediation in two different perspectives: it could harness solar energy for environmental clean-up, where the COF has been explored as a robust metal-free photocatalyst for wastewater treatment and as an adsorbent for iodine capture. In our endeavor of wastewater treatment, we have conducted the photodegradation of rose bengal (RB) and methylene blue (MB) as model pollutants since these are extremely toxic, are health hazard, and bioaccumulative in nature. The catalyst C6-TRZ-TPA COF showed a very high catalytic efficiency of 99% towards the degradation of 250 parts per million (ppm) of RB solution in 80 min under visible light irradiation with the rate constant of 0.05 min-1. Further, C6-TRZ-TPA COF is found to be an excellent adsorbent as it efficiently adsorbed radioactive iodine from its solution as well as from the vapor phase. The material exhibits a very rapid iodine capturing tendency with an outstanding iodine vapor uptake capacity of 4832 mg g-1.

Controlled synthesis of Ru-single-atoms on ordered mesoporous phosphine polymers for microwave-assisted conversion of biomass-derived sugars to artificial sweeteners.

Atomically dispersed metal-single-atoms have become a frontier in solid catalysis due to their characteristic electronic properties. However, for biomass conversion, employing metal-single-atoms as catalysts is rather challenging since they suffer from poor selectivity and yield due to inadequate metal-support interactions. We show here that Ru/triphenylphosphine (PPh)-based ordered mesoporous polymers afford high yields of reduced sugars, xylitol (yield ∼95%) and sorbitol (yield ∼65%) in a microwave reactor with formic acid as the only hydrogen donor. We have established a unique relationship within Ru/triphenylphosphine that shows an important ligand effect, in contrast to, Ru/triphenylamine and Ru/catechol. The tailored electronic properties in Ru/phosphine were thoroughly examined by using state-of-the-art experimental techniques viz. EXAFS, XANES, XPS, DRIFTS and HAADF-STEM. The resulting phosphine-modified catalysts show a promotion in activity and selectivity towards less vulnerable aldehydes for hydrogenation, further confirmed by DFT calculations. This finding reveals a new protocol to tailor the activity of metal-single-atoms utilizing functional porous polymers as nanoreactors.

Correction: Thiadiazole containing N- and S-rich highly ordered periodic mesoporous organosilica for efficient removal of Hg(II) from polluted water.

Correction for 'Thiadiazole containing N- and S-rich highly ordered periodic mesoporous organosilica for efficient removal of Hg(II) from polluted water' by Asim Baumik et al., Chem. Commun., 2020, 56, 3963-3966, DOI 10.1039/D0CC00407C.

Pretreatment of lignocellulosic biomass: A review on recent advances.

Depleting fossil reserves and growing energy needs have raised the demand for an alternative and clean energy source. The use of ubiquitously available lignocellulosic biomass for developing economic and eco-friendly large scale biorefinery applications has provided the much-needed impetus in this regard. The pretreatment process is a vital step for biomass transformation into added value products such as sugars, biofuels, etc. Different pretreatment approaches are employed to overcome the recalcitrance of lignocellulosic biomass and expedite its disintegration into individual components- cellulose, hemicellulose, and lignin. The conventional pretreatment methods lack sustainability and practicability for industrial scale up. The review encompasses the recent advances in selective physical and chemical pretreatment approaches such as milling, extrusion, microwave, ammonia fibre explosion, eutectic solvents etc. The study will allow a deeper understanding of these pretreatment processes and increase their scope as sustainable technologies for developing modern biorefineries.

Mesoporous Porphyrin-Silica Nanocomposite as Solid Acid Catalyst for High Yield Synthesis of HMF in Water.

Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chlorosulfonic acid enabled sulfonic acid functionalization, and the resulting material (PorPOPS) showed excellent activity and durability for the conversion of fructose to 5-hydroxymethyl furfural (HMF) in green solvent water. PorPOPS composite was characterized by N2 sorption, FTIR, TGA, CHNS, FESEM, TEM and XPS techniques, justifying the successful synthesis of organic networks and the grafting of sulfonic acid sites (5 wt%). Furthermore, a high surface area (260 m2/g) and the presence of distinct mesopores of ~15 nm were distinctly different from the porphyrin containing sulfonated porous organic polymer (FePOP-1S). Surprisingly the hybrid PorPOPS showed an excellent yield of HMF (85%) and high selectivity (>90%) in water as compared to microporous pristine-FePOP-1S (yield of HMF = 35%). This research demonstrates the requirement of organic modification on silica surfaces to tailor the activity and selectivity of the catalysts. We foresee that this research may inspire further applications of biomass conversion in water in future environmental research.

CO2 hydrogenation over functional nanoporous polymers and metal-organic frameworks.

CO2 is one of the major environmental pollutants and its mitigation is attracting huge attention over the years due to continuous increase in this greenhouse gas emission in the atmosphere. Being environmentally hazardous and plentiful presence in nature, CO2 utilization as C1 resource into fuels and feedstock is very demanding from the green chemistry perspectives. To accomplish this CO2 utilization issue, functional organic materials like porous organic polymers (POPs), covalent organic frameworks (COFs) as well as organic-inorganic hybrid materials like metal-organic frameworks (MOFs), having characteristics of large surface area, high thermal stability and tunability in the porous nanostructures play significant role in designing the suitable catalyst for the CO2 hydrogenation reactions. Although CO2 hydrogenation is a widely studied and emerging area of research, till date review exclusively focused on designing POPs, COFs and MOFs bearing reactive functional groups is very limited. A thorough literature review on this matter will enrich our knowledge over the CO2 hydrogenation processes and the catalytic sites responsible for carrying out these chemical transformations. We emphasize recent state-of-the art developments in POPs/COFs/MOFs having unique functionalities and topologies in stabilizing metallic NPs and molecular complexes for the CO2 reduction reactions. The major differences between MOFs and porous organics are critically summarized in the outlook section with the aim of the future benefit in mitigating CO2 emission from ambient air.

Metal-Organic Polymer-Derived Interconnected Fe-Ni Alloy by Carbon Nanotubes as an Advanced Design of Urea Oxidation Catalysts.

The electrochemical urea oxidation reaction (UOR) is considered as a promising renewable source for harvesting energy from waste. We report a new synthetic design approach to produce an iron-nickel alloy nanocatalyst from a metal-organic polymer (MOP) by a single-step carbonization process at 500 °C, thus forming a core-shell of iron-nickel-coated carbon (C@FeNi) nanostructures wired by embedded carbon nanotubes (CNTs) (CNT/C@FeNi). Powder X-ray diffraction confirmed the formation of metallic FeNi3 alloy nanoparticles (∼20 to 28 nm). Our experimental results showed that MOP containing CNTs acquired an interconnected hierarchical topology, which prevented the collapse of its microstructure during pyrolysis. Hence, CNT/C@FeNi shows higher porosity (10 times) than C@FeNi. The electrochemical UOR in alkaline electrolytes on these catalysts was studied using cyclic voltammetry (CV). The result showed a higher anodic current (3.5 mA cm-2) for CNT/C@FeNi than for C@FeNi (1.1 mA cm-2) at 1.5 V/RHE. CNT/C@FeNi displayed good stability in chronoamperometry experiments and a lower Tafel slope (33 mV dec-1) than C@FeNi (41.1 mV dec-1). In this study, CNT/C@FeNi exhibits higher exchange current density (3.2 µA cm-2) than does C@FeNi (2 µA cm-2). The reaction rate orders of CNT/C@FeNi and C@FeNi at a kinetically controlled potential of 1.4 V/RHE were 0.5 and 0.9, respectively, higher than the 0.26 of ß-Ni(OH)2, Ni/Ni(OH)2 electrodes. The electrochemical impedance result showed a lower charge-transfer resistance for CNT/C@FeNi (61 Ω·cm-2) than for C@FeNi (162 Ω·cm-2), due to faster oxidation kinetics associated with the CNT linkage. Moreover, CNT/C@FeNi exhibited a lower Tafel slope and resistance and higher heterogeneity (25.2 × 10-5 cm s-1), as well as relatively high faradic efficiency (68.4%) compared to C@FeNi (56%). Thus, the carbon-coated FeNi3 core connected by CNT facilitates lower charge-transfer resistance and reduces the UOR overpotential.

Thiadiazole containing N- and S-rich highly ordered periodic mesoporous organosilica for efficient removal of Hg(ii) from polluted water.

A new N- and S-rich highly ordered periodic mesoporous organosilica material DMTZ-PMO bearing thiadiazole and thiol moieties inside the pore-wall of a 2D-hexagonal nanomaterial has been synthesized. DMTZ-PMO shows a very high surface area (971 m2 g-1), and can be used for efficient and fast removal of Hg2+ from polluted water with a very high Hg2+ uptake capacity of 2081 mg g-1.

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.

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.

Ultrasmall Platinum Stabilized on Triphenylphosphine-Modified Silica for Chemoselective Hydrogenation.

Chemoselective hydrogenation of substrates with more than one functional group that could be hydrogenated is quite challenging and is of fundamental importance. Here, the enhanced chemoselectivity of ultrasmall (<1 nm) platinum nanoparticles (NPs) stabilized on silica modified with triphenylphosphine (PSiO2 ) in hydrogenation reactions is reported. Platinum NPs on PSiO2 exhibit much higher selectivity than those on SiO2 in the hydrogenation of acetophenone to 1-phenylethanol (99.9 versus 36 %) and hydrogenation of phenylacetylene to styrene (85 versus 52 %). The results of NMR spectroscopy, X-ray photoelectron spectroscopy, and in situ CO adsorption FTIR spectroscopy indicate the existence of strong interactions between triphenylphosphine and Pt NPs. Consequently, Pt NPs on PSiO2 have smaller particle sizes and more positive Pt 4 f binding energy than those of Pt/SiO2 ; these are the main contributors to the superior chemoselectivity of Pt NPs. The organically modified silica could act as an efficient solid ligand for tuning the catalytic performance of metal NPs.

A luminescent nanoporous hybrid material based drug delivery system showing excellent theranostics potential for cancer.

A novel hybrid nanoporous material (LNH-1) bearing a tris(propyliminomethyl)-phloroglucinol fluorescent moiety in the framework has been designed and administration of an LNH-1 based drug delivery system containing doxorubicin to cancer cells showed inhibition of proliferation, suggesting its future potential theranostics application in cancer.

One-pot thioetherification of aryl halides with thiourea and benzyl bromide in water catalyzed by Cu-grafted furfural imine-functionalized mesoporous SBA-15.

Surface functionalization of SBA-15 followed by its reaction with Cu(OAc)(2) has been carried out to develop a new Cu-grafted functionalized mesoporous material, which catalyzes one-pot three component coupling of different aryl halides with thiourea and benzyl bromide in aqueous medium to produce aryl thioethers in very good yields (80-88%).

Porphyrin based porous organic polymers: novel synthetic strategy and exceptionally high CO2 adsorption capacity.

Iron containing porous organic polymers (Fe-POPs) have been synthesized by a facile one-pot bottom-up approach to porphyrin chemistry by an extended aromatic substitution reaction between pyrrole and aromatic dialdehydes in the presence of small amount of Fe(III). The Fe-POPs possess very high BET surface area, large micropores and showed excellent CO(2) capture (~19 wt%) at 273 K/1 bar.

Facile C-S coupling reaction of aryl iodide and thiophenol catalyzed by Cu-grafted furfural functionalized mesoporous organosilica.

A new functionalized mesoporous organosilica has been designed via Schiff-base condensation of furfural and 3-aminopropyltriethoxy-silane (APTES) followed by its hydrothermal co-condensation with tetraethylorthosilicate (TEOS) in the presence of a cationic surfactant CTAB. Subsequent reaction of this mesoporous organosilica with Cu(OAc)(2) in absolute ethanol leads to the formation of a new Cu(II)-grafted mesoporous organosilica catalyst 1. Powder XRD, HR TEM, FE SEM, N(2) sorption and FT IR spectroscopic tools are used to characterize the materials. This Cu-anchored mesoporous material acts as an efficient, reusable catalyst in the aryl-sulfur coupling reaction between aryl iodide and thiophenol for the synthesis of value added diarylsulfides.