Elevated temperature-driven coordinative reconstruction of an unsaturated single-Ni-atom structure with low valency on a polymer-derived matrix for the electrolytic oxygen evolution reaction.

A high-temperature pyrolysis-controlled coordination reconstruction resulted in a single-Ni-atom structure with a Ni-Nx-C structural unit (x = N atom coordinated to Ni). Pyrolysis of Ni-phen@ZIF-8-RF at 700 °C resulted in NiNP-NC-700 with predominantly Ni nanoparticles. Upon elevating the pyrolysis temperature from 700 to 900 °C, a coordination reconstruction offers Ni-Nx atomic sites in NiSA-NC-900. A combined investigation with X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and soft X-ray L3-edge spectroscopy suggests the stabilization of low-valent Niδ+ (0 < δ < 2) in the Ni-N-C structural units. The oxygen evolution reaction (OER) is a key process during water splitting in fuel cells. However, OER is a thermodynamically uphill reaction with multi-step proton-coupled electron transfer and sluggish kinetics, due to which there is a need for a catalyst that can lower the OER overpotentials. The adsorption energy of a multi-step reaction on a single metal atom with coordination unsaturation tunes the adsorption of each oxygenated intermediate. The promising OER activity of the NiSA-NC-900/NF anode on nickel foam was followed by the overall water splitting (OWS) using using NiSA-NC-900/NF as anode and Pt coil as the cathodic counterpart, wherein a cell potential of 1.75 V at 10 mA cm-2 was achieved. The cell potential recorded with Pt(-)/(+)NiSA-NC-900/NF was much lower than that obtained for other cells, i.e., Pt(-)/NF and NF(-)/(+)NF, which enhances the potentials of low-valent NiSAs for insightful understanding of the OER. At a constant applied potential of 1.61 V (vs. RHE) for 12 h, an small increase in current for initial 0.6 h followed by a constant current depicts the fair stability of catalyst for 12 h. Our results offer an insightful angle into the OER with a coordinatively reconstructed single-Ni-atom structure at lower valency (<+2).

DFT and experimental studies of the facet-dependent oxygen vacancies modulated WS2/BiOCl-OV S-scheme structure for enhanced photocatalytic removal of ciprofloxacin from wastewater.

The present study explores visible light-assisted photodegradation of ciprofloxacin hydrochloride (CIP) antibiotic as a promising solution to water pollution. The focus is on transforming the optical and electronic properties of BiOCl through the generation of oxygen vacancies (OVs) and the exposure of (110) facets, forming a robust S-scheme heterojunction with WS2. The resultant OVs mediated composite with an optimal ratio of WS2 and BiOCl-OV (4-WS2/BiOCl-OV) demonstrated remarkable efficiency (94.3%) in the visible light-assisted photodegradation of CIP antibiotic within 1.5 h. The CIP degradation using 4-WS2/BiOCl-OV followed pseudo-first-order kinetics with the rate constant of 0.023 min-1, outperforming bare WS2, BiOCl, and BiOCl-OV by 8, 6, and 4 times, respectively. Density functional theory (DFT) analysis aligned well with experimental results, providing insights into the structural arrangement and bandgap analysis of the photocatalysts. Liquid chromatography-mass spectrometry (LC-MS) analysis utilized for identifying potentially degraded products while scavenging experiments and electron paramagnetic resonance (EPR) spin trapping analysis elucidated the S-scheme charge transfer mechanism. This research contributes to advancing the design of oxygen vacancy-mediated S-scheme systems in the realm of photocatalysis, with potential implications for addressing water pollution concerns.

Wastewater Treatment Using Membrane Bioreactor Technologies: Removal of Phenolic Contaminants from Oil and Coal Refineries and Pharmaceutical Industries.

Huge amounts of noxious chemicals from coal and petrochemical refineries and pharmaceutical industries are released into water bodies. These chemicals are highly toxic and cause adverse effects on both aquatic and terrestrial life. The removal of hazardous contaminants from industrial effluents is expensive and environmentally driven. The majority of the technologies applied nowadays for the removal of phenols and other contaminants are based on physio-chemical processes such as solvent extraction, chemical precipitation, and adsorption. The removal efficiency of toxic chemicals, especially phenols, is low with these technologies when the concentrations are very low. Furthermore, the major drawbacks of these technologies are the high operation costs and inadequate selectivity. To overcome these limitations, researchers are applying biological and membrane technologies together, which are gaining more attention because of their ease of use, high selectivity, and effectiveness. In the present review, the microbial degradation of phenolics in combination with intensified membrane bioreactors (MBRs) has been discussed. Important factors, including the origin and mode of phenols' biodegradation as well as the characteristics of the membrane bioreactors for the optimal removal of phenolic contaminants from industrial effluents are considered. The modifications of MBRs for the removal of phenols from various wastewater sources have also been addressed in this review article. The economic analysis on the cost and benefits of MBR technology compared with conventional wastewater treatments is discussed extensively.

O and S co-doping induced N-vacancy in graphitic carbon nitride towards photocatalytic peroxymonosulfate activation for sulfamethoxazole degradation.

Doping-induced vacancy engineering of graphitic carbon nitride (GCN) is beneficial for bandgap modulation, efficient electronic excitation, and facilitated charge carrier migration. In this study, synthesis of oxygen and sulphur co-doped induced N vacancies (OSGCN) by the hydrothermal method was performed to activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) antibiotic degradation and H2 production. The results from experimental and DFT simulation studies validate the synergistic effects of co-dopants and N-vacancies, i.e., bandgap lowering, electron-hole pairs separation, and high solar energy utilization. The substitution of sp2 N atom by O and S co-dopants causes strong delocalization of HOMO-LUMO distribution, enhancing carrier mobility, increasing reactive sites, and facilitating charge-carrier separation. Remarkably, OSGCN/PMS photocatalytic system achieved 99.4% SMX degradation efficiency and a high H2 generation rate of 548.23 µ mol g-1 h-1 within 60 min and 36 h, respectively under visible light irradiations. The SMX degradation kinetics was pseudo-first-order with retained recycling efficiency up to 4 catalytic cycles. The results of EPR and chemical scavenging experiments revealed the redox action of reactive oxidative species, wherein 1O2 was the dominant reactive species in SMX degradation. The identification of formed intermediates and the SMX stepwise degradation pathway was investigated via LC-MS analysis and DFT studies, respectively. The results from this work anticipated deepening the understanding of PMS activation by substitutional co-doping favoring N-vacancy formation in GCN lattice for improved photocatalytic activity.

Ultrastable Conjugated Microporous Polymers Containing Benzobisthiadiazole and Pyrene Building Blocks for Energy Storage Applications.

In recent years, conjugated microporous polymers (CMPs) have become important precursors for environmental and energy applications, compared with inorganic electrode materials, due to their ease of preparation, facile charge storage process, π-conjugated structures, relatively high thermal and chemical stability, abundance in nature, and high surface areas. Therefore, in this study, we designed and prepared new benzobisthiadiazole (BBT)-linked CMPs (BBT-CMPs) using a simple Sonogashira couplings reaction by reaction of 4,8-dibromobenzo(1,2-c;4,5-c')bis(1,2,5)thiadiazole (BBT-Br2) with ethynyl derivatives of triphenylamine (TPA-T), pyrene (Py-T), and tetraphenylethene (TPE-T), respectively, to afford TPA-BBT-CMP, Py-BBT-CMP, and TPE-BBT-CMP. The chemical structure and properties of BBT-CMPs such as surface areas, pore size, surface morphologies, and thermal stability using different measurements were discussed in detail. Among the studied BBT-CMPs, we revealed that TPE-BBT-CMP displayed high degradation temperature, up to 340 °C, with high char yield and regular, aggregated sphere based on thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), respectively. Furthermore, the Py-BBT-CMP as organic electrode showed an outstanding specific capacitance of 228 F g-1 and superior capacitance stability of 93.2% (over 2000 cycles). Based on theoretical results, an important role of BBT-CMPs, due to their electronic structure, was revealed to be enhancing the charge storage. Furthermore, all three CMP polymers featured a high conjugation system, leading to improved electron conduction and small bandgaps.

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine.

New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on 1H and 13C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 °C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 °C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (Td10 = 478 °C) and char yield (66 wt%) after thermal polymerization at 240 °C. An investigation of the thermal and luminescence properties of metal-porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-BZ/Ni and Por-BZ/Zn complexes significantly, to 241 and 231 °C, respectively. The metal ions acted as the effective promoter and catalyst for the thermal polymerization of the Por-BZ monomer, and also improved the thermal stabilities after thermal polymerization.

Lignin-Derived Syringol and Acetosyringone from Palm Bunch Using Heterogeneous Oxidative Depolymerization over Mixed Metal Oxide Catalysts under Microwave Heating.

Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al2O3 or SiO2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K2CO3 extracted lignin catalyzed by Cu-Fe/SiO2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al2O3 catalyst was lower (49.52 wt%) compared with that from Cu-Fe/SiO2 catalyst (63.87 wt%), Cu-Fe/Al2O3 catalyst provided the greater selectivity of main two value-added products, syringol and acetosyrigone, at 54.64% and 23.65%, respectively (78.29% total selectivity of two products) from the NaOH extracted lignin. The findings suggested a promising method for syringol and acetosyringone production from the oxidative heterogeneous lignin depolymerization under low power intensity microwave heating within a short reaction time of 30 min.

Advances in lignin valorization towards bio-based chemicals and fuels: Lignin biorefinery.

Lignin is one of the most promising renewable sources for aromatic hydrocarbons, while effective depolymerization towards its constituent monomers is a particular challenge because of the structural complexity and stability. Intensive research efforts have been directed towards exploiting effective valorization of lignin for the production of bio-based platform chemicals and fuels. The present contribution aims to provide a critical review of key advances in the identification of exact lignin structure subjected to various fractionation technologies and demonstrate the key roles of lignin structures in depolymerization for unique functionalized products. Various technologies (e.g., thermocatalytic approaches, photocatalytic conversion, and mechanochemical depolymerization) are reviewed and evaluated in terms of feasibility and potential for further upgrading. Overall, advances in pristine lignin structure analysis and conversion technologies can facilitate recovery and subsequent utilization of lignin towards tailored commodity chemicals and fungible fuels.

A Novel Method for the Pentosan Analysis Present in Jute Biomass and Its Conversion into Sugar Monomers Using Acidic Ionic Liquid.

Recently, ionic liquids (ILs) are used for biomass valorization into valuable chemicals because of their remarkable properties such as thermal stability, lower vapor pressure, non-flammability, higher heat capacity, and tunable solubility and acidity. Here, we demonstrate a method for the synthesis of C5 sugars (xylose and arabinose) from the pentosan present in jute biomass in a one-pot process by utilizing a catalytic amount of Brønsted acidic 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate IL. The acidic IL is synthesized in the lab and characterized using NMR spectroscopic techniques for understanding its purity. The various properties of BAIL are measured such as acid strength, thermal and hydrothermal stability, which showed that the catalyst is stable at a higher temperature (250 °C) and possesses very high acid strength (Ho 1.57). The acidic IL converts over 90% of pentosan into sugars and furfural. Hence, the presenting method in this study can also be employed for the evaluation of pentosan concentration in other kinds of lignocellulosic biomass.

Direct Production of Furfural in One-pot Fashion from Raw Biomass Using Brønsted Acidic Ionic Liquids.

The conversion of raw biomass into C5-sugars and furfural was demonstrated with the one-pot method using Brønsted acidic ionic liquids (BAILs) without any mineral acids or metal halides. Various BAILs were synthesized and characterized using NMR, FT-IR, TGA, and CHNS microanalysis and were used as the catalyst for raw biomass conversion. The remarkably high yield (i.e. 88%) of C5 sugars from bagasse can be obtained using 1-methyl-3(3-sulfopropyl)-imidazolium hydrogen sulfate ([C3SO3HMIM][HSO4]) BAIL catalyst in a water medium. Similarly, the [C3SO3HMIM][HSO4] BAIL also converts the bagasse into furfural with very high yield (73%) in one-pot method using a water/toluene biphasic solvent system.