Powdered silk: A promising biopolymer for the treatment of dye contaminated water.

Discharge of textile dye effluents into water bodies is creating stress to aquatic life and contaminating water resources. In this study, a new biopolymer adsorbent silk fibroin (SF) was prepared from Bombyx mori silk fibroin (SF) and used for removal of Solochrome Black-T (SB-T) from water. This innovative adsorbent exhibits an exceptional adsorption capacity of 20.08 mg/g, achieving a removal efficiency of approximately 98.6 % within 60 min. Notably, the powdered SF adsorbent demonstrates rapid kinetics, surpassing the performance of previously reported similar adsorbents in adsorption capacity and reaction speed. The molecular weight and particle diameter of the material were observed to be > 1.243 kDa and 3 µm, respectively. The experimental investigations were performed on different parameters, viz., adsorbent dosage, contact time, repeatability, and desorption-adsorption study. The experimental data well fit for the Langmuir model (R2 = 0.937, qmax = 20.08 mg/g) and the pseudo-second-order kinetics (R2 = 0.921 and qe = 1.496 mg/g). Compared to the adsorbents reported in the literature, the newly prepared SF showed high adsorption capacity and faster kinetics to address real-life situations. The novelty of this work extends beyond its remarkable adsorption capabilities. The SF adsorbent offers a cost-effective, sustainable solution and regenerable adsorption material with minimal negative environmental impacts. This regenerability, with its versatility and broad applicability, positions powdered SF fibroin as a transformative technology in water treatment and environmental protection.

Nanophotonics triggered thermally enhanced solar water disinfection bottles for slum dwellers.

Among several existing technologies, solar pasteurization is widely accepted as a reliable and cost-effective method for the removal of microbial pathogens from water. This work reports nanophotonics-triggered thermally enhanced solar water disinfection bottles (nano-SODIS) designed rationally by coating plasmonic carbon nanoparticles (CNP) on the outer surface for the targeted pathogen inactivation from water. The cost-effective CNP nanophotonic material used in this work has high efficiency in harvesting solar radiation and dissipating the heat locally. It has broad absorption efficiency to cover the entire solar spectrum; hence, it is capable to generate multiple scattering. It has also properties of boosting of photon absorption and focusing the light within a constrained spatial region, resulting in powerful and targeted heating that inactivates microorganisms in near proximity. These CNPs were used to coat the nano-SODIS water bottles that achieved the highest temperature of 65-70 °C within 90 min of exposure to solar radiation with a consequent six-log reduction. The disinfection period was reduced by a factor of 3 compared to the conventional solar disinfection system. The treated water was further assessed for 7 days, which confirmed the complete absence of bacteria and no sign of regeneration after storing for a longer period. The SODIS bottles coated with CNP thus overcome the problem of limited solar absorption by acquiring higher broadband absorption potential and thus achieving comparatively high disinfection efficiency. The broad band absorption of CNP was confirmed through UV-DRS absorption spectra. The nano-SODIS bottles designed and constructed in this work are simple, durable, and user friendly in nature and have been deployed in the rural and slums areas of Nagpur, Delhi, and Mumbai, India to provide pathogen-free potable water and to improve the health of local poor communities.

'Green firecrackers' with reduced barium emissions in particulate matter.

Ambient air quality is affected due to the emission of pollutants on a large scale after the bursting of firecrackers. Traditionally in all firecrackers, barium (Ba) compounds are used as oxidizers and also to impart green colour flame. Combustion products of barium compounds are water soluble and readily absorbed by the body affecting human health. Thus, the inherent risk of Ba pollution due to the bursting of firecrackers has consequent health effects. To reduce the ambient air pollution caused due to burning of conventional firecrackers, CSIR NEERI has developed reduced emission firecrackers (green crackers). This is achieved by reducing the amount of chemicals, barium nitrate, shell size and addition of additives such as zeolite and iron oxide. This study aims to specifically investigate the influence of additives on the level of barium in reduced emission firecrackers. Four types of conventional and reduced emission firecrackers were selected and tested inside a firecracker emission testing facility to check the levels of barium in PM10 and PM2.5. The measured mean concentrations of all types of reduced emission crackers (green crackers) provided by fireworks manufacturers show significantly reduced barium concentration by 30-60% compared to conventional crackers depending on the type of firecrackers, shell size and amount of chemicals used. The possible reason for reduced Ba level is attributed to i) reduced usage of Ba(NO3)2 and ii) formation of heavy density compounds, leading to soil fallout.

Occurrence of phthalates in facemasks used in India and its implications for human exposure.

Synthetic polymers with additives are used in the manufacturing of face masks (FMs); hence, FMs could be a potential source of exposure to phthalic acid esters (PAEs). India stands second in the world in terms of the FMs usage since the beginning of Covid-19 pandemic. However, little is known about the PAEs content of FMs used in India. Some PAEs, such as DEHP and DBP are suspected endocrine disrupting chemicals (EDCs); hence, wearing FM may increase the risk of exposure to these EDCs. In this study, we collected 91 samples of FMs from eight Indian cities and analyzed for five PAEs viz. DMP, DEP, DBP, BBP, and DEHP. The PAEs contents in FMs ranged from 101.79 to 27,948.64 ng/g. The carcinogenic risk of N 95 with filter, N-95, and cloth masks was higher than the threshold levels. The findings indicate the need to control PAEs in FMs through regulatory actions.

Metal nitride-based nanostructures for electrochemical and photocatalytic hydrogen production.

The over-dependence on fossil fuels is one of the critical issues to be addressed for combating greenhouse gas emissions. Hydrogen, one of the promising alternatives to fossil fuels, is renewable, carbon-free, and non-polluting gas. The complete utilization of hydrogen in every sector ranging from small to large scale could hugely benefit in mitigating climate change. One of the key aspects of the hydrogen sector is its production via cost-effective and safe ways. Electrolysis and photocatalysis are well-known processes for hydrogen production and their efficiency relies on electrocatalysts, which are generally noble metals. The usage of noble metals as catalysts makes these processes costly and their scarcity is also a limiting factor. Metal nitrides and their porous counterparts have drawn considerable attention from researchers due to their good promise for hydrogen production. Their properties such as active metal centres, nitrogen functionalities, and porous features such as surface area, pore-volume, and tunable pore size could play an important role in electrochemical and photocatalytic hydrogen production. This review focuses on the recent developments in metal nitrides from their synthesis methods point of view. Much attention is given to the emergence of new synthesis techniques, methods, and processes of synthesizing the metal nitride nanostructures. The applications of electrochemical and photocatalytic hydrogen production are summarized. Overall, this review will provide useful information to researchers working in the field of metal nitrides and their application for hydrogen production.

Silk fibroin: a promising bio-material for the treatment of heavy metal-contaminated water, adsorption isotherms, kinetics, and mechanism.

Silk is the strongest natural biopolymer produced by silk worms possessing superior adsorbent properties and thus extensively used in various applications. The present study involved the preparation of powder form of a silk fibroin materials and their application in adsorption of heavy metals, particularly, iron from aqueous solution. The morphological and structural characteristic properties of this promising materials were examined by using different analytical techniques. Batch experiments were conducted within feasible parametric ranges to understand the effect of dose, time, concentration, pH, and reusability. Silk fibroin was effective for iron adsorption over a wide range of pH 6 to 10. The adsorption removal efficiency of 98% was attained for removal of iron from contaminated water at moderate dose of 0.25 g and contact time of 60 min, which is unprecedented by considering the environment benign nature of the material. The data was examined in different isotherm models wherein it fitted best in Langmuir adsorption model. Similarly, Langmuir isotherm model, with R2 value of 0.984 and KL 0.412 and maximum adsorption capacity as 12.82 mg g-1, suggests monolayer adsorption. Kinetic study with better R2 value of 0.941 represented the pseudo-second order kinetics governed by the chemisorption reaction. To understand the practical applicability of silk fibroin, the repeatability study up to 5 cycles were performed. The findings are very encouraging which confirmed the usage of silk fibroin as adsorbent for multiple cycles with marginal decrease in adsorption efficiency. Eventually, the material was tested for iron removal in real contaminated water which revealed its potential and selectivity for removal of iron in different matrix.

Arsenite removal from drinking water by bark-based magnetic iron oxide particle (BMIOP): a column study.

The removal of arsenite [As(III)] from drinking water was investigated in a column at flow rates of 2.0 and 5.0 mL/min (up-flow direction) using bark-based magnetic iron oxide particles (BMIOP) prepared by coating (Fe(NO3)3.9H2O) over Tamarindus Indica bark. The BMIOP was compared with regenerated BMIOP, commercial activated carbon, commercial activated alumina (Al2O3). At 2.0 mL/min, empty bed contact time (EBCT), breakthrough time (BT), the volume of treated water and breakthrough capacity (BC) on fresh BMIOP were found to be 6.8 min, 33.15 h, 4.380 L and 0.742 mg/g, respectively, and at 5.0 mL/min, were found to be 4.1 min, 13 h, 3.675 L and 0.453 mg/g respectively. EBCT, BT and BC were increased by 65.85%, 155% and 63.79%, respectively, as the flow rate was reduced from 5.0 to 2.0 mL/min. After regeneration of BMIOP, EBCT, BT, saturated time, BC and saturation capacity (SC) were reduced by 21.95%, 15.38%, 55.15%, 16.78% and 29.71%, respectively. The BC of fresh BMIOP was increased by factors 4.15, 3.60 and 1.20 and SC by factors 9.51, 7.88 and 1.42 compared to commercial activated carbon, commercial activated Al2O3 and regenerated BMIOP, respectively. Logit model could be used for the design of the adsorption column. Thomas model and artificial neural network (ANN) were applied to predict the characteristic column parameters useful for process design. Quality of treated water meets BIS requirements. Toxicity Characteristic Leaching Procedure (TCLP) and semi-dynamic tests show that the exhausted BMIOP is safe for disposal in a secure landfill; hence, BMIOP has been proved to separate As(III) from water.

Thermite reaction driven pyrotechnic formulation with promising functional performance and reduced emissions.

Green pyrotechnics/firecrackers reported herein are driven by thermite reactions for self-contained and self-sustained exothermic chemical reactions to make heat and sound by the usage of minimal fuel (aluminum), oxidizer (potassium nitrate), and Sulfur. These firecrackers have the potential for generating less emissions (70%) compared to commercial firecracker-based counterparts due to the presence of additives and are therefore designated as "Green firecrackers" or reduced emissions firecrackers. The functional performance and long-term stability of the composition was investigated through sound measurement and different tests, including ageing, thermal stability, and moisture test. The thermodynamics of the facilitated thermite reaction was cross-checked with experimental and theoretical methods. Prevalent mechanism for a substantial reduction in emissions to the tune of about 70% has been discussed. Cost of the green firecrackers is at par with the commercial firecrackers as cost of raw materials being used to prepare the formulation is comparable to the relatively toxic oxidizer substituted. "Green firecrackers" developed and reported here are environmentally benign in nature with higher business potential as far as a green chemistry-based sustainable solution for the society is required.

Reduced graphene oxide -MnO2 nanocomposite for CO2 capture from flue gases at elevated temperatures.

The newly prepared reduced graphene oxide-MnO2 (rGO-MnO2) nanocomposite has exhibited highly selective CO2 adsorption from gaseous mixtures at elevated temperatures. The Mn2+ basic sites are scattered over the rGO-MnO2 nanocomposite which produce an effective BET surface area of 710 m2 g-1 for selective CO2 capture. The selective adsorption of CO2 (5.87 mmol g-1) over N2 (0.36 mmol g-1) and CH4 (0.41 mmol g-1) at 298 K/1 bar was achieved by the nanocomposite. The heat of adsorption followed a unique correlation with the quantity of CO2 adsorbed and fits well to the Fowler-Guggenheim equation. The mechanism of CO2 adsorption on the nanocomposite was complemented with molecular modelling and simulations. The rGO-MnO2 have shown better CO2 adsorption capacity of 28.5 mmol g-1 at 323 K/20 bar as compared to zeolite derivatives, MOFs, and carbons as reported in the literature. The formation of inert frameworks with 3-6 nm porous structure in the nanocomposite thermally stabilizes to capture CO2 repeatedly. The nanocomposite with adsorption capacity of 3.69 mmol g-1 at 373 K/1 bar is quite close to real-life conditions for flue gas treatment.

Graphene/fluorescein dye-based sensor for detecting As(III) in drinking water.

A complex of reduced graphene oxide (rGO) and fluorescein (FL) dye nanoparticles of size between 50 and 100 nm has been prepared and its sensing performance for detection of As(III) in drinking water has been reported. When As(III) binds to the rGO-FL nanoparticles the relative quenching of fluorescence was increased with increase in As(III) concentration thus provide two linear calibration ranges (0-4.0 mmol L-1 and 4.0-10 mmol L-1). The fluorescence quenching mechanism was investigated by using time-resolved fluorescence spectroscopy and molecular modeling. The detection limit of this sensor has been determined as equal to 0.96 µg L-1 which is about 10 times lower than the WHO stipulated standard for As(III) in drinking water (10 µg L-1). The analytical performance and potential application of the nanosensor was compared to commercial field kits used in arsenic monitoring. The sensor proposed in this study is fast, sensitive and accurate for detection of As(III) in drinking water and environmental samples.

High performance CO2 capture at elevated temperatures by using cenospheres prepared from solid waste, fly ash.

Cenospheres (CS) are spherical shaped inorganic frameworks present in with fly ash which is generated from coal-fired thermal power plants. These spherical structures were functionalized with imidazole and amine moieties to capture CO2 selectively from flue gases at elevated temperature. The functionalized CS have shown a high selectivity for CO2 adsorption (4.68 mmol g-1) over N2 (0.46 mmol g-1) at 333 K/1 bar from a simulated flue gas (0.15 CO2 and 0.85 N2, v%) composition of thermal power plants. When the moisture content reached to 30 vol% the adsorption capacity of CS materials was reduced to 20 vol% as compared to dry flue gas. The functionalized CS can be used repeatedly for 50 cycles without losing its adsorption capacity. The cost estimate for CO2 capture by using the proposed adsorption system would be $12.01/ton of CO2 which is lower as compared to amine absorption system and zeolite-based adsorption system reported in the literature. The CS materials are prepared from solid wastes reduce the cost of production and their large scale manufacturing is technically feasible to capture CO2 from industrial flue gases efficiently in near future.

Synthesis of Ni2P/CdS and Pt/TiO2 nanocomposite for photoreduction of CO2 into methanol.

It is a great challenge to convert thermochemically stable CO2 into value-added products such as CH4, CH3OH, CO via utilizing solar energy. It is also a difficult task to develop an efficient catalyst for the reduction of CO2. We have designed and synthesized noble metal-free photocatalytic nanostructure Ni2P/CdS and Pt/TiO2 for conversion of CO2 to methanol in the presence of sacrificial donor triethylamine (TEA) and hydrogen peroxide. The synthesised catalysts physicochemical properties were studied by using several spectroscopic techniques like; XRD, UV-DRS, XPS, TEM, SEM and PL. Quantification of methanol by GC-MS showed encouraging results of 1424.8 and 2843 µmol g-1 of catalyst for Pt/TiO2 and 5 wt% Ni2P/CdS composites, respectively. Thus, Ni2P/CdS is a promising catalyst with higher productivity and significant selectivity than in-vogue catalysts.

Detection of nickel by chemo and fluoro sensing technologies.

Sensing technology for heavy metal detection is very crucial for recent decades as the detection method is very easy, rapid, and does not require any pre-treatment of the sample. Nickel is a trace element in the human body and basically a moderate toxic element. There is a limited number of chemo and fluoro sensors reported for nickel as compared to other transition metal ion. Therefore, there is a need for the detailed structure and property studies of the nickel-probes as the knowledge can help in the upcoming development of probes for the nickel. In this review, we have discussed about different colorimetric, fluorimetric and fluorescent chemosensor and their structure, characterization, detection limit, association constant, media, and bio-imaging studies if they are active.

Molecularly imprinted microparticles (microMIPs) embedded with reduced graphene oxide for capture and destruction of E.coli in drinking water.

In this article for the first time, we have reported, a facile way for the creation of E.coli impressions in the polymer for selective capture and to destroy E. coli in drinking water. This microporous imprinted polymer has shown the existence of micrometer size rod shape cavities with the population of 2.45 × 102 ± 60 imprints per cm2. Adsorption capacity of the polymer for E.coli was 103 CFU mg-1. This microporous imprinted polymer captured 99% of the bacteria within 30 min at initial concentration of 109 CFU mL-1. The non-imprinted polymer prepared without the bacteria imprinting reported only 40% of the bacteria removal even after 60 min. The reduced graphene oxide was embedded in the microporous imprinted polymer and it reported minimum inhibitory concentration at 7.4 mg L-1. Within 10 min, reduced graphene oxide completely kills the E.coli while microporous imprinted polymer was embedded with the reduced graphene oxide takes about 13 min to disinfect the water. The reduced graphene oxide nanoparticles were near the imprinted cavity to generate localized temperature between 180 and 210 °C to kill the bacterial cells trapped inside the imprinted cavities of the polymer. The thermal atomic force microscope with the specialized heated probe tips were used to determine the localized temperature in the polymers. The localized thermal energy would be responsible for the production of superoxides, which were as similar to photolysis reactions, and would be further improving antibacterial activity. The combination of selective capture and destruction of pathogens in a single molecular construct improves disinfection of drinking water.

Enhanced H2 production from dehydrogenation of sodium borohydride over the ternary Co0.97Pt0.03/CeO x nanocomposite grown on CGO catalytic support.

The development of low-cost materials for the 100% dehydrogenation of metal hydrides is highly essential to vitalize the chemical hydride-based hydrogen economy. In this context, the ternary Co-Ce-Pt nanocomposite immobilized on functionalized catalytic support CGO is synthesized by the one step chemical reduction approach and has been directly employed for the ethanolysis of sodium borohydride. The co-operative effect of CGO and the synergy between metallic nanoparticles is investigated to determine the highest rate of hydrogen (H2) production. The maximum hydrogen generation rate (HGR) of 41.53 L (min g M )-1 is achieved with the Co0.97Pt0.03/CeO x /CGO nanohybrid from the alkaline ethanolysis of sodium borohydride (SB). In addition, the resultant nanohybrid exhibited a relatively low activation energy of 21.42 kJ mol-1 for the ethanolysis of SB. This enhanced catalytic activity may be attributed to the intermetallic charge transport among metallic Pt, Co/Co3O4, and CeO x counterparts. Moreover, the catalytic support CGO provides mesoporous functionalized surface and its intercalated GO layers promote charge transport. These results indicate that the resultant catalytic system described here for the dehydrogenation of SB can offer a portable and low-cost H2 supply for various fuel cell applications.

Plasmonics driven engineered pasteurizers for solar water disinfection (SWADIS).

Rampant environmental pollution is the most ubiquitous concern of current world. A sustainable panacea to overarching contamination of water-borne pathogens demands cheap and eco-friendly oriented research. Solar energy is effortlessly accessible in most of the weather conditions and can be used for water decontamination. In this context, Solar Water Disinfection (SWADIS) appears to be feasible solution. Herein we are reporting newly developed Carbon nanoparticles (CNP) which shows absorption of light in broad region extending from Ultraviolet-Visible (UV) to Infrared Spectroscopy (IR). This CNP with pronounced photothermal effect has been used for SWADIS. Photothermal effect of plasmonic nanomaterials has massive potential and has exploited for disinfection of water. Moving towards practical device design we have developed an efficient CNP based Multipurpose Solar Pasteurizer (MSP) and Nano-Solar Pasteurizer (NSP) which can efficiently perform the SWADIS. Result shows that upon irradiation under natural solar radiation pasteurizers can thermally inactivate the bacteria. The system proves to be able to perform 100% bacterial inactivation in sunny days. We also conducted bacterial inactivation experiments by simulating 106 CFU mL-1 concentration of E. coli in water to mimic field conditions. Results are evident that pasteurizers achieved 100% bacterial inactivation within period of ˜45 min under sunlight.

Development of bark-based magnetic iron oxide particle (BMIOP), a bio-adsorbent for removal of arsenic (III) from water.

Novel low-cost bark-based magnetic iron oxide particles (BMIOPs) were synthesized and investigated for the removal of As(III) in drinking water. The synthesized BMIOP had a saturation magnetization value of 38.62 emug-1 which was found to be enough for the magnetic separation of exhausted BMIOP after As(III) adsorption. Parameters like agitation speed, adsorbent dosage, contact time, pH, temperature, and initial concentration were thoroughly investigated. Langmuir, Freundlich, and Dubinin-Radushkevich isotherms were used for the modeling of experiments and observed a maximum adsorption (19.61 mg g-1) of As(III) by Langmuir isotherm. Kinetics of As(III) sorption were well correlated with the coefficients in pseudo-first-order than the pseudo-second-order rate equation. Thermodynamic parameter investigation revealed that As(III) sorption process is endothermic, feasible, and spontaneous. BMIOP emerged as less expensive adsorbent for the abatement of arsenic ion from the drinking water. BMIOP showed 13.58 mg g-1 adsorption capacity when As(V) alone is present, while it is 9.43 and 7.04 mg g-1 for As(V) and As(III), respectively, when present together in the water. Graphical Abstract ᅟ.

Removal of arsenic(III) from water by magnetic binary oxide particles (MBOP): Experimental studies on fixed bed column.

Magnetic binary oxide particles (MBOP) were prepared by template method using chitosan in the laboratory for the removal of As(III) from water. The prepared MBOP has super paramagnetic property which is sufficient for magnetic separation. Column study was performed at two different flow rates of 2.0ml/min and 5.0ml/min and comparison was made with regenerated MBOP, commercial activated carbon and commercial activated alumina. It is observed that fresh MBOP has higher breakthrough time and capacity than regenerated MBOP by a factor of 1.25 and 1.37 respectively. In Logit method, the values of K (adsorption rate constant) and N (adsorption capacity coefficient) were obtained as 0.2066 (L/mgh) and 1014(mg/L) for 5.0ml/min flow rate. All the drinking water parameters are within the limit of BIS 10500-2012. Toxicity characteristic leaching procedure (TCLP) and semi dynamic tests were performed for the mix ratios of 01:02:01, 01:02:05 and 01:02:10 and were found safe for the disposal.

Copper-manganese mixed oxides: CO2-selectivity, stable, and cyclic performance for chemical looping combustion of methane.

Chemical looping combustion (CLC) is a key technology for oxy-fuel combustion with inherent separation of CO2 from a flue gas, in which oxygen is derived from a solid oxygen carrier. Multi-cycle CLC performance and the product selectivity towards CO2 formation were achieved using mixed oxide of Cu and Mn (CuMn2O4) (Fd3[combining macron]m, a = b = c = 0.83 nm) as an oxygen carrier. CuMn2O4 was prepared by the co-precipitation method followed by annealing at 900 °C using copper(II) nitrate trihydrate and manganese(II) nitrate tetrahydrate as metal precursors. CuMn2O4 showed oxygen-desorption as well as reducibility at elevated temperatures under CLC conditions. The lattice of CuMn2O4 was altered significantly at higher temperature, however, it was reinstated virtually upon cooling in the presence of air. CuMn2O4 was reduced to CuMnO2, Mn3O4, and Cu2O phases at the intermediate stages, which were further reduced to metallic Cu and MnO upon the removal of reactive oxygen from their lattice. CuMn2O4 showed a remarkable activity towards methane combustion reaction at 750 °C. The reduced phase of CuMn2O4 containing Cu and MnO was readily reinstated when treated with air or oxygen at 750 °C, confirming efficient regeneration of the oxygen carrier. Neither methane combustion efficiency nor oxygen carrying capacity was altered with the increase of CLC cycles at any tested time. The average oxygen carrying capacity of CuMn2O4 was estimated to be 114 mg g(-1), which was not altered significantly with the repeated CLC cycles. Pure CO2 but no CO, which is one of the possible toxic by-products, was formed solely upon methane combustion reaction of CuMn2O4. CuMn2O4 shows potential as a practical CLC material both in terms of multi-cycle performance and product selectivity towards CO2 formation.

Nanostructured Mn-Fe Binary Mixed Oxide: Synthesis, Characterization and Evaluation for Arsenic Removal.

Adsorption of arsenic on bimetallic Mn and Fe mixed oxide was carried out using both field as well as simulated water. The material was synthesized using hydrothermal method and characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Langmuir and Freundlich adsorption isotherms were computed using batch adsorption studies to determine the adsorption capacity of Mn-Fe binary mixed oxide for arsenic. Adsorption capacity for MFBMO obtained from Freundlich model was found to be 2.048 mg/g for simulated water and 1.084 mg/g for field water. Mn-Fe binary mixed oxide was found to be effective adsorbent for removal of arsenic from water.