Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H2O2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

Stabilizing a Platinum1 Single-Atom Catalyst on Supported Phosphomolybdic Acid without Compromising Hydrogenation Activity.

In coordination chemistry, catalytically active metal complexes in a zero- or low-valent state often adopt four-coordinate square-planar or tetrahedral geometry. By applying this principle, we have developed a stable Pt1 single-atom catalyst with a high Pt loading (close to 1 wt %) on phosphomolybdic acid(PMA)-modified active carbon. This was achieved by anchoring Pt on the four-fold hollow sites on PMA. Each Pt atom is stabilized by four oxygen atoms in a distorted square-planar geometry, with Pt slightly protruding from the oxygen planar surface. Pt is positively charged, absorbs hydrogen easily, and exhibits excellent performance in the hydrogenation of nitrobenzene and cyclohexanone. It is likely that the system described here can be extended to a number of stable SACs with superior catalytic activities.

Furan-based acetylating agent for the chemical modification of proteins.

We have synthesized a furan-based acetylating agent, 2,5-bisacetoxymethylfuran (BAMF) from carbohydrate derived 5-hydroxymethylfurfural (HMF) and studied its acetylation activity with amines and cytochrome c. The results show that BAMF can modify proteins in biological conditions without affecting their structure and function. The modification of cytochrome c with BAMF occurred through the reduction of heme center, but there was no change in the coordination property of iron and the tertiary structure of cytochrome c. Further analysis using MALDI-TOF-MS spectrometer suggests that BAMF selectively targeted lysine amino acid of cytochrome c under our experimental conditions. Kinetics study revealed that the modification of cytochrome c with BAMF took place at faster rates than aspirin.

Evaporation of water droplets on Pt-surface in presence of external electric field--A molecular dynamics study.

Evaporation of a sessile droplet on a hot solid substrate is an important problem in fluid mechanics. It is relevant to theoretical issues in heat transfer as well as several practical applications. This study investigates the spreading and evaporation of a nanoscale water droplet on a solid platinum surface. The major objective was to analyze the effect of an external electric field on these phenomena. Varying the intensity and direction of the external electric field, a series of molecular dynamics simulations were carried out to understand these phenomena at a molecular level. The results reveal that a horizontal electric field assists in droplet spreading, whereas a vertical electric field enhances the rate of evaporation for a certain range of field intensities. It also shows that the substrate temperature plays an important role in such processes. It is seen that the effect of an external electric field on droplet evaporation becomes significant at an intermediate range of surface temperatures and this effect is not clearly visible for either very high or very low range of surface temperatures.

Sustainable Biomaterials: Current Trends, Challenges and Applications.

Biomaterials and sustainable resources are two complementary terms supporting the development of new sustainable emerging processes. In this context, many interdisciplinary approaches including biomass waste valorization and proper usage of green technologies, etc., were brought forward to tackle future challenges pertaining to declining fossil resources, energy conservation, and related environmental issues. The implementation of these approaches impels its potential effect on the economy of particular countries and also reduces unnecessary overburden on the environment. This contribution aims to provide an overview of some of the most recent trends, challenges, and applications in the field of biomaterials derived from sustainable resources.

Integration of poly-3-(hydroxybutyrate-co-hydroxyvalerate) production by Haloferax mediterranei through utilization of stillage from rice-based ethanol manufacture in India and its techno-economic analysis.

Haloferax mediterranei has potential for economical industrial-scale production of polyhydroxyalkanoate (PHA) as it can utilize cheap carbon sources, has capacity for nonsterile cultivation and allows simple product recovery. Molasses-based Indian distilleries are converting themselves to cereal-based distilleries. Waste stillage (14 l) of rice-based ethanol industry was used for the production of PHA by H. mediterranei in the simple plug-flow reactor configuration of the activated sludge process. Cells utilized stillage and accumulated 63 ± 3 % PHA of dry cell weight and produced 13.12 ± 0.05 g PHA/l. The product yield coefficient was 0.27 while 0.14 g/l h volumetric productivity was reached. Simultaneous lowering of 5-day biochemical oxygen demand and chemical oxygen demand values of stillage by 82 % was attained. The biopolymer was characterized as poly-3-(hydroxybutyrate-co-17.9 mol%-hydroxyvalerate) (PHBV). Directional properties of decanoic acid jointly with temperature-dependent water solubility in decanoic acid were employed for two-step desalination of the spent stillage medium in a cylindrical baffled-tank with an immersed heater and a stirrer holding axial and radial impellers. 99.3 % of the medium salts were recovered and re-used for PHA production. The cost of PHBV was estimated as US$2.05/kg when the annual production was simulated as 1890 tons. Desalination contributed maximally to the overall cost. Technology and cost-analysis demonstrate that PHA production integrated with ethanol manufacture is feasible in India. This study could be the basis for construction of a pilot plant.

Pyrolytic urban mining of waste printed circuit boards: an enviro-economic analysis.

E-waste, a global environmental concern resulting from supply chain inefficiency, also offers the opportunity to recover valuable materials, including general and rare earth metals. Waste printed circuit boards (WPCBs) are integral components of e-waste that contains substantial amounts of precious metals, making them a valuable waste category. Pyrolysis has emerged as a promising method for material recovery from WPCBs. Hence, pyrolytic urban mining of WPCBs offers an excellent avenue for resource recovery, redirecting valuable materials back into the supply chain. Under the current study, experimental investigation has been conducted to explore the recovery of materials from WPCBs through pyrolysis followed by process simulation, economic analysis, and life cycle assessment (LCA). An Aspen Plus simulation was conducted to model the pyrolysis of WPCBs and subsequent product recovery using a non-equilibrium kinetic model, which represents a unique approach in this study. Another distinct aspect is the comprehensive assessment of environmental and economic sustainability. The economic analysis has been carried out using Aspen economic analyzer whereas the LCA of WPCB pyrolysis has been conducted using the SimaPro software. The experimental investigation reveals yield of solid residues are about 75-84 wt.%, liquid yields of 6-13 wt.%, and gas yields of 4-21 wt.%, which is in well agreement with the Aspen Plus simulation results. The economic analysis for an e-waste pyrolysis plant with an annual feed rate of 2000 t reveals that the total capital cost of a pyrolysis plant is nearly $51.3 million, whereas the total equipment cost is nearly $2.7 million and the total operating cost is nearly $25.6 million. The desired rate of return is 20% per year and the payback period is 6 years with a profitability index of 1.25. From the LCA, the major impact categories are global warming, fossil resource scarcity, ozone formation in human health, ozone formation in terrestrial ecosystems, fine particulate matter formation, and water consumption. The findings of this study can serve as a guideline for e-waste recyclers, researchers, and decision-makers in establishing circular economy.

Designed Precursor for the Controlled Synthesis of Highly Active Atomic and Sub-nanometric Platinum Catalysts on Mesoporous Silica.

The development of new methods to synthesize nanometric metal catalysts has always been an important and prerequisite step in advanced catalysis. Herein, we design a stable nitrogen ligated Pt complex for the straightforward synthesis by carbonization of uniformly sized atomic and sub-nanometric Pt catalysts supported on mesoporous silica. During the carbonization of the Pt precursor into active Pt species, the nitrogen-containing ligand directed the decomposition in a controlled fashion to maintain uniform sizes of the Pt species. The nitrogen ligand had a key role to stabilize the single Pt atoms on a weak anchoring support like silica. The Pt catalysts exhibited remarkable activities in the hydrogenation of common organic functional groups with turnover frequencies higher than in previous studies. By a simple post-synthetic treatment, we could selectively remove the Pt nanoparticles to obtain a mixture of single atoms and nanoclusters, extending the applicability of the present method.

Environmental impact of biomass based polygeneration - A case study through life cycle assessment.

Multi-generation or polygeneration is considered to be a potential sustainable energy solution. To assess environmental sustainability of multi-generation, life cycle assessment (LCA) is a useful tool. In this paper, environmental impact of polygeneration using an agro waste (rice straw) is assessed by LCA. Then it is compared with stand alone conventional plants with same utility outputs. Power, ethanol, heating and cooling are utility outputs of the polygeneration plant. System boundary for this polygeneration is defined for surplus biomass only. Exergy based allocation method is used for this analysis. Results of LCA are shown through both mid-point and end-point indicators. Results indicate that polygeneration with surplus rice straw is more environment-friendly than conventional stand-alone generation of same utilities.

Environmental impact of an agro-waste based polygeneration without and with CO2 storage: Life cycle assessment approach.

Life cycle assessment (LCA) is the most scientific tool to measure environmental sustainability. Poly-generation is a better option than single-utility generation due to its higher resource utilization efficiency and more flexibility. Also biomass based polygeneration with CO2 capture and storage may be useful being 'net negative' greenhouse gas emission option. But this 'negativity' should be studied and confirmed through LCA. In this paper, cradle-to-gate life cycle assessment of a straw based polygeneration without and with CO2 storage is studied. Results show that captured CO2 of this polygeneration should be stored to get a net negative energy system. However, biomass distribution density, ethanol production rate and CO2 transportation distance affect the net GHG emission. For this polygeneration system, exergy based allocation should be preferred.

Rational control of nano-scale metal-catalysts for biomass conversion.

Nano-scale metal particles have huge potential due to their wide range of diverse catalytic applications. Recently, they have found numerous applications in the field of biomass conversion. The proposed contribution is aimed at providing a brief account of remarkable recent findings and advances in the design of metal-based nanocatalysts for biomass valorization. We have discussed the rational control of the size, shape, composition and surface properties of nano-scale metal catalysts. Following that, the interplay between various structural parameters and the catalytic properties in the transformation of cellulose, chitin, lignin and lipids has been critically discussed.

Encapsulated Laccases for the Room-Temperature Oxidation of Aromatics: Towards Synthetic Low-Molecular-Weight Lignins.

A new approach for the encapsulation of laccases with enhanced activity and stability by biomimetic silica mineralisation is reported. A range of lignin model compounds, which includes syringol, syringyl acid, 4-vinylphenol, gallic acid, vanillic acid and guaiacol, was oxidised to lignin-type polymers by the silica-immobilised laccase systems at room temperature. The oxidation rate of the immobilised systems was lower than that of the free enzyme counterparts, but interesting products were observed with the new bio-catalytic materials, which showed reusability and good stability.

Techno-economic evaluation of a polygeneration using agricultural residue--a case study for an Indian district.

Presently, most of world electricity and other energy services are catered by fossil fuel resources. This is unsustainable in the long run both with respect to energy security and climate change problems. Fuel switching, specifically using biomass may partially address this problem. Polygeneration is an efficient way of delivering multiple utility outputs with one or more inputs. Decentralized small or large scale polygeneration using alternative fuels may be a future sustainable solution. In this paper, a techno-economic evaluation of a polygeneration with four utility outputs and rice straw as input has been reported. Results of the simulation and real-life data as inputs are used for the techno-economic analysis. The analysis is specific for a district in the state of West Bengal of India. Results show that such a plant has strong potential to qualify in techno-economic performance in addition to higher efficiency and lower CO2 emission.

Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed.

Mechanochemical synthesis of advanced nanomaterials for catalytic applications.

Mechanochemical synthesis emerged as the most advantageous, environmentally sound alternative to traditional routes for nanomaterials preparation with outstanding properties for advanced applications. Featuring simplicity, high reproducibility, mild/short reaction conditions and often solvent-free condition (dry milling), mechanochemistry can offer remarkable possibilities in the development of advanced catalytically active materials. The proposed contribution has been aimed to provide a brief account of remarkable recent findings and advances in the mechanochemical synthesis of solid phase advanced catalysts as opposed to conventional systems. The role of mechanical energy in the synthesis of solid catalysts and their application is critically discussed as well as the influence of the synthesis procedure on the physicochemical properties and the efficiency of synthesized catalysts is studied. The main purpose of this feature article is to highlight the possibilities of mechanochemical protocols in (nano)materials engineering for catalytic applications.

Gasification of biomass in a fixed bed downdraft gasifier--a realistic model including tar.

This study presents a model for fixed bed downdraft biomass gasifiers considering tar also as one of the gasification products. A representative tar composition along with its mole fractions, as available in the literature was used as an input parameter within the model. The study used an equilibrium approach for the applicable gasification reactions and also considered possible deviations from equilibrium to further upgrade the equilibrium model to validate a range of reported experimental results. Heat balance was applied to predict the gasification temperature and the predicted values were compared with reported results in literature. A comparative study was made with some reference models available in the literature and also with experimental results reported in the literature. Finally a predicted variation of performance of the gasifier by this validated model for different air-fuel ratio and moisture content was also discussed.

One-pot conversions of lignocellulosic and algal biomass into liquid fuels.

The one-pot conversion of lignocellulosic and algal biomass into a liquid fuel, 2,5-dimethylfuran (DMF), has been achieved by using a multicomponent catalytic system comprising [DMA]⁺ [CH3SO3]⁻ (DMA=N,N-dimethylacetamide), Ru/C, and formic acid. The synthesis of DMF from all substrates was carried out under mild reaction conditions. The reaction progressed via 5-hydroxyemthylfurfural (HMF) in the first step followed by hydrogenation and hydrogenolysis of HMF with the Ru/C catalyst and formic acid as a hydrogen source. This report discloses the effectiveness of the Ru/C catalyst for the first time for DMF synthesis from inexpensive and readily abundant biomass sources, which gives a maximum yield of 32 % DMF in 1 h. A reaction route involving 5-(formyloxymethyl)furfural (FMF) as an intermediate has been elucidated based on the ¹H and ¹³C NMR spectroscopic data. Another promising biofuel, 5-ethoxymethylfurfural (EMF), was also synthesized with high selectivity from polymeric carbohydrate-rich biomass substrates by using a Brønsted acidic ionic liquid catalyst, that is [DMA]⁺ [CH3SO3]⁻, by etherification of HMF in ethanol.

Self-assembled TiO2 nanospheres by using a biopolymer as a template and its optoelectronic application.

Self-assembled TiO(2) nanoparticulate materials with well-defined spherical morphologies were synthesized by using a biopolymer sodium alginate as a template under different synthesis conditions. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) techniques were used to characterize the TiO(2) nanoparticles. N(2) sorption analysis revealed the moderately good surface area (124.0 m(2) g(-1)) and pore volume (0.44 cm(3) g(-1)) of these TiO(2) nanoparticles. The biopolymer templating pathway leads to good-quality self-assembled TiO(2) nanoparticles with dimensions of ca. 10-12 nm within the synthesis temperature range of 0-60 °C. These porous TiO(2) nanomaterials showed high photogenerated current in the presence of a dye (Rose Bengal), used as a sensitizer for several photo on/off cycles.