Carbon-based and carbon-supported nanomaterials for the catalytic conversion of biomass: a review

Catalytic conversion of biomass and waste into chemicals and fuels is gaining interest to reach a circular economy. Here, we review carbon-based and carbon-supported nanocatalysts for biomass conversion with focus on catalyst types and synthesis, optimization, mechanisms and three-dimension catalytic structures. Catalystic materials include amorphous carbon, graphene, graphene oxide, carbon nanotubes and carbon nanofibers.

     

Nanomaterials for biofuel production using lignocellulosic waste

Production of biofuels using second-generation, non-food, lignocellulosic waste biomass is a sustainable approach that solve the economic issues of fossil fuels and environmental pollution. The major issues of biofuel production are biomass complexity, pretreatment, enzyme denaturation and cost. This article reviews the application of nanomaterials for biofuel production from various lignocellulosic wastes.     

High reduction of 4-nitrophenol using reduced graphene oxide/Ag synthesized with tyrosine

There is a demand for the development of environmental friendly methods for the synthesis of graphene composites. Reduced graphene oxide/silver (RGO/Ag) nanocomposites are very good catalysts. Here, we propose a simple, green method for the synthesis of RGO/Ag nanocomposite using the amino acid tyrosine as bioreductant and stabilizing agent. RGO/Ag nanocomposite was characterized by using various analytical techniques and studied for its catalytic degradation of 4-nitrophenol. Results of attenuated total reflectance Fourier transform infrared spectroscopy and Zeta potential at ?55 mV reveal the surface capping of tyrosine onto the reduced graphene oxide nanosheets. RGO/Ag nanocomposites show excellent catalytic reduction of 4-nitrophenol with NaBH₄, when compared to actual individual silver nanoparticles.     

Recent advances in antimony removal using carbon-based nanomaterials: A review

• The synthesis and physicochemical properties of various CNMs are reviewed. • Sb removal using carbon-based nano-adsorbents and membranes are summarized. • Details on adsorption behavior and mechanisms of Sb uptake by CNMs are discussed. • Challenges and future prospects for rational design of advanced CNMs are provided. Recently, special attention has been deserved to environmental risks of antimony (Sb) element that is of highly physiologic toxicity to human. Conventional coagulation and ion exchange methods for Sb removal are faced with challenges of low efficiency, high cost and secondary pollution. Adsorption based on carbon nanomaterials (CNMs; e.g., carbon nanotubes, graphene, graphene oxide, reduced graphene oxide and their derivatives) may provide effective alternative because the CNMs have high surface area, rich surface chemistry and high stability. In particular, good conductivity makes it possible to create linkage between adsorption and electrochemistry, thereby the synergistic interaction will be expected for enhanced Sb removal. This review article summarizes the state of art on Sb removal using CNMs with the form of nano-adsorbents and/or filtration membranes. In details, procedures of synthesis and functionalization of different forms of CNMs were reviewed. Next, adsorption behavior and the underlying mechanisms toward Sb removal using various CNMs were presented as resulting from a retrospective analysis of literatures. Last, we prospect the needs for mass production and regeneration of CNMs adsorbents using more affordable precursors and objective assessment of environmental impacts in future studies.     

磺化石墨烯对小麦幼苗生长及生理生化指标的影响

随着石墨烯生产量和使用量的不断增大,其对生态环境的风险逐渐引起了环境学家的关注。采用水培试验,探究了磺化石墨烯(SGO)对小麦幼苗的生长、抗氧化酶活性及脂质过氧化的影响。结果表明:在培养10 d后,低浓度磺化石墨烯对小麦根系的生长有显著促进作用(P0.05),200 mg·L-1浓度处理与对照处理相比提高了84.3%,随着浓度增加促进作用逐渐减弱,1 000 mg·L-1时与对照相比提高了19.9%。但对小麦地上部的生长没有影响。磺化石墨烯处理的小麦幼苗根系和叶片组织中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、过氧化物酶(POD)及丙二醛(MDA)都呈现先下降后上升的趋势。当磺化石墨烯浓度低于200 mg·L-1时,处理组小麦抗氧化酶的活性及MDA含量相对于对照处理大都有所降低,说明低浓度时磺化石墨烯没有对小麦的生长产生氧化胁迫,这与磺化石墨烯可能具有一定的抗氧化能力有关,而高浓度时由于产生氧化胁迫使各项生理生化指标逐渐上升。本实验结果为石墨烯材料对植物的毒理学研究提供了基础数据。     

Three-phase partitioning for the separation of proteins,enzymes, biopolymers,oils and pigments: a review

Environmental Chemistry Letters - Modern biomass and organic waste are becoming major, carbon-neutral sources of fine chemicals, biomolecules and fuels to replace fossil fuel products. As a...     

Nanomaterials for water pollution monitoring and remediation

Water shortage and pollution are serious challenges for many countries. Nanomaterials are promising new tools for water quality management due to unique physicochemical properties, high economic benefit, high removal efficiency and environmental friendliness. Here we describe four types of nanomaterials used for water treatment: nanofiltration membranes, photocatalytic nanomaterials, adsorption nanomaterials and reducing nanomaterials. We discuss their properties, applications and mechanisms for pollutant removal. We also review nanomaterials used for water quality monitoring, notably nanomaterials used for the detection of trace pollutants and pathogens. These nanomaterials include carbon nanotubes, magnetic nanoparticles, noble metal nanomaterials and quantum dots.     

A homogeneous and low-cost biosorbent for Cd,Pb and Cu removal from aqueous effluents

Heavy metal pollution of aqueous effluents is a matter of widespread concern. The use of low-cost materials for the adsorption of heavy metals seems to be a suitable choice for waste water treatment. Polyporus tenuiculus, easily cultivated on lignocellulosic waste, was assayed for Cu, Pb and Cd removal from aqueous solutions. Pb was removed more efficiently. Kinetics studies suggested a pseudo-second-order reaction and equilibrium was reached in ～ 30 min in all cases. The metal-sorption data were analysed according to several two-parameter isotherms. Data better fitted the Langmuir model for the three metals. A great dependence of metal adsorption with pH was observed. Characterisation of both the biomass and the complex metal-biomass was performed by FT-IR and SEM-EDX. Results suggest an ion exchange mechanism.     

Sulfamethoxazole removal from polluted water by immobilized photocatalysis

The photocatalytic activity of TiO₂ deposits (Degussa P25 and Millennium PC500) has been studied using sulfamethoxazole (SMX) as a model water pollutant and a UV fluorescent lamp as a light source (365 nm). Both catalysts have shown very similar properties in the photocatalytic degradation of SMX. Special attention has been given to the effect of the irradiation time, pH, and pollutant concentration. No mass-transfer limitations are observed. The degradation of SMX is accelerated at low concentration, and the photocatalytic degradation kinetics obey the Langmuir–Hinshelwood model, allowing the adsorption and apparent rate constants to be determined for both catalysts.     

Effects of nano carbon black and single-layer graphene oxide on settlement,survival and swimming behaviour of Amphibalanus amphitrite larvae

The effects of two carbon-based nanomaterials, nano-sized carbon black (nCB), and single-layer graphene oxide (GO) on settlement of Amphibalanus amphitrite (Cirripedia, Crustacea) cypris larvae (cyprids) were assessed after 24, 48, and 72 h of exposure. Additionally, the effects of these nanomaterials on the mortality and swimming behaviour of the nauplius larvae (nauplii) of the same organism were determined after 24 and 48 h. The data indicate that nCB is more effective as a potential antisettlement agent than single-layer GO; moreover, nCB did not show any adverse effects on the larvae. The swimming behaviour of II stage nauplii of A. amphitrite exposed to a suspension of nCB was inhibited only at very high nCB concentrations (≥0.5 mg/mL). Single-layer GO, on the contrary, showed lower antisettlement effects and was more active in altering the survival and inhibiting the swimming behaviour of the nauplii. An indication of the toxic or non-toxic mechanisms of the antisettlement properties of both of these nanomaterials is provided by the reversibility of the antisettlement activity. In conclusion, we propose nCB as an innovative antifouling nanomaterial that shows low toxicity towards the model organism (crustaceans) used in this study.     

Methods to convert lignocellulosic waste into biohydrogen,biogas, bioethanol,biodiesel and value-added chemicals: a review

Environmental Chemistry Letters - In the context of climate change and the circular economy, there is an urgent need to develop biofuels and value-added chemicals from lignocellulosic waste such as...     

Nanomaterials for environmental burden reduction, waste treatment, and nonpoint source pollution control: a review

Nanomaterials are applicable in the areas of reduction of environmental burden, reduction/treatment of industrial and agricultural wastes, and nonpoint source (NPS) pollution control. First, environmental burden reduction involves green process and engineering, emissions control, desulfurization/denitrification of nonrenewable energy sources, and improvement of agriculture and food systems. Second, reduction/treatment of industrial and agricultural wastes involves converting wastes into products, groundwater remediation, adsorption, delaying photocatalysis, and nanomembranes. Third, NPS pollution control involves controlling water pollution. Nanomaterials alter physical properties on a nanoscale due to their high specific surface area to volume ratio. They are used as catalysts, adsorbents, membranes, and additives to increase activity and capability due to their high specific surface areas and nano-sized effects. Thus, nanomaterials are more effective at treating environmental wastes because they reduce the amount of material needed.     

Chemical,physical and biological methods to convert lignocellulosic waste into value-added products. A review

Environmental Chemistry Letters - Actual agricultural practices produce about 998 million tonnes of agricultural waste per year. Therefore, converting lignocellulosic wastes into energy, chemicals,...     

Applications of nanomaterials in water treatment and environmental remediation

Nanotechnology has revolutionized plethora of scientific and technological fields; environmental safety is no exception. One of the most promising and well- developed environmental applications of nanotechnology has been in water remediation and treatment where different nanomaterials can help purify water through different mechanisms including adsorption of heavy metals and other pollutants, removal and inactivation of patho- gens and transformation of toxic materials into less toxic compounds. For this purpose, nanomaterials have been produced in different shapes, integrated into various composites and functionalized with active components. Nanomaterials have also been incorporated in nanostructured catalytic membranes which can in turn help enhance water treatment. In this article, we have provided a succinct review of the most common and popular nanomaterials （titania, carbon nanotubes （CNTs）, zero-valent iron, dendrimers and silver nanomaterials） which are currently used in environmental remediation and particularly in water purification. The catalytic properties and functionalities of the mentioned materials have also been discussed.     

金属及其氧化物催化降解多氯联苯的研究进展

催化降解因其高的反应速率和降解彻底性,在氯代有机物的削减中得到广泛应用.目前研究较多的催化剂为零价态和氧化态的碱金属和碱土金属、过渡金属及贵金属,包括单金属和双金属两种.这类催化剂表面活性位点多样,在氯代有机物的降解中显示出优异的活性.多氯联苯(Polychlorinated Biphenyls,简称PCBs)是一类有毒难降解的持久性有机污染物.本文阐述了不同价态的单金属和双金属催化剂催化降解PCBs的反应机理,并介绍了影响反应速率和产物选择性的因素.并对金属及其氧化物催化降解PCBs的应用现状做了评述,对该技术的发展进行展望.     

Ammonia adsorption on graphene and graphene oxide: a first-principles study

Motivated by the recent realization of graphene sensor to detect gas molecules that are harmful to the environment, the ammonia adsorption on graphene or graphene oxide (GO) was investigated using first-principles calculation. The optimal adsorption and orientation of the NH₃ molecules on the graphene surfaces were determined, and the adsorption energies (E _b) as well as the Mulliken charge transfers of NH₃ were calculated. The E _b for the graphene are small and seem to be independent of the sites and orientations. The surface epoxy or hydroxyl groups can promote the adsorption of NH₃ on the GO; the enhancement of the E _b for the hydroxyl groups is greater than that for the epoxy groups on the surface. The charge transfers from the molecule to the surfaces also exhibit the same trend. The Brönsted acid sites and Lewis acid sites could stably exist on the GO with surface hydroxyl groups and on the basal, respectively.     

Interaction of carbonaceous nanomaterials with wastewater biomass

Increasing production and use of carbonaceous nanomaterials (NMs) will increase their release to the sewer system and to municipal wastewater treatment plants. There is little quantitative knowledge on the removal of multi-walled carbon nanotubes (MWCNTs), graphene oxide (GO), or few-layer graphene (FLG) from wastewater into the wastewater biomass. As such, we investigated the quantification of GO and MWCNTs by UV-Vis spectrophotometry, and FLG using programmable thermal analysis (PTA), respectively. We further explored the removal of pristine and oxidized MWCNTs (O-MWCNTs), GO, and FLG in a biomass suspension. At least 96% of pristine and O-MWCNTs were removed from the water phase through aggregation and 30-min settling in presence or absence of biomass with an initial MWCNT concentration of 25 mg·L⁻¹. Only 65% of GO was removed with biomass concentration at or above 1,000 mg·L⁻¹ as total suspended solids (TSS) with the initial GO concentration of 25 mg·L⁻¹. As UV-Vis spectrophotometry does not work well on quantification of FLG, we studied the removal of FLG at a lower biomass concentration (50 mg TSS·L⁻¹) using PTA, which showed a 16% removal of FLG with an initial concentration of 1 mg·L⁻¹. The removal data for GO and FLG were fitted using the Freundlich equation (R² = 0.55, 0.94, respectively). The data presented in this study for carbonaceous NM removal from wastewater provides quantitative information for environmental exposure modeling and life cycle assessment.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

Catalytic decomposition of hypochlorite ion in petrochemical plant waste water

During the incineration of the chlorinated hydrocarbons originating as the side products in vinyl chloride plant, hypochlorite ion appears as a pollutant in plant waste water. To remove it to the permitted level of 2 mg/l the process of the catalytic oxidation by cobalt (II, III) oxide, followed by sodium sulphite treatment has been chosen. It was shown that the above choice gives satisfactory results. The influence of some parameters such as retention time, effluent pH and temperature versus removal efficiency have been determined.     

Synthesis, physicochemical characterizations and catalytic performance of Pd/carbon-zeolite and Pd/carbon-CeO2 nanocatalysts used for total oxidation of xylene at low temperatures

In this work, xylene removal from waste gas streams was investigated via catalytic oxidation over Pd/carbon-zeolite and Pd/carbon-CeO₂ nanocatalysts. Activated carbon was obtained from pine cone chemically activated using ZnCl₂ and modified by H₃PO₄. Natural zeolite of clinoptilolite was modified by acid treatment with HCl, while nano-ceria was synthesized via redox method. Mixed supports of carbon-zeolite and carbonceria were prepared and palladium was dispersed over them via impregnation method. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller surface area (BET), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) techniques. Characterization of nanocatalysts revealed a good morphology with an average particle size in a nano range, and confirmed the formation of nano-ceria with an average crystallite size below 60 nm. BET analysis indicated a considerable surface area for catalysts (～1000 m²·g^?1). FTIR patterns demonstrated that the surface groups of synthesized catalysts are in good agreement with the patterns of materials applied in catalyst synthesis. The performance of catalysts was assessed in a low-pressure catalytic oxidation pilot in the temperature range of 100° C-250°C. According to the reaction data, the synthesized catalysts have been shown to be so advantageous in the removal of volatile organic compounds (VOCs), representing high catalytic performance of 98% for the abatement of xylene at 250°C. Furthermore, a reaction network is proposed for catalytic oxidation of xylene over nanocatalysts.