Unveiling the potential of cellulose, chitosan and polylactic acid as precursors for the production of green carbon nanofibers with controlled morphology and diameter.

Carbon nanofibers (CNFs) are very promising materials with application in many fields, such as sensors, filtration systems, and energy storage devices. This study aims to explore the use of eco-friendly biopolymers for CNF production, finding novel, suitable and sustainable precursors and thus prioritising environmentally conscious processes and ecological compatibility. Polymeric nanofibers (PNFs) using cellulose acetate, polylactic acid, and chitosan as precursors were successfully prepared via electrospinning. Rheological testing was performed to determine suitable solution concentrations for the production of PNFs with controlled diameter and appropriate morphology. Their dimensions and structure were found to be significantly influenced by the solution concentration and electrospinning flow rate. Subsequently, the electrospun green nanofibers were subject to stabilisation and carbonisation to convert them into CNFs. Thermal behaviour and chemical/structural changes of the nanofibers during stabilisation were investigated by means of thermogravimetric analysis and Fourier-transform infrared spectroscopy, while the final morphology of the fibers after stabilisation and carbonisation was examined through scanning electron microscopy to determine the optimal stabilisation parameters. The optimal fabrication parameters for cellulose and chitosan-based CNFs with excellent morphology and thermal stability were successfully established, providing valuable insight and methods for the sustainable and environmentally friendly synthesis of these promising materials.

Taguchi optimisation of the synthesis of vine-pruning-waste hydrochar as potential adsorbent for pesticides in water.

This research aimed to synthesise an effective hydrochar adsorbent from vineyard pruning wastes to remove emerging contaminants as a potential valorisation product. The adsorption capacity of the hydrochar was optimised using the Taguchi method. Four synthesis variables were evaluated: hydrothermal reaction temperature, use of H3PO4 as a catalyst, number of acetone washes, and type of chemical cold activation. The simultaneous adsorption of five model pesticides (clothianidin (CTD), acetamiprid (ACE), 2,4-D, metalaxyl (MET), and atrazine (ATZ)) at an initial pH of 7 was studied. At optimum conditions, the hydrochar presented a total adsorption capacity of 22.7 µmol/g, representing a 2.7-fold improvement with respect to pristine hydrochar performance. High percentage removals were achieved for all pollutants (85 % CTD, 94 % ACE, 86 % MET, and 95 % ATZ) except for 2,4-D (4 %). This research provides a valuable reference for developing hydrochar adsorbents for pollution control and the valorisation of biomass wastes.

Influencing factors and mechanism of CO2 adsorption capacity of FA-based carbon sequestration materials.

Carbon dioxide mineral carbonisation is a means to achieve permanent carbon dioxide storage, this paper to solid waste materials as the main raw material to prepare fly ash-based carbon dioxide storage materials. Through the design of carbon dioxide adsorption experimental setup to study the main factors affecting the adsorption capacity of the fly ash-based storage materials, the experimental results show that, the fly ash mass fraction decreased from 90 to 10%, the water-cement ratio increased from 0.4 to 0.8 when the CO2 adsorption of fly ash-based materials increased by 82% and 30%, respectively. The effect of strong alkali on CO2 adsorption capacity was also investigated in this paper, and the results showed that the CO2 adsorption of the fly ash-based material sample with 10 ml NaOH added increased by 197% compared with that of the sample with 5 ml NaOH added, whereas the adsorption amount was reduced by 85% when 25 ml NaOH was added instead, which was attributed to the accelerated hydration process of the material due to the excessive alkalinity that consumed the calcium and magnesium ions in the material, and at the same time the production of hydration products hindered the transport of CO2 within the material, which led to a decrease in CO2 adsorption.

Improving green hydrogen production from Chlorella vulgaris via formic acid-mediated hydrothermal carbonisation and neural network modelling.

This study investigates the formic acid-mediated hydrothermal carbonisation (HTC) of microalgae biomass to enhance green hydrogen production. The effects of combined severity factor (CSF) and feedstock-to-suspension ratio (FSR) are examined on HTC gas formation, hydrochar yield and quality, and composition of the liquid phase. The hydrothermal conversion of Chlorella vulgaris was investigated in a CSF and FSR range of -2.529 and 2.943; and 5.0 wt.% - 25.0 wt.%. Artificial neural networks (ANNs) were developed based on experimental data to model and analyse the HTC process. The results show that green hydrogen formation can be increased up to 3.04 mol kg-1 by applying CSF 2.433 and 12.5 wt.% FSR reaction conditions. The developed ANN model (BR-2-11-9-11) describes the hydrothermal process with high testing and training performance (MSEz = 1.71E-06 & 1.40E-06) and accuracy (R2 = 0.9974 & R2 = 0.9781). The enhanced H2 yield indicates an effective alternative green hydrogen production scenario at low temperatures using high-moisture-containing biomass feedstocks.

Calcium-pyro-hydrochar derived from the spent mushroom substrate as a functional sorbent of Pb2+ and Cd2+ from aqueous solutions.

A calcium-pyro-hydrochar (Ca-PHC) can be distinguished as a novel sorbent of Pb2+ and Cd2+ from an aqueous solution. It was obtained using hydrothermal treatment of the spent mushroom substrate (SMS), followed by a CaCl2·5H2O activation and pyrolysis. The characterisation of chars before and after modifications was done by scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and Fourier transform infrared (FTIR). Batch experiments were performed to examine Ca-PHC's sorption properties and binding mechanisms to selected metal ions. The maximum sorption capacities of Ca-PHC for Pb2+ and Cd2+ were 297 mg g-1, and 131 mg g-1, respectively. The obtained results demonstrated that the sorption of Pb2+ and Cd2+ by Ca-PHC follows a pseudo-second kinetic model and Freundlich isotherm. The binding of the selected metals onto Ca-PHC was enabled by the ion-exchange mechanism, surface complexation, mineral precipitation and cation-π interaction. Thermodynamic parameters indicate that metal ions binding by Ca-PHC are spontaneous and endothermic. Due to the high adsorption capacities, the obtained Ca-PHC has good potential for application in industrial wastewater treatment. In addition, the demonstrated use of SMS highlights another possibility of applying this specific biomass relevant to sustainable and economical waste management in the growing mushroom industry.

Revisiting the Effect of Pyrolysis Temperature and Type of Activation on the Performance of Carbon Electrodes in an Electrochemical Capacitor.

Hierarchical porous carbons are known to enhance the electrochemical features of electrodes in electrochemical capacitors. However, the contribution of surface oxygen and the resulting functionalities and wettability, along with the role of electrical conductivity and degree of amorphous or crystalline nature in the micro-mesoporous carbons, are not yet clear. This article considers the effect of carbonisation temperature (500-900 °C) and the type of activation (CO2, KOH) on the properties mentioned above in case of carbon xerogels (CXs) to understand the resulting electrochemical performances. Depending on the carbonisation temperature, CX materials differ in micropore surface area (722-1078 m2 g-1) while retaining a mesopore surface area ~300 m2 g-1, oxygen content (3-15%, surface oxygen 0-7%), surface functionalities, electrical conductivity (7 × 10-6-8 S m-1), and degree of amorphous or crystalline nature. Based on the results, electrochemical performances depend primarily on electrical conductivity, followed by surface oxygen content and meso-micropore connectivity. The way of activation using a varied extent of CO2 exposure and KOH concentrations played differently in CX in terms of pore connectivity from meso- to micropores and their contributions and degree of oxidation, and resulted in different electrochemical behaviours. Such performances of activated CXs depend solely on micro-mesopore features.

Carbon material produced by hydrothermal carbonisation of food waste as an electrode material for supercapacitor application: A circular economy approach.

This study aims to use landfill leachate (LL) as an aqueous medium during hydrothermal carbonisation (HTC) of food waste to produce hydrochar (FWH-LL-C), which could be used as an electrode material in energy storage devices. The structural properties and electrochemical performance of the hydrochar were compared to that obtained using distilled water as a reaction medium (FWH-DW-C). The results showed that there is a difference in Brunauer-Emmett-Teller (BET) surface area of FWH-LL-C (220 m2 gm-1) and FWH-DW-C (319 m2 gm-1). The electrochemical properties were comparable, with FWH-LL-C having 227 F g-1 specific capacitance at 1 A g-1 current density and FWH-DW-C having 235 F g-1 specific capacitance at 1 A g-1 current density. Furthermore, at a power density of 634 W kg-1, FWH-DW-C achieved the highest energy density of 14.4 Wh kg-1. The energy retention capacity of the electrode was 98% which indicate that the material has an excellent energy storage capacity. The findings suggested that LL could be used as an alternative source of aqueous media during the HTC of food waste to produce hydrochar which could be used as an effective electrode material in supercapacitors.

Energy recovery from garden and park waste by hydrothermal carbonisation and anaerobic digestion.

Hydrothermal carbonisation (HTC) can transform wet lignocellulosic biomass, which is not considered an effective biofuel for energy production at the industrial level, into a carbonaceous product called hydrochar (HC) that is suitable for combustion and a process water (PW). PW is an interesting by-product that can be valorised for biogas production via anaerobic digestion (AD). This study presents a new approach for the valorisation of garden and park wastes (GPW) by integrating HTC to generate HC for energy production, while PW is subjected to AD for biogas production. The hydrothermal treatment was performed at 180, 210, and 230 °C, yielding HC with improved physicochemical properties, such as an elevated higher heating value (21-25 MJ kg-1); low ash (<5 wt.%), nitrogen (1.3 wt.%), and sulphur (0.2 wt.%) contents; better fuel ratio (0.4-0.6); and a broad comprehensive combustibility index (8.0×10-7 to 9.6×10-7 min-2 °C-3). AD of the generated PW was conducted under mesophilic conditions (35 °C), resulting in a methane production in the range of 253-326 mL g-1 CODadded and COD removal of up to 65%. The combination of HTC and AD allowed the recovery of 91% and 94% of the energy content feedstock, as calculated from the combustion of HC and methane, respectively.

Anaerobic digestion of untreated and treated process water from the hydrothermal carbonisation of spent coffee grounds.

This study investigates the long-term performance of the mesophilic (35 °C) anaerobic mono-digestion of process waters (PW) from the hydrothermal carbonisation (HTC) of spent coffee grounds. At an organic loading rate (OLR) of 0.4 gCOD L-1 d-1, initial instability was seen, but after 40 days and supplementary alkalinity, the digestion stabilised with the chemical oxygen demand (COD) in the untreated PW degraded with 37.8-64.6% efficiency and the yield of methane at 0.16 L gCOD-1. An increase in OLR to 0.8 gCOD L-1 d-1 caused a collapse in biogas production, and resulted in severe instability in the reactor, characterised by falling pH and an increasing volatile fatty acid concentration. Comparatively, the digestion of a treated PW (concentrated in nanofiltration and reverse osmosis after removal of the fouling fraction), at OLR between 0.4 and 0.8 gCOD L-1 d-1, was stable over the entire 117 days of treated PW addition, yielded methane at 0.21 L gCOD-1 and the COD was degraded with an average efficiency of 93.5% - the highest efficiency the authors have seen for HTC PW. Further anaerobic digestion of untreated PW at an average OLR of 0.95 gCOD L-1 d-1 was stable for 38 days, with an average COD degradation of 69.6%, and methane production between 0.15 and 0.19 L gCOD-1. The digestion of treated PW produced significantly higher COD degradation and methane yield than untreated PW, which is likely to be related to the removal of refractory and inhibitory organic material in the post-HTC treatment by adsorption of hydrophobic material.

Sustainable Hydrothermal and Solvothermal Synthesis of Advanced Carbon Materials in Multidimensional Applications: A Review.

The adoption of green technology is very important to protect the environment and thus there is a need for improving the existing methods for the fabrication of carbon materials. As such, this work proposes to discuss, interrogate, and propose viable hydrothermal, solvothermal, and other advanced carbon materials synthesis methods. The synthesis approaches for advanced carbon materials to be interrogated will include the synthesis of carbon dots, carbon nanotubes, nitrogen/titania-doped carbons, graphene quantum dots, and their nanocomposites with solid/polymeric/metal oxide supports. This will be performed with a particular focus on microwave-assisted solvothermal and hydrothermal synthesis due to their favourable properties such as rapidity, low cost, and being green/environmentally friendly. These methods are regarded as important for the current and future synthesis and modification of advanced carbon materials for application in energy, gas separation, sensing, and water treatment. Simultaneously, the work will take cognisance of methods reducing the fabrication costs and environmental impact while enhancing the properties as a direct result of the synthesis methods. As a direct result, the expectation is to impart a significant contribution to the scientific body of work regarding the improvement of the said fabrication methods.

Sustainable management and recycling of food waste anaerobic digestate: A review.

Anaerobic digestion (AD) is a widely used technology to valorise food waste for biogas production yet a considerable amount of digestate remains under-utilised. Sustainable management and recycling of the nutrient-rich food waste anaerobic digestate (FWD) is highly desirable for closing resource loop and actualising circular economy. This work reviews the distinct properties of FWD and the existing treatment technologies. FWD shows great prospects as a nutrient source for microalgal cultivation and biofuel production. Emerging technologies such as thermal conversion (e.g., pyrolysis and hydrothermal treatment) of FWD into value-added products such as functionalised biochar/hydrochar with diverse applications would be attractive and warrant further research investigation. Integrated AD with subsequent valorisation facilities is highly encouraged to achieve complete utilisation of resources and reduce carbon emissions.

Effect of thermal treatments on chiral nematic cellulose nanocrystal films.

The ability to manipulate the optical appearance of materials is essential in virtually all products and areas of technology. Structurally coloured chiral nematic cellulose nanocrystal (CNC) films proved to be an excellent platform to design optical appearance, as their response can be moulded by organising them in hierarchical architectures. Here, we study how thermal treatments influence the optical appearance of structurally coloured CNC films. We demonstrate that the CNCs helicoidal architecture and the chiral optical response can be maintained up to 250 °C after base treatment and cross-linking with glutaraldehyde, while, alternatively, an exposure to vacuum allows for the helicoidal arrangement to be further preserved up to 900 °C, thus producing aromatic chiral carbon. The ability to retain the helicoidal arrangement, and thus the visual appearance, in CNC films up to 250 °C is highly desirable for high temperature colour-based industrial applications and for passive colorimetric heat sensors. Similarly, the production of chiral carbon provides a new type of conductive carbon for electrochemical applications.

Hydrothermal carbonisation of mechanically dewatered digested sewage sludge-Energy and nutrient recovery in centralised biogas plant.

This study aimed to assess the role of hydrothermal carbonisation (HTC) in digestate processing in centralised biogas plants receiving dewatered sludge from regional wastewater treatment plants and producing biomethane and fertilisers. Chemically conditioned and mechanically dewatered sludge was used as such (total solids (TS) 25%) or as diluted (15% TS) with reject water in 30 min or 120 min HTC treatments at 210 °C, 230 °C or 250 °C, and the produced slurry was filtered to produce hydrochars and filtrates. The different hydrochars contributed to 20-55% of the original mass, 72-88% of the TS, 74-87% of the energy content, 71-92% of the carbon, above 86% of phosphorous and 38-64% of the nitrogen present in the original digestates. The hydrochars' energy content (higher heating values were 11.3-12.2 MJ/kg-TS) were similar to that of the digestates, while the ash contents increased (from 43% up to 57%). HTC treatments produced filtrates in volumes of 42-76% of the dewatered digestate, having a soluble chemical oxygen demand (SCOD) of 28-44 g/L, of which volatile fatty acids (VFAs) contributed 10-34%, and methane potentials of 182-206 mL-CH4/g-SCOD without any major indication of inhibition. All 32 pharmaceuticals detected in the digestates were below the detection limit in hydrochars and filtrates, save for ibuprofen and benzotriazole in filtrate, while heavy metals were concentrated in the hydrochars but below the national limits for fertiliser use, save for mercury. The integration of HTC to a centralised biogas plant was extrapolated to enhance the annual biogas production by 5% and ammonium recovery by 25%, and the hydrochar was estimated to produce 83 GJ upon combustion or to direct 350 t phosphorous to agriculture annually.

Valorisation of macroalgae via the integration of hydrothermal carbonisation and anaerobic digestion.

This study investigates the integration of hydrothermal carbonisation (HTC) with anaerobic digestion (AD) as a valorisation route for two macroalgae species; S. latissima (SL) and F. serratus (FS). HTC reactions were conducted at temperatures of 150 °C, 200 °C and 250 °C, with resulting hydrochars, process waters and hydrothermal slurries assessed for biomethane potential yields. Un-treated SL generated similar biomethane levels compared to all SL slurries. Whereas all FS slurries improved biomethane yields compared to un-treated FS. Hydrochars represent a greater energy carrier if used as a solid fuel, rather than a feedstock for anaerobic digestion. Integrating HTC and AD, through hydrochar combustion and process water digestion has a greater energetic output than anaerobic digestion of the un-treated macroalgae. Treatment at 150 °C, with separate utilisation of products, can improve the energetic output of S. latissima and F. serratus by 47% and 172% respectively, compared to digestion of the un-treated macroalgae.

Highly Chlorinated Polyvinyl Chloride as a Novel Precursor for Fibrous Carbon Material.

Pure, highly chlorinated polyvinyl chloride (CPVC), with a 63 wt % of chlorine, showed a unique-thermal-pyrolytic-phenomenon that meant it could be converted to carbon material through solid-phase carbonisation rather than liquid-phase carbonisation. The CPVC began to decompose at 270 °C, with a rapid loss in mass due to dehydrochlorination and novel aromatisation and polycondensation up to 400 °C. In this study, we attempted to prepare carbon fibre (CF) without oxidative stabilisation, using the aforementioned CPVC as a novel precursor. Through the processes of solution spinning and solid-state carbonisation, the spun CPVC fibre was directly converted to CF, with a carbonisation yield of 26.2 wt %. The CPVC-derived CF exhibited a relatively smooth surface; however, it still demonstrated a low mechanical performance. This was because the spun fibre was not stretched during the heat treatment. Tensile strength, Young's modulus and elongation values of 590 ± 84 MPa, 50 ± 8 GPa, and 1.2 ± 0.2%, respectively, were obtained from the CPVC spun fibre, with an average diameter of 19.4 µm, following carbonisation at 1600 °C for 5 min.

Comparative environmental assessment of end-of-life carbonaceous water treatment adsorbents.

This study evaluates and compares the environmental impacts arising from the disposal of different carbonaceous sorbents used for wastewater treatment. Three different adsorption materials were considered, i.e. activated carbon, biochar and hydrochar, and three end-of-life management approaches, i.e. incineration, regeneration and landfilling. The highest overall environmental impact was of Carcinogenic effects and Freshwater Ecotoxicity due to emissions of heavy metals during production of all types of sorbents. The use of materials with higher adsorption capacities and regeneration of carbonaceous materials were considered and shown to be an efficient way for reducing the overall environmental impacts of the different adsorbents. The compensation of fossil fuel incineration by using recovered heat led to negative impacts in all categories. Recirculation of HTC process water reduced the impact on Freshwater Ecotoxicity and Eutrophication.

Phosphorus recovery from process waste water made by the hydrothermal carbonisation of spent coffee grounds.

This study investigates the recovery of phosphorus from the process water obtained through hydrothermal carbonisation (HTC) of a 'wet' biomass waste, namely spent coffee grounds. HTC was shown to liberate more than 82% of the total phosphorus in the grounds in the form of dissolved ortho-phosphate. Nanofiltration was used to concentrate the inorganic nutrients of the HTC process water, achieving a mass concentration factor of 3.9 times. The natural stoichiometry of phosphorus, magnesium and ammoniacal nitrogen in the nanofiltration retentate was favourable for struvite precipitation. 92.8% of aqueous phosphorus was recovered as struvite through simple pH adjustment, yielding a total phosphorus recovery of 75% from the feedstock spent coffee grounds.

Structure and electrochemical properties of carbon nanostructures derived from nickel(II) and iron(II) phthalocyanines.

Mesoporous carbons containing up to 3.6 at.% N and 4.4 at.% O and exhibiting graphitic character have been prepared from Ni(II) and Fe(II) phthalocyanines by direct pyrolysis or by HTC + pyrolysis, and subsequently applied as supercapacitor materials. No mesoporous templates or doping post-treatments were used, and the catalytic effect of Ni(II) and Fe(II), naturally present in the precursor molecules, allowed obtaining graphitic carbons at temperatures ≤ 900 °C. Metals were encapsulated in the core of onion-like structures with no contact with the electrolyte, so that electrodes were prevented from degradation during device operation. The materials exhibited high rate capabilities up to 1 V s-1, higher interfacial capacitances than a wide variety of materials possessing higher surface areas, and high capacitance retentions up to 99% at 5 A g-1 current density throughout 10 000 charge-discharge cycles. The electrochemical performances of the phthalocyanine-derived carbons are due to their graphitic character and to the pseudocapacitance contribution of the surface groups through Faradaic reactions. This work opens a new way to obtain carbon materials from a great family of metal phthalocyanines, since the central metal and the radicals of the latter can be varied to tune the carbon properties for specific applications.

Valorisation of food waste via hydrothermal carbonisation and techno-economic feasibility assessment.

Food waste constitutes a remarkable portion of municipal solid waste. About one-third of the global food waste produced is lost with the food supply chain. Food waste in many countries is still dumped of in landfill or incinerated simultaneously with other municipal wastes. Food waste requires proper management and recycling techniques in order to minimise its environmental burden and risk to human life. Despite considerable research on food waste conversion still, there is a shortage of comprehensive reviews of the published literature. In this review, we provide a mini global perspective of food waste with special emphasis on New Zealand and their conversion into the useful material through hydrothermal carbonisation (HTC). Other thermal technologies such as incineration and pyrolysis are also briefly discussed. The review discusses why HTC is more suitable thermal technology than others, which are currently available. Recognising the importance of techno-economic feasibility of HTC, we present a cost analysis on the production of value-added products via HTC with examples taken from the literature to gather information in the feasibility assessment process. Finally, key challenges and future directions for a better productive way of handling food waste are being suggested.

One stage olive mill waste streams valorisation via hydrothermal carbonisation.

An olive waste stream mixture, coming from a three phase-continuous centrifugation olive oil mill industry, with a typical wet basis mass composition of olive pulp 39 wt%, kernels 5 wt% and olive mill waste water 56 wt%, was subjected to hydrothermal carbonisation (HTC) at 180, 220 and 250 °C for a 3-hour residence time in a 2-litre stainless steel electrically heated batch reactor. The raw feedstock and corresponding hydrochars were characterised in terms of proximate and ultimate analyses, higher heating values and energy properties. Results showed an increase in carbonisation of samples with increasing HTC severity and an energy densification ratio up to 142% (at 250 °C). Hydrochar obtained at 250 °C was successfully pelletised using a lab scale pelletiser without binders or expensive drying procedures. Energy characterisation (HHV, TGA), ATR-FTIR analysis, fouling index evaluation and pelletisation results suggested that olive mill waste hydrochars could be used as energy dense and mechanical stable bio-fuels. Characterisation of HTC residues in terms of mineral content via induced coupled plasma optical emission spectroscopy (ICP-OES) as well as Total and Dissolved Organic Carbon enabled to evaluate their potential use as soil improvers. Nutrients and polyphenolic compounds in HTC liquid fractions were evaluated for the estimation of their potential use as liquid fertilisers. Results showed that HTC could represent a viable route for the valorisation of olive mill industry waste streams.