Biorenewable hydrogen production through biomass gasification: A review and future prospects.

Hydrogen is recognized as one of the cleanest energy carriers, which can be produced from renewable biomass as a promising feedstock to achieve sustainable bioeconomy. Thermochemical technologies (e.g., gasification and pyrolysis) are the main routes for hydrogen production from biomass. Although biomass gasification, including steam gasification and supercritical water gasification, shows a high potential in field-scale applications, the selectivity and efficiency of hydrogen production need improvement to secure cost-effective industrial applications with high atom economy. This article reviews the two main-stream biomass-to-hydrogen technologies and discusses the significance of operating conditions and considerations in the catalytic system design. Challenges and prospects of hydrogen production via biomass gasification are explored to advise on the critical information gaps that require future investigations.

Impact of hydronium ions on the Pd-catalyzed furfural hydrogenation.

In aqueous mediums, the chemical environment for catalytic reactions is not only comprised of water molecules but also of corresponding ionized species, i.e., hydronium ions, which can impact the mechanism and kinetics of a reaction. Here we show that in aqueous-phase hydrogenation of furfural on Pd/C, increasing the hydronium ion activities by five orders of magnitude (from pH 7 to pH 1.6) leads to an increase of less than one order of magnitude in the reaction rate. Instead of a proton-coupled electron transfer pathway, our results show that a Langmuir-Hinshelwood mechanism describes the rate-limiting hydrogen addition step, where hydrogen atom adsorbed on Pd is transferred to the carbonyl C atom of the reactant. As such, the strength of hydrogen binding on Pd, which decreases with increasing hydronium ion concentration (i.e., 2 kJ molH2-1 per unit pH), is a decisive factor in hydrogenation kinetics (rate constant +270%). In comparison, furfural adsorption on Pd is pH-independent, maintaining a tilted geometry that favors hydrogen attack at the carbonyl group over the furan ring.

Valorization of humins from food waste biorefinery for synthesis of biochar-supported Lewis acid catalysts.

To close the carbon loop of biomass waste valorization, it is imperative to utilize the unavoidable by-products such as humins, a carbonaceous residue with complex and heterogeneous composition. In this study, starch-rich rice waste was effectively converted into value-added chemicals (e.g., 5-hydroxymethylfurfural) under microwave heating at 160 °C using AlCl3 as the catalyst. The solid by-products, i.e., humins, were then valorized as a raw material for fabricating biochar-supported Lewis acid catalysts. The humins were collected and pretreated by AlCl3 as the impregnation agent, followed by carbonization. Detailed characterization revealed several AlO species on the biochar surface plausibly in the amorphous state. The oxygen-containing functional groups of humins might serve as anchoring sites for the Al species during impregnation. The humins-derived biochars exhibited good catalytic activity toward glucose-to-fructose isomerization, a common biorefinery reaction catalyzed by Lewis acids. A fructose yield of up to 14 Cmol% could be achieved under microwave heating at 160 °C for 20 min in water as the greenest solvent. Such catalytic performance was comparable with the previously reported Al-based catalysts derived from wood waste and graphene/graphitic oxide. This study herein highlights humins as a low-cost alternative source of carbon for the preparation of renewable solid catalysts, proposing a novel practice for recycling by-products from food waste valorization to foster circular economy and sustainable development.

A cross-region analysis of commercial food waste recycling behaviour.

To tackle the crisis associated with the rising commercial food waste generation, it is imperative to comprehend how corporates' recycling behaviour is influenced by different industry structures and economies. This study aims to fill in the information gap that various factors might be affecting corporates' recycling behaviour in two different economies due to environmental inequality by comparing upper-middle-income region (Malaysia) and high-income region (Hong Kong), respectively. A questionnaire survey regarding food waste management according to the Theory of Planned Behaviour was conducted with representatives coming from diverse industries of the hotel, food and beverage, and property management. The questionnaire responses were evaluated based on quantitative structural equation modelling and correlation analysis. The analysis results showed that the model fit the data well, explaining 78% of the variance in recycling behaviour. The findings demonstrated that the most substantial factor on individual's recycling intention by Malaysian commercial food waste generators was perceived behavioural control, and logistics and management incentives. Subjective norms demonstrated significant and adverse effects on the behaviour of food waste recycling. The variable of administrative incentives and corporate support presented strong positive correlations with moral attitudes as well as logistics and management incentives. Hotel industries from both Hong Kong and Malaysia have a higher acceptance level on human resources regarding food waste recycling. In comparison, food and beverage industries from both regions have a lower acceptance level. These findings could enrich our knowledge of the concerns in establishing regional policy strategies to encourage economic behavioural changes for sustainable development.

Size-activity threshold of titanium dioxide-supported Cu cluster in CO oxidation.

Development of non-noble metal cluster catalysts, aiming at concurrently high activity and stability, for emission control systems has been challenging because of sintering and overcoating of clusters on the support. In this work, we reported the role of well-dispersed copper nanoclusters supported on TiO2 in CO oxidation under industrially relevant operating conditions. The catalyst containing 0.15 wt% Cu on TiO2 (0.15 CT) exhibited a high dispersion (59.1%), a large specific surface area (381 m2/gCu), a small particle size (1.77 nm), and abundant active sites (75.8% Cu2O). The CO oxidation activity measured by the turnover frequency (TOF) was found to be enhanced from 0.60 × 10-3 to 3.22 × 10-3 molCO·molCu-1·s-1 as the copper loading decreased from 5 to 0.15 wt%. A CO conversion of approximately 60% was still observed in the supported cluster catalyst with a Cu loading of 5 wt% at 240 °C. No deactivation was observed for catalysts with low copper loading (0.15 and 0.30 CT) after 8 h of time-on-stream, which compares favorably with less stable Au cluster-based catalysts reported in the literature. In contrast, catalysts with high copper loading (0.75 and 5 CT) showed deactivation over time, which was ascribed to the increase in copper particle size due to metal cluster agglomeration. This study elucidated the size-activity threshold of TiO2-supported Cu cluster catalysts. It also demonstrated the potential of the supported Cu cluster catalyst at a typical temperature range of diesel engines at light-load. The supported Cu cluster catalyst could be a promising alternative to noble metal cluster catalysts for emission control systems.

Sustainable food waste management towards circular bioeconomy: Policy review, limitations and opportunities.

Research attention is increasingly drawn on constructing a circular bioeconomy and enhancing the value of material flows. Circular bioeconomy aims to achieve sustainable consumption and production with reduction of greenhouse gas emission. This study identifies research gaps on how circular bioeconomy can be achieved through sustainable food waste management by comparing the similarities and differences in concepts of bioeconomy and circular economy, reviewing the benefits and limitations of the existing policies, and evaluating the global situations of food waste and its management on household and commercial basis to promote circular bioeconomy. Future development on food waste management is expected to capitalise on the multi-functionality of products, boundary and allocation in a circular system, and trade-off between food waste and resources. With future technological advances, food waste management in circular bioeconomy policy can facilitate the accomplishment of sustainable development goals.

Tailoring acidity and porosity of alumina catalysts via transition metal doping for glucose conversion in biorefinery.

Efficient conversion of food waste to value-added products necessitates the development of high-performance heterogeneous catalysts. This study evaluated the use of Al2O3 as a low-cost and abundant support material for fabricating Lewis acid catalysts, i.e., through the in-situ doping of Cu, Ni, Co, and Zr into Al2O3 followed by calcination. The characterisation results show that all catalysts were mainly amorphous. In particular, adding the transition metals to the Al2O3 matrix resulted in the increase of acidity and meso-/micro-pores. The catalysts were evaluated in the conversion of glucose, which can be easily derived from starch-rich food waste (e.g., bread waste) via hydrolysis, to fructose in biorefinery. The results indicate that the Ni-doped Al2O3 (Al-Ni-C) achieved the highest fructose yield (19 mol%) and selectivity (59 mol%) under heating at 170 °C for 20 min, of which the performance falls into the range reported in literature. In contrast, the Zr-doped Al2O3 (Al-Zr-C) presented the lowest fructose selectivity despite the highest glucose conversion, meaning that the catalyst was relatively active towards the side reactions of glucose and intermediates. The porosity and acidity, modified via metal impregnation, were deduced as the determinants of the catalytic performance. It is noteworthy that the importance of these parameters may vary in a relative sense and the limiting factor could shift from one parameter to another. Therefore, evaluating physicochemical properties as a whole, instead of the unilateral improvement of a single parameter, is encouraged to leverage each functionality for cost-effectiveness. This study provides insights into the structure-performance relationships to promote advance in catalyst design serving a sustainable food waste biorefinery.

Influence of green solvent on levulinic acid production from lignocellulosic paper waste.

Lignocellulosic wastes constitute a significant portion of the municipal solid waste, which should be valorised for the synthesis of value-added chemicals to achieve circular bioeconomy. This study evaluates the use of γ-valerolactone (GVL) and acetone as green co-solvents to produce levulinic acid (LA) from lignocellulosic paper towel waste at different temperatures using dilute H2SO4. At the highest reaction temperature (200 °C), H2O-only system achieved ~15 Cmol% of LA at maximum. while GVL/H2O and acetone/H2O co-solvent systems enhanced the depolymerisation of paper towel waste and the subsequent conversion to LA, with the highest yield amounted to ~32 Cmol%. Acetone/H2O solvent system generated ~17 Cmol% LA at a lower temperature (180 °C), while higher temperature induced polymerisation of soluble sugars and intermediates, hindering further conversion to LA. In contrast, the availability of soluble sugars was higher in the GVL/H2O system, which favoured the production of LA at higher temperatures.

Novel M (Mg/Ni/Cu)-Al-CO3 layered double hydroxides synthesized by aqueous miscible organic solvent treatment (AMOST) method for CO2 capture.

Layered double hydroxides (LDHs) have been intensively studied in recent years owing to their great potential in CO2 capture. However, the severe aggregation between platelets and low surface area restricted it from exhibiting very high CO2 adsorption capacity and CO2/N2 selectivity. In this research, we for the first time synthesized Ni-Al-CO3 and Cu-Al-CO3 LDHs using aqueous miscible organic solvent treatment (AMOST) method. The as-synthesized materials were evaluated for CO2 adsorption at three different temperatures (50, 80, 120 °C) applicable to post-combustion CO2 capture. Characterized with XRD, N2 adsorption-desorption, TEM, EDX, and TGA, we found the newly synthesized Ni-Al-CO3 LDH showed a nano-flower-like morphology comprising randomly oriented 2D nanoplatelets with both high surface area (249.45 m2/g) and pore volume (0.59 cc/g). Experimental results demonstrated that un-calcined Ni-Al-CO3 LDH is superior in terms of CO2 capture among the three LDHs, with a maximum CO2 adsorption capacity of 0.87 mmol/g and the ideal CO2/N2 selectivity of 166 at 50 °C under 1200 mbar for typical flue gas CO2/N2 composition (CO2:N2 = 15:85, v/v). This is the first report of a delaminated Ni-Al-CO3 LDH showing better CO2 capture performance than the well-reported optimal Mg layered double hydroxide.

Exfoliated Ni-Al LDH 2D nanosheets for intermediate temperature CO2 capture.

CO2 capture is projected as one of the pragmatic approaches to deal with the global warming phenomenon. Adsorption-based CO2 capture is considered an economically attractive option to reduce CO2 emission. The success of the adsorption-based capture primarily relies on adsorbents and thus a variety of adsorbents have been investigated in the literature. We here report a high surface area (210.2 m2/g) exfoliated Ni-Al LDH nanoplatelet as a promising candidate for CO2 capture at an intermediate temperature of 200 °C applicable to integrated gasification combined cycle (IGCC) and sorption enhanced water gas shift (SEWGS) reactions. The materials were well characterized by PXRD, TGA, FTIR, TEM, ICP-OES, and N2 adsorption surface area, and pore size distribution techniques. A unique nanoflower morphology comprising of exfoliated LDH platelets of ca. 5 layer thickness was obtained. The CO2 capture capacity (0.66 mmol/g) of the exfoliated Ni-Al LDH nanoplatelet is comparable to that of the widely reported Mg-Al LDH-derived mixed oxides and MgO-based adsorbents. Provided that Ni-Al and other transition metal LDH materials are known to exhibit superior catalytic properties for CO2 methanation, this work could pave the way for development of dual-functional materials for CO2 capture and conversion.

Microwave-assisted low-temperature hydrothermal treatment of red seaweed (Gracilaria lemaneiformis) for production of levulinic acid and algae hydrochar.

In this study, red seaweed (Gracilaria lemaneiformis) food waste with high carbohydrate content was valorized into levulinic acid (LA) and algae hydrochar through microwave-assisted low-temperature hydrothermal treatment in dilute acid solution. Various parameters including treatment temperature (160-200 °C), reaction time (1-40 min), acid concentration (0-0.6 M), and biomass-to-liquid ratio (1%-10%, w/v) were examined. The energy efficiency and carbon recovery of the proposed process were investigated. Under the experimental conditions of 5% (w/v) biomass loading, 0.2 M H2SO4, 180 °C, and 20 min, the highest levulinic acid yield of 16.3 wt% was produced. The resulting hydrochar showed approximately 45-55% energy yield and higher heating values of 19-25 MJ kg-1. The energy efficiency of the present study (1.31 × 10-6 g LA/J) was comparable to those of the conventional hydrothermal treatment of lignocellulosic biomass, while the reaction time (20 min) was much shorter with a high carbon recovery (73.3%).

Extended theory of planned behaviour for promoting construction waste recycling in Hong Kong.

Changing individual's recycling attitude and behaviour is of utmost importance in achieving sustainable construction and demolition (C&D) waste management, yet it has often been underachieved. To understand the motivations for recycling, this study identifies and prioritizes the key factors that affect C&D waste recycling behaviour of various stakeholders in Hong Kong (i.e., representatives from construction-waste-related organizations, environmental consultants and contractors, and government engineers) in a quantitative manner using statistical tools. Different from traditional C&D waste behavioural determinants studies, this paper utilizes an integrated analytical method through semi-structured interviews and survey questionnaire on the basis of Theory of Planned Behaviour (TPB). Qualitative thematic analysis and quantitative frequency analysis were performed to analyse responses from semi-structured interviews and questionnaires, followed by correlation analysis to quantify the relationships between factors. Results indicated that four key factors: (i) regulatory compliance, (ii) economic incentives, (iii) accreditation scheme, and (iv) logistics and management incentives directly influenced recycling behaviour of individuals. Regulatory compliance was the most determining factor for consultants, contractors, experts, and government officials, whereas economic incentives were of great concern to the public. Under the factor of economic incentives, strong positive relationships were identified between disposal costs and collection and sorting costs, thus increasing waste disposal charging fee may promote recycling behaviour. In comparison, accreditation scheme deserved better recognition to facilitate a closed-loop material flow in the construction industry. These findings help to devise more effective and stakeholder-oriented policy tools to raise awareness and encourage behavioural change towards C&D waste recycling, and assist policy makers to establish regulations and practices for sustainable resource management.

Potentially toxic elements in solid waste streams: Fate and management approaches.

Solid wastes containing potentially toxic elements (PTEs) are widely generated around the globe. Critical concerns have been raised over their impacts on human health and the environment, especially for the exposure to PTEs during the transfer and disposal of the wastes. It is important to devise highly-efficient and cost-effective treatment technologies for the removal or immobilisation of PTEs in solid wastes. However, there is an inadequate overview of the global flow of PTEs-contaminated solid wastes in terms of geographical distribution patterns, which is vital information for decision making in sustainable waste management. Moreover, in view of the scarcity of resources and the call for a circular economy, there is a pressing need to recover materials (e.g., precious metals and rare earth elements) from waste streams and this is a more sustainable and environmentally friendly practice compared with ore mining. Therefore, this article aims to give a thorough overview to the global flow of PTEs and the recovery of waste materials. This review first summarises PTEs content in various types of solid wastes; then, toxic metal(loid)s, radioactive elements, and rare earth elements are critically reviewed, with respect to their patterns of transport transformation and risks in the changing environment. Different treatments for the management of these contaminated solid wastes are discussed. Based on an improved understanding of the dynamics of metal(loid) fates and a review of existing management options, new scientific insights are provided for future research in the development of high-performance and sustainable treatment technologies for PTEs in solid wastes.

Multifunctional iron-biochar composites for the removal of potentially toxic elements, inherent cations, and hetero-chloride from hydraulic fracturing wastewater.

This paper evaluates a novel sorbent for the removal of potentially toxic elements, inherent cations, and hetero-chloride from hydraulic fracturing wastewater (FWW). A series of iron-biochar (Fe-BC) composites with different Fe/BC impregnation mass ratios (0.5:1, 1:1, and 2:1) were prepared by mixing forestry wood waste-derived BC powder with an aqueous FeCl3 solution and subsequently pyrolyzing them at 1000 °C in a N2-purged tubular furnace. The porosity, surface morphology, crystalline structure, and interfacial chemical behavior of the Fe-BC composites were characterized, revealing that Fe chelated with CO bonds as COFe moieties on the BC surface, which were subsequently reduced to a CC bond and nanoscale zerovalent Fe (nZVI) during pyrolysis. The performance of the Fe-BC composites was evaluated for simultaneous removal of potentially toxic elements (Cu(II), Cr(VI), Zn(II), and As(V)), inherent cations (K, Na, Ca, Mg, Ba, and Sr), hetero-chloride (1,1,2-trichlorethane (1,1,2-TCA)), and total organic carbon (TOC) from high-salinity (233 g L-1 total dissolved solids (TDS)) model FWW. By elucidating the removal mechanisms of different contaminants, we demonstrated that Fe-BC (1:1) had an optimal reducing/charge-transfer reactivity owing to the homogenous distribution of nZVI with the highest Fe0/Fe2+ ratio. A lower Fe content in Fe-BC (0.5:1) resulted in a rapid exhaustion of Fe0, while a higher Fe content in Fe-BC (2:1) caused severe aggregation and oxidization of Fe0, contributing to its complexation/(co-)precipitation with Fe2+/Fe3+. All of the synthesized Fe-BC composites exhibited a high removal capacity for inherent cations (3.2-7.2 g g-1) in FWW through bridging with the CO bonds and cation-π interactions. Overall, this study illustrated the potential efficacy and mechanistic roles of Fe-BC composites for (pre-)treatment of high-salinity and complex FWW.

Photo-Fenton abatement of aqueous organics using metal-organic frameworks: An advancement from benchmark zeolite.

A new and environmentally benign photocatalyst is introduced in this study, which was synthesized via incipient wetness impregnation onto MIL-47(V) using an ethanolic Fe(III) chloride solution. The resultant materials were characterized by XRD, FE-SEM, and HR-TEM analyses. The photocatalytic capability of Fe/MIL-47 towards removal of methylene blue (MB) was evaluated in comparison to MIL-53(Al), Cu/MIL-47, and Fe/zeolite-Y. The unmodified MIL-47 achieved 55% MB removal after 20-min exposure to UV/H2O2, through photodegradation as the dominant mechanism. Incorporation of Fe species into MIL-47 significantly increased the MB removal rate by 2.4-fold and accomplished nearly complete removal (98.2%) in 60 min, outcompeting the performance of Cu/MIL-47 and Fe/zeolite-Y. Based on the results of XRD, the impregnation of Fe retained the crystalline characteristics of MIL-47. The significance of temperature, catalyst dose, pH, and molar ratio of H2O2:MB was also evaluated in governing the photocatalytic activity of Fe/MIL-47. The reusability of Fe/MIL-47 was evidenced through its repetitive uses in MB photodegradation. The current work highlighted the potential of Fe impregnation for modification of MOFs in order to fabricate highly efficient and water-stable heterogeneous photocatalyst for degradation of organic pollutants. With the use of an economical and environmentally safe reagent (i.e., Fe), robust photocatalyst can exhibit high sustainability to warrant clean environmental remediation.

Valorization of lignocellulosic fibres of paper waste into levulinic acid using solid and aqueous Brønsted acid.

This study aims to produce levulinic acid (LA) from paper towel waste in environment-friendly and economically feasible conditions, and evaluate the difference using solid and aqueous Brønsted acids. Direct dehydration of glucose to LA required sufficiently strong Brønsted acidity, where Amberlyst 36 demonstrated rapid production of approximately 30Cmol% of LA in 20min. However, the maximum yield of LA was limited by mass transfer. In contrast, the yield of LA gradually increased to over 40Cmol% in 1M H2SO4 at 150°C in 60min. The SEM images revealed the conversion in dilute acids under microwave at 150°C resulting in swelling structures of cellulose, which were similar to the pre-treatment process with concentrated acids. Further increase in reaction temperature to 200°C significantly shortened the reaction time from 60 to 2.5min, which saved the energy cost as revealed in preliminary cost analysis.

Phosphoric acid-activated wood biochar for catalytic conversion of starch-rich food waste into glucose and 5-hydroxymethylfurfural.

The catalytic activity of engineered biochar was scrutinized for generation of glucose and hydroxymethylfurfural (HMF) from starch-rich food waste (bread, rice, and spaghetti). The biochar catalysts were synthesized by chemical activation of pinewood sawdust with phosphoric acid at 400-600 °C. Higher activation temperatures enhanced the development of porosity and acidity (characterized by COPO3 and CPO3 surface groups), which imparted higher catalytic activity of H3PO4-activated biochar towards starch hydrolysis and fructose dehydration. Positive correlations were observed between HMF selectivity and ratio of mesopore to micropore volume, and between fructose conversion and total acid density. High yields of glucose (86.5 Cmol% at 150 °C, 20 min) and HMF (30.2 Cmol% at 180 °C, 20 min) were produced from rice starch and bread waste, respectively, over H3PO4-activated biochar. These results highlighted the potential of biochar catalyst in biorefinery as an emerging application of engineered biochar.

Lignin valorization for the production of renewable chemicals: State-of-the-art review and future prospects.

Lignin is an abundant biomass resource in aromatic structure with a low price in market, which can serve as renewable precursors of value-added products. However, valorization rate of annually produced lignin is less than 2%, suggesting the need for technological advancement to capitalize lignin as a versatile feedstock. In recent years, efficient utilization of lignin has attracted wide attention. This paper summarizes the research advances in the utilization of lignin resources (mainly in the last three years), with a particular emphasis on two major approaches of lignin utilization: catalytic degradation into aromatics and thermochemical treatment for carbon material production. Hydrogenolysis, direct pyrolysis, hydrothermal liquefaction, and hydrothermal carbonization of lignin are discussed in detail. Based on this critical review, future research directions and development prospects are proposed for sustainable and cost-effective lignin valorization.

Production of 5-hydroxymethylfurfural from starch-rich food waste catalyzed by sulfonated biochar.

Sulfonated biochar derived from forestry wood waste was employed for the catalytic conversion of starch-rich food waste (e.g., bread) into 5-hydroxymethylfurfural (HMF). Chemical and physical properties of catalyst were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area, and elemental analysis. The conversion of HMF was investigated via controlling the reaction parameters such as catalyst loading, temperature, and reaction time. Under the optimum reaction conditions the HMF yield of 30.4 Cmol% (i.e., 22 wt% of bread waste) was achieved in the mixture of dimethylsulfoxide (DMSO)/deionized-water (DIW) at 180 °C in 20 min. The effectiveness of sulfonated biochar catalyst was positively correlated to the density of strong/weak Brønsted acidity (SO3H, COOH, and OH groups) and inversely correlated to humins content on the surface. With regeneration process, sulfonated biochar catalyst displayed excellent recyclability for comparable HMF yield from bread waste over five cycles.

Plenty of room for carbon on the ground: Potential applications of biochar for stormwater treatment.

Low impact development (LID) systems are increasingly used to manage stormwater, but they have limited capacity to treat stormwater-a resource to supplement existing water supply in water-stressed urban areas. To enhance their pollutant removal capacity, infiltration-based LID systems can be augmented with natural or engineered geomedia that meet the following criteria: they should be economical, readily available, and have capacity to remove a wide range of stormwater pollutants in conditions expected during intermittent infiltration of stormwater. Biochar, a carbonaceous porous co-product of waste biomass pyrolysis/gasification, meets all these criteria. Biochar can adsorb pollutants, improve water-retention capacity of soil, retain and slowly release nutrients for plant uptake, and help sustain microbiota in soil and plants atop; all these attributes could help improve removal of contaminants in stormwater treatment systems. This article discusses contaminant removal mechanisms by biochar, summarizes specific biochar properties that enhance targeted contaminants removal from stormwater, and identifies challenges and opportunities to retrofit biochar in LID to optimize stormwater treatment.