Biofuel production,hydrogen production and water remediation by photocatalysis,biocatalysis and electrocatalysis

The energy crisis and environmental pollution have recently fostered research on efficient methods such as environmental catalysis to produce biofuel and to clean water. Environmental catalysis refers to green catalysts used to breakdown pollutants or produce chemicals without generating undesirable by-products. For example, catalysts derived from waste or inexpensive materials are promising for the circular economy. Here we review environmental photocatalysis, biocatalysis, and electrocatalysis, with focus on catalyst synthesis, structure, and applications. Common catalysts include biomass-derived materials, metal–organic frameworks, non-noble metals nanoparticles, nanocomposites and enzymes. Structure characterization is done by Brunauer–Emmett–Teller isotherm, thermogravimetry, X-ray diffraction and photoelectron spectroscopy. We found that water pollutants can be degraded with an efficiency ranging from 71.7 to 100%, notably by heterogeneous Fenton catalysis. Photocatalysis produced dihydrogen (H₂) with generation rate higher than 100 μmol h⁻¹. Dihydrogen yields ranged from 27 to 88% by methane cracking. Biodiesel production reached 48.6 to 99%.

     

Direct production of hydroxymethylfurfural from raw grape berry biomass using ionic liquids and metal chlorides

We report for the first time the direct conversion of raw grape berry biomass to hydroxymethylfurfural (HMF) using ionic liquid solvents with metal chloride catalysts. Exploiting raw plant biomass as a biorefinery feedstock is innovative for sustainable chemical industry. The use of the raw biomass to synthesize compounds can indeed lead to less energy consumption and less CO₂ emissions. Using raw plant biomass skips pretreatment steps that are required to produce biomaterials such as carbohydrates or cellulosic biomass. Here, grape berry biomass was used as a raw chemical feedstock for the production of hydroxymethylfurfural, a key platform intermediate for syntheses of future renewable biofuels. We examined 3 ionic liquid solvents, 3 reaction temperatures, 5 chloride catalysts, and 5 concentrations of HCl. We found an increasing HMF yields depending on reaction conditions. 1-octyl-3-methylimidazolium chloride was most effective for HMF synthesis. Addition of HCl or metal chlorides alone showed little improvement. The highest HMF yield of about 100 mg HMF per mL of grape biomass extract was obtained using 0.3 M HCl, [OMIM]Cl, and CrCl₂ at 100°C for 3 h. Our study provides a model system of sustainable production of valuable compounds from raw plant biomass.     

A gradient of mercury concentrations in Scottish single malt whiskies

Mercury (Hg) concentrations were measured in 26 Scottish single malt whiskies, and all found to be very low (<10 ng L⁻¹), posing no threat to human health through reasonable levels of consumption. However, a significant south-to-north declining gradient in Hg concentrations was observed reflecting that reported for atmospheric deposition. We speculate that this gradient could be due to a combination of contemporary deposition and the legacy of industrial mercury emissions and deposition over the last 200 years affecting concentrations in local waters used in whisky production. As UK atmospheric emissions of mercury have declined by 90 % since the 1970s, we suggest that whisky being produced today should have even lower Hg concentrations when consumed in 10- to 15-years time. This reduction may be compromised by the remobilisation of contaminants stored in catchment soils being transferred to source waters, but is very unlikely to raise the negligible health risk due to Hg from Scottish single malt whisky consumption.

     

The impact of artisanal gold mining,ore processing and mineralization on water quality in Marmato,Colombia

Marmato, Colombia, has been an important centre of gold mining since before the first Spanish colonizers arrived in 1536. The Marmato deposit is hosted in a dacite and andesite porphyry stock as sheeted sulphide-rich veinlet systems. The district is currently experiencing a surge in both major mining projects and artisanal mining, driven by sustained high gold prices. Ore from small-scale and artisanal gold mining is processed in numerous small mills (entables) around Marmato, which impact surface water quality through the discharge of milled waste rock slurry, highly alkaline cyanide-treated effluent, and high dissolved metal loads. To investigate the impact of artisanal mining and ore processing, water samples were collected in January 2012 from streams around Marmato. The average dissolved metal concentrations in impacted streams were Zn, 78 mg L^?1; Pb, 0.43 mg L^?1; Cu, 403 µg L^?1 Cd, 255 µg L^?1; As, 235 µg L^?1; Ni, 67 µg L^?1; Co, 55 µg L^?1; Sb, 7 µg L^?1; and Hg, 42 ng L^?1, exceeding World Health Organization drinking water guidelines. In addition, arsenic speciation was conducted in-situ and indicated that 91–95% of inorganic arsenic species is in the form of As(V). Spatial analysis of the data suggests that entables processing ore for artisanal miners are the main contributor to water pollution, with high sediment loads, alkalinity and elevated concentrations of dissolved arsenic, cadmium, mercury and lead, caused by the processing of gold-bearing sulphides in the entables. Geochemical data from surface water were compared to a comprehensive data set of whole rock analyses from drill core and channel samples from the deposit, indicating that the deposit is significantly enriched in gold, silver, lead, zinc, arsenic, antimony, and cadmium compared to crustal averages, which is reflected in the surface water geochemistry. However, elevated mercury levels in surface water cannot be explained by enrichment of mercury in the deposit and strongly suggest that mercury is being added to concentrates during ore processing to amalgamate fine gold.

     

Occurrence,toxicity and adsorptive removal of the chloramphenicol antibiotic in water: a review

Chloramphenicol is a broad-spectrum bacterial antibiotic used against conjunctivitis, meningitis, plague, cholera, and typhoid fever. As a consequence, chloramphenicol ends up polluting the aquatic environment, wastewater treatment plants, and hospital wastewaters, thus disrupting ecosystems and inducing microbial resistance. Here, we review the occurrence, toxicity, and removal of chloramphenicol with emphasis on adsorption techniques. We present the adsorption performance of adsorbents such as biochar, activated carbon, porous carbon, metal–organic framework, composites, zeolites, minerals, molecularly imprinted polymers, and multi-walled carbon nanotubes. The effect of dose, pH, temperature, initial concentration, and contact time is discussed. Adsorption is controlled by π–π interactions, donor–acceptor interactions, hydrogen bonding, and electrostatic interactions. We also discuss isotherms, kinetics, thermodynamic data, selection of eluents, desorption efficiency, and regeneration of adsorbents. Porous carbon-based adsorbents exhibit excellent adsorption capacities of 500–1240 mg g^?1. Most adsorbents can be reused over at least four cycles.

     

Efficient adsorption of carbon dioxide and methane on activated carbon prepared from glycerol with potassium acetate

In the context of global warming and the energy crisis, emissions to the atmosphere of greenhouse gases such as carbon dioxide (CO₂) and methane (CH₄) should be reduced, and biomethane from landfill biogas should be recycled. For this, there is a need for affordable technologies to capture carbon dioxide, such as adsorption of biogas on activated carbon produced from industrial wastes. Here we converted glycerol, a largely available by-product from biodiesel production, into activated carbon with the first use of potassium acetate as an activating agent. We studied adsorption of CO₂ and CH₄ on activated carbon. The results show that activated carbon adsorb CO₂ up to 20% activated carbon weight at 250 kPa, and 9% at atmospheric pressure. This is explained by high specific surface areas up to 1115 m²g⁻¹. Moreover, selectivity values up to 10.6 are observed for the separation of CO₂/CH₄. We also found that the equivalent CO₂ emissions from activated carbon synthesis are easily neutralized by their use, even in a small biogas production unit.

     

Catalytic reduction of water pollutants: knowledge gaps,lessons learned,and new opportunities

● Advances, challenges, and opportunities for catalytic water pollutant reduction. ● Cases of Pd-based catalysts for nitrate, chlorate, and perchlorate reduction. ● New functionalities developed by screening and design of catalytic metal sites. ● Facile catalyst preparation approaches for convenient catalyst optimization. ● Rational design and non-decorative effort are essential for future work. In this paper, we discuss the previous advances, current challenges, and future opportunities for the research of catalytic reduction of water pollutants. We present five case studies on the development of palladium-based catalysts for nitrate, chlorate, and perchlorate reduction with hydrogen gas under ambient conditions. We emphasize the realization of new functionalities through the screening and design of catalytic metal sites, including (i) platinum group metal (PGM) nanoparticles, (ii) the secondary metals for improving the reaction rate and product selectivity of nitrate reduction, (iii) oxygen-atom-transfer metal oxides for chlorate and perchlorate reduction, and (iv) ligand-enhanced coordination complexes for substantial activity enhancement. We also highlight the facile catalyst preparation approach that brought significant convenience to catalyst optimization. Based on our own studies, we then discuss directions of the catalyst research effort that are not immediately necessary or desirable, including (1) systematic study on the downstream aspects of under-developed catalysts, (2) random integration with hot concepts without a clear rationale, and (3) excessive and decorative experiments. We further address some general concerns regarding using H₂ and PGMs in the catalytic system. Finally, we recommend future catalyst development in both “fundamental” and “applied” aspects. The purpose of this perspective is to remove major misconceptions about reductive catalysis research and bring back significant innovations for both scientific advancements and engineering applications to benefit environmental protection.     

High removal of nitrogen and phosphorus from black-odorous water using a novel aeration-adsorption system

Black-odorous waters are an increasingly common phenomenon characterized by excessive levels of nutrients, the formation of metal sufide precipitates, volatile sulfurous compounds, low dissolved oxygen and high chemical oxygen demand. Black-odorous waters frequently occur in lake and river systems where inputs have restricted circulation. The key remediation issue is the removal of nitrogen and phosphorus. Here, we present a novel aeration-adsorption system using fiber balls and we study treatment parameters and removal mechanism. Kinetics and changes of the solid phase were followed using Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. Results show complete removal of ammonia N, initially at 31 mg/L, and 92.8% removal of total nitrogen, initially at 29 mg/L, after a 24 h reaction time at pH 9.67. At pH 5.67 and 9.67, total phosphorus and phosphate could be significantly reduced by 90–92% at 3.2–5.2 mg/L after 24 h. Treatment met China’s integrated wastewater discharge standards, demonstrating an effective and robust treatment capability. First-order and second-order kinetic models provided a good fit to the treatment data, indicating physical and chemical adsorption were involved in the treatment reactions. The reaction mechanism involved hydrogen substitution and binding to oxygen. These results present a cost effective and robust approach for the removal of N and P from black, odorous water, providing opportunity to abate environmental contamination.

     

Synthesis and potential applications of cyclodextrin-based metal–organic frameworks: a review

Metal–organic frameworks are porous polymeric materials formed by linking metal ions with organic bridging ligands. Metal–organic frameworks are used as sensors, catalysts for organic transformations, biomass conversion, photovoltaics, electrochemical applications, gas storage and separation, and photocatalysis. Nonetheless, many actual metal–organic frameworks present limitations such as toxicity of preparation reagents and components, which make frameworks unusable for food and pharmaceutical applications. Here, we review the structure, synthesis and properties of cyclodextrin-based metal–organic frameworks that could be used in bioapplications. Synthetic methods include vapor diffusion, microwave-assisted, hydro/solvothermal, and ultrasound techniques. The vapor diffusion method can produce cyclodextrin-based metal–organic framework crystals with particle sizes ranging from 200 nm to 400 μm. Applications comprise food packaging, drug delivery, sensors, adsorbents, gas separation, and membranes. Cyclodextrin-based metal–organic frameworks showed loading efficacy of the bioactive compounds ranging from 3.29 to 97.80%.

     

Cost,environmental impact,and resilience of renewable energy under a changing climate: a review

Energy derived from fossil fuels contributes significantly to global climate change, accounting for more than 75% of global greenhouse gas emissions and approximately 90% of all carbon dioxide emissions. Alternative energy from renewable sources must be utilized to decarbonize the energy sector. However, the adverse effects of climate change, such as increasing temperatures, extreme winds, rising sea levels, and decreased precipitation, may impact renewable energies. Here we review renewable energies with a focus on costs, the impact of climate on renewable energies, the impact of renewable energies on the environment, economy, and on decarbonization in different countries. We focus on solar, wind, biomass, hydropower, and geothermal energy. We observe that the price of solar photovoltaic energy has declined from $0.417 in 2010 to $0.048/kilowatt-hour in 2021. Similarly, prices have declined by 68% for onshore wind, 60% for offshore wind, 68% for concentrated solar power, and 14% for biomass energy. Wind energy and hydropower production could decrease by as much as 40% in some regions due to climate change, whereas solar energy appears the least impacted energy source. Climate change can also modify biomass productivity, growth, chemical composition, and soil microbial communities. Hydroelectric power plants are the most damaging to the environment; and solar photovoltaics must be carefully installed to reduce their impact. Wind turbines and biomass power plants have a minimal environmental impact; therefore, they should be implemented extensively. Renewable energy sources could decarbonize 90% of the electricity industry by 2050, drastically reducing carbon emissions, and contributing to climate change mitigation. By establishing the zero carbon emission decarbonization concept, the future of renewable energy is promising, with the potential to replace fossil fuel-derived energy and limit global temperature rise to 1.5 °C by 2050.

     

Enhanced desorption of fluoxetine from polyethylene terephthalate microplastics in gastric fluid and sea water

There are concerns that microplastics act as a vector of pharmaceuticals in the aquatic environment. Most studies have focussed on pharmaceutical adsorption and have not investigated desorption in the various matrices that microplastics enter. Therefore we studied the desorption of the antidepressant drug fluoxetine from polyethylene terephthalate (PET) microplastics in river water, sea water, and simulated gastric and intestinal fluids. We found that most desorption occurred rapidly, within a few hours of exposure. Fluoxetine desorption fitted well to the Freundlich isotherm with r² values ranging from 0.97 to 0.99. Desorption decreased in the following order: gastric fluid at 20 °C and 37 °C; sea water at 20 °C; intestinal fluid at 20 °C and 37 °C; then river water at 20 °C. The little difference in desorption in gastrointestinal fluids at 20 °C and 37 °C suggests a similar exposure risk to cold- and warm-blooded organisms following PET microplastic ingestion. Total desorption following sequential incubation 2 h in gastric fluid then 4 h in intestinal fluid to mimic gastrointestinal digestion was 37% at 20 °C and 41% at 37 °C. Interestingly, higher desorption of 18–23% occurred in sea water compared to river water, of 4–11%. Under a worst-case scenario, more than 44 mg kg⁻¹ body weight d⁻¹ or more than 52 mg kg⁻¹ body weight d⁻¹ of PET microplastics from river water or sea water, respectively, need to be consumed to exceed the mammalian acceptable daily intake for fluoxetine. Further studies are needed on microplastic ingestion and the bioavailability of adsorbed pharmaceuticals to a range of exposed aquatic organisms.

     

Novel synthetic approaches and TWC catalytic performance of flower-like Pt/CeO2

A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 catalysts were characterized by X-Ray Diffraction （XRD）, Scanning Electron Microscope （SEM）, Transmission Electron Microscope （TEM）, N2 adsorption, and hydrogen temperature programmed reduction （HE-TPR） techniques. The catalytic performance of the catalysts for treating automobile emission was studied relative to samples prepared by the conventional wetness impregnation method. The Pt/CeO2 catalysts fabricated by this novel method showed high specific surface area and metal dispersion, excellent three-way catalytic activity, and good thermal stability. The strong interaction between the Pt nanoparticles and CeO2 improved the thermal stability. The Ce4＋ ions were incorporated into the surfactant chains and the Pt nanoparticles were stabilized through an exchange reaction of the surface hydroxyl groups. The SEM results demonstrated that the Pt/CeO2 catalysts had a typical three-dimensional （3D） hierarchical porous struc- ture, which was favorable for surface reaction and enhanced the exposure degree of the Pt nanoparticles. In brief, the flower-like Pt/CeO2 catalysts prepared by UAMR-hydrothermal method exhibited a higher Pt metal dispersion, smaller particle size, better three-way catalytic activity, and improved thermal stability versus conven- tional materials.     

Photocatalytic degradation of indole in UV/TiO2: optimization and modelling using the response surface methodology (RSM)

The aim of our research is to apply experimental design methodology to the optimization of photocatalytic degradation of indole present in wastewater. Heterogeneous photocatalysis for the oxidation of organic biorecalcitrant pollutants in water is an environmental promising method. We used the response surface methodology (RSM) for the modelization and optimization of the photodegradation of indole in the presence of titanium dioxide. The effect of indole concentration, UV intensity and stirring speed on the yield of indole degradation was determined. According to the mathematic optimization of the process, the optimum point when 100% of degradation is achieved is given by the following values: UV intensity = 250 W/m², stirring speed = 536.36 tr/min and initial indole concentration = 10.10 mg/l.     

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.

     

The origin of high hydrocarbon groundwater in shallow Triassic aquifer in Northwest Guizhou,China

Original high hydrocarbon groundwater represents a kind of groundwater in which hydrocarbon concentration exceeds 0.05 mg/L. The original high hydrocarbon will significantly reduce the environment capacity of hydrocarbon and lead environmental problems. For the past 5 years, we have carried out for a long-term monitoring of groundwater in shallow Triassic aquifer in Northwest Guizhou, China. We found the concentration of petroleum hydrocarbon was always above 0.05 mg/L. The low-level anthropogenic contamination cannot produce high hydrocarbon groundwater in the area. By using hydrocarbon potential, geochemistry and biomarker characteristic in rocks and shallow groundwater, we carried out a comprehensive study in Dalongjing (DLJ) groundwater system to determine the hydrocarbon source. We found a simplex hydrogeology setting, high-level water–rock–hydrocarbon interaction and obviously original hydrocarbon groundwater in DLJ system. The concentration of petroleum hydrocarbon in shallow aquifer was found to increase with the strong water–rock interaction. Higher hydrocarbon potential was found in the upper of Guanling formation (T₂g³) and upper of Yongningzhen formation (T₁yn⁴). Heavily saturated carbon was observed from shallow groundwater, which presented similar distribution to those from rocks, especially from the deeper groundwater. These results indicated that the high concentrations of original hydrocarbon in groundwater could be due to the hydrocarbon release from corrosion and extraction out of strata over time.

     

Metallic and bimetallic phosphides-based nanomaterials for photocatalytic hydrogen production and water detoxification: a review

Environmental Chemistry Letters - Providing sustainable energy and cleaning water pollution are actually&nbsp;major societal issues requiring new catalysts. In particular,&nbsp;transition...     

Optimizing biomass pathways to bioenergy and biochar application in electricity generation,biodiesel production,and biohydrogen production

The current energy crisis, depletion of fossil fuels, and global climate change have made it imperative to find alternative sources of energy that are both economically sustainable and environmentally friendly. Here we review various pathways for converting biomass into bioenergy and biochar and their applications in producing electricity, biodiesel, and biohydrogen. Biomass can be converted into biofuels using different methods, including biochemical and thermochemical conversion methods. Determining which approach is best relies on the type of biomass involved, the desired final product, and whether or not it is economically sustainable. Biochemical conversion methods are currently the most widely used for producing biofuels from biomass, accounting for approximately 80% of all biofuels produced worldwide. Ethanol and biodiesel are the most prevalent biofuels produced via biochemical conversion processes. Thermochemical conversion is less used than biochemical conversion, accounting for approximately 20% of biofuels produced worldwide. Bio-oil and syngas, commonly manufactured from wood chips, agricultural waste, and municipal solid waste, are the major biofuels produced by thermochemical conversion. Biofuels produced from biomass have the potential to displace up to 27% of the world's transportation fuel by 2050, which could result in a reduction in greenhouse gas emissions by up to 3.7 billion metric tons per year. Biochar from biomass can yield high biodiesel, ranging from 32.8% to 97.75%, and can also serve as an anode, cathode, and catalyst in microbial fuel cells with a maximum power density of 4346 mW/m². Biochar also plays a role in catalytic methane decomposition and dry methane reforming, with hydrogen conversion rates ranging from 13.4% to 95.7%. Biochar can also increase hydrogen yield by up to 220.3%.

     

Methods for chemical conversion of plastic wastes into fuels and chemicals. A review

Plastics are utilized in various materials that are useful in everyday life. As the usage of plastics increases, the disposal of plastic materials has become a major issue, calling for recycling methods. Here, we review the different methods to recycle plastics, with focus on catalytic cracking. We present catalysts, cracking mechanisms, and we compare the various treatment methodologies. Several attempts were made by researchers to increase the efficiency of the cracking process using different catalysts and reactors. Many studies reveal high quality products are obtained by catalytic cracking, which consumes low energy and produces lesser residues when compared to other treatment technologies.

     

Spectrophotometric determination of trifluralin in commercial formulations and agricultural samples using factorial design

A simple spectrophotometric method was developed for determination of trifluralin in commercial formulation and food samples. The method was based on the hydrolysis of trifluralin with sodium hydroxide to form 2,6-dinitro-4-trifluoromethylaniline. The resultant aniline group was diazotized with nitrate in acidic media and the diazotized product was coupled with β-naphthol to form red colored product having λ_max 550 nm. The reaction conditions were optimized for hydrolysis as well as for the diazotization reaction. The Beer’s law was obeyed over the range of 0.2–17 μg mL⁻¹ with molar absorptivity of 1.5 × 10⁴ L mol⁻¹ cm⁻¹. The relative standard deviation was found to be 3.6%. A two level factorial design of 2³ was used for optimization of all parameters. The influence of different factors and their interactions on the final azo dye formation were also studied from these factorial designs. The method has been applied successfully for the analysis of commercial formulations and agricultural samples. The recovery for the determination of trifluralin was found to be in the range 95–97%.     

Rapid release of heavy metals and anions from polyethylene laminated paper cups into hot water

Polyethylene laminated disposable paper cups are commonly used as a container for hot drinks, yet there is limited knowledge on the transfer of contaminants from the cup to the drink. Here we poured 95^?C hot water in 14 cups, to simulate the preparation of hot beverage for daily use. We studied the water composition after 15 min by inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography. Results show the presence of metals such as vanadium, chromium, copper, cobalt and arsenic at concentration ranging from 0.04 to 1.80 µg/L. Nitrate, nitrite, chloride, bromate, fluoride and sulfate ions were also detected at concentration from 0.003 to 49.21 mg/L. All concentrations are below the WHO maximum permissible limits in drinking water. However, the levels of vanadium at 1.24 µg/L and fluoride ions at 1.03 mg/L are likely to induce a health risk by bioaccumulation after long-term water ingestion. Therefore paper cups composition should be modified to avoid the release of contaminants in hot drinks.