Investigating the Metal-TiO2 Influence for Highly Selective Photocatalytic Oxidation of Methane to Methanol.

Methane conversion to valuable chemicals is a highly challenging and desirable reaction. Photocatalysis is a clean pathway to drive this chemical reaction, avoiding the high temperature and pressure of the syngas process. Titanium dioxide, being the most used photocatalyst, presents challenges in controlling the oxidation process, which is believed to depend on the metal sites on its surface that function as heterojunctions. Herein, we supported different metals on TiO2 and evaluated their activity in methane photooxidation reactions. We showed that Ni-TiO2 is the best photocatalyst for selective methane conversion, producing impressively high amounts of methanol (1.600 µmol·g-1) using H2O2 as an oxidant, with minimal CO2 evolution. This performance is attributed to the high efficiency of nickel species to produce hydroxyl radicals and enhance H2O2 utilization as well as to induce carrier traps (Ti3+ and SETOVs sites) on TiO2, which are crucial for C-H activation. This study sheds light on the role of catalyst structure in the proper control of CH4 photoconversion.

Aluminosilicate and zeolitic materials synthesis using alum sludge from water treatment plants: Challenges and perspectives.

Alum sludge (AS) is a by-product generated from drinking water treatment and produced in large amounts around the world. Its chemical composition makes this waste an emerging alternative source of silicon and aluminum for aluminosilicates or zeolite material production, which can add value to residues and contribute to the circular economy process on a global scale. In this sense, and considering the scarcity of information about AS, this review shows data collection about AS in different countries, including generation, chemical composition, and disposal information. The reuse of AS is discussed based on circular economy and the environmental gains derived from such approaches are highlighted, including the possibility of utilization with other residues (e.g., ash, bioproducts, etc). Moreover, this review shows and discusses the benefits and challenges of AS reuse in the synthesis process and how it can be a sustainable raw material for aluminosilicates and zeolite synthesis. The most common conditions (conventional or non-conventional) in zeolite synthesis from AS are mentioned and advantages, limitations and trends are discussed. The discussions and data presented can improve the AS management and reuse legislations, which certainly will collaborate with sustainable AS use and circular economy processes.

Cobalt Oxide on Boron-Doped Graphitic Carbon Nitride as Bifunctional Photocatalysts for CO2 Reduction and Hydrogen Evolution.

In this work, the prepared cobalt oxide decorated boron-doped g-C3N4 (CoOx/g-C3N4) heterojunction exhibits remarkable activity in CO2 reduction (CO2RR), resulting in high yields of CH3COOH (∼383 µmol·gcatalyst-1) and CH3OH (∼371 µmol·gcatalyst-1) with 58% selectivity to C2+ under visible light. However, the same system leads to high H2 evolution (HER) by increasing the cobalt oxide content, suggesting that the selectivity and preference for the CO2RR or HER depend on oxide decoration. By comparing HER and CO2RR evolution in the same system, this work provides critical insights into the catalytic mechanism, indicating that the CoOx/g-C3N4 heterojunction formation is necessary to foster high visible light photoactivity.

Revealing the Structure Formation on Polyglycerol Citrate Polymers-An Environmentally Friendly Polyester as a Seed-Coating Material.

A detailed structural investigation of a promising bio-based polymer, polyglycerol citrate polyester, obtained by the bulk polycondensation of glycerol (Gly) against citric acid (Cit) under mild reaction was performed. The reaction in conditions with and without catalyst use (sulfuric acid, H2SO4) was investigated, showing evidence that it is possible to modify the polymer solubility according to the ratio and catalyst utilization. 13C and 1H NMR indicated that synthesis catalyzed with Cit excess leads to higher esterification degrees of citrate groups. In contrast, the Gly moieties are more prominent in catalyzed polymers regardless of the excess monomers. Overall, a successful conversion of Gly and Cit into polyesters was attained even without catalysis, enabling a simple route for the large-scale production of this green material to be used as a coating material. This polymer has been shown to be well-suited for coating seeds and might be a promising material for similar agricultural applications. Tests on soybean seed coating with a PGCit solution of 75% indicated that the seed quality and germination rate were not affected by the PGCit coating, concluding that this polymer is suitable for this application.

Miniaturized Carbon Fiber Paper Electrodes for In Situ High Resolution NMR Analyses.

Combining spectroscopic techniques with electrochemistry is a promising strategy, as it allows the detailed investigation of the species that are consumed and produced by the reaction in real time. However, as with any in situ coupling technique, the junction between NMR and electrochemistry presents some challenges, notably the distortion of NMR signals due to the placement of electrodes close to or within the detection region. In this work, miniaturized electrodes made of carbon fiber paper were developed and later modified with platinum. Platinum decoration by cathodic deposition was chosen, as platinum is a prominent element in electrocatalysis, able to catalyze a large variety of reactions. To evaluate the efficiency of this electrochemical system, the oxidation of ascorbic acid was used as a model reaction. It was observed that the electrodes caused substantial signal distortion when placed within the detection region (full width at half-maximum equal to 1.46 Hz), whereas no distortion was observed when the electrodes were placed 1 mm above the detection region (full width at half-maximum equal to 0.95 Hz). With this system, it was also possible to monitor the magnetoelectrolysis effect, caused by the interaction of the magnetic field with the flowing ions, leading to a doubling of the ascorbic acid oxidation rate, compared to the reaction performed without a magnetic field. In addition to its low cost and simplicity in preparation, the developed electrode system allows the electrode surface to be easily modified with other suitable catalysts.

Struvite-based composites for slow-release fertilization: a case study in sand.

Struvite (St) recovered from wastewaters is a sustainable option for phosphorus (P) recovery and fertilization, whose solubility is low in water and high in environments characterized by a low pH, such as acidic soils. To broaden the use of struvite in the field, its application as granules is recommended, and thus the way of application should be optimized to control the solubility. In this study struvite slow-release fertilizers were designed by dispersing St particles (25, 50, and 75 wt%) in a biodegradable and hydrophilic matrix of thermoplastic starch (TPS). It was shown that, in citric acid solution (pH = 2), TPS promoted a steadier P-release from St compared to the pure St pattern. In a pH neutral sand, P-diffusion from St-TPS fertilizers was slower than from the positive control of triple superphosphate (TSP). Nevertheless, St-TPS featured comparable maize growth (i.e. plant height, leaf area, and biomass) and similar available P as TSP in sand after 42 days of cultivation. These results indicated that St-TPS slow P release could provide enough P for maize in sand, achieving a desirable agronomic efficiency while also reducing P runoff losses in highly permeable soils.

Encapsulation of Trichoderma harzianum with nanocellulose/carboxymethyl cellulose nanocomposite.

This study proposes the use of green matrices of cellulose nanocrystals (CNC) and a nanocomposite of CNC with carboxymethyl cellulose (CMC) for efficiently encapsulating the plant biocontrol agent Trichoderma harzianum. Beads containing spores of the microorganism were produced by dripping dispersions of the polymers into a CaCl2 coagulation bath, resulting in the crosslinking of CNC chains by Ca2+ ions. SEM micrographs evidenced the T. harzianum spores in the encapsulation matrices. X-ray microtomography confirmed the random distribution of the microorganism within the polymeric matrix and the presence of internal pores in the CNC:CMC:spores beads. Encapsulation in the CNC:CMC nanocomposite favored growth of the fungus after 10 days of storage at room temperature, which could be attributed to the presence of internal pores and to the extra carbon source provided by the CMC. The results indicated that CNC:CMC nanocomposites are promising materials for protecting and delivering microbial inoculants for agricultural applications.

Zinc loading in urea-formaldehyde nanocomposites increases nitrogen and zinc micronutrient fertilization efficiencies in poor sand substrate.

Agricultural output needs significant increases to feed the growing population. Fertilizers are essential for plant production systems, with nitrogen (N) being the most limiting nutrient for plant growth. It is commonly supplied to crops as urea. Still, due to volatilization, up to 50 % of the total N application is lost. Slow or controlled release fertilizers are being developed to reduce these losses. The co-application of zinc (Zn) as a micronutrient can increase N absorption. Thus, we hypothesize that the controlled delivery of both nutrients (N and Zn) in an integrated system can improve uptake efficiency. Here we demonstrate an optimized fertilizer nanocomposite based on urea:urea-formaldehyde matrix loaded with ZnSO4 or ZnO. This nanocomposite effectively stimulates maize development, with consequent adequate N uptake, in an extreme condition - a very nutrient-poor sand substrate. Our results indicate that the Zn co-application is beneficial for plant development. However, there were advantages for ZnO due to its high Zn content. We discuss that the dispersion favors the Zn delivery as the nanoparticulated oxide in the matrix. Concerning maize development, we found that root morphology is altered in the presence of the fertilizer nanocomposite. Increased root length and surface area may improve soil nutrient uptake, potentially accompanied by increased root exudation of essential compounds for N release from the composite structure.

Selective methane photooxidation into methanol under mild conditions promoted by highly dispersed Cu atoms on crystalline carbon nitrides.

Here we report a photocatalytic system based on crystalline carbon nitrides (PHI) and highly dispersed transition metals (Fe, Co and Cu) for controlled methane photooxidation to methanol under mild conditions. The Cu-PHI catalyst showed a remarkable methanol production (2900 µmol g-1) in 4 hours, with a turnover number of 51 moles of oxygenated liquid product per mole of Cu. To date, this result is the highest value for methane oxidation under mild conditions (1 bar, 25 °C).

Co-fertilization of Sulfur and Struvite-Phosphorus in a Slow-Release Fertilizer Improves Soybean Cultivation.

In face of the alarming world population growth predictions and its threat to food security, the development of sustainable fertilizer alternatives is urgent. Moreover, fertilizer performance should be assessed not only in terms of yield but also in root system development, as it impacts soil fertility and crop productivity. Fertilizers containing a polysulfide matrix (PS) with dispersed struvite (St) were studied for S and P nutrition due to their controlled-release behavior. Soybean cultivation in a closed system with St/PS composites provided superior biomass compared to a reference of triple superphosphate (TSP) with ammonium sulfate (AS), with up to 3 and 10 times higher mass of shoots and roots, respectively. Root system architectural changes may explain these results, with a higher proliferation of second order lateral roots in response to struvite ongoing P delivery. The total root length was between 1,942 and 4,291 cm for plants under St/PS composites and only 982 cm with TSP/AS. While phosphorus uptake efficiency was similar in all fertilized treatments (11-14%), St/PS achieved a 22% sulfur uptake efficiency against only 8% from TSP/AS. Overall, the composites showed great potential as efficient slow-release fertilizers for enhanced soybean productivity.

Unveiling the Solubilization of Potassium Mineral Rocks in Organic Acids for Application as K-Fertilizer.

Organic acids produced by soil microorganisms can be useful to promote the release of potassium (K) from potassium mineral rocks (KR), but the complexity of low reactivity minerals limits K solubilization and their use as fertilizer. Here, we investigate the ways that different organic acids (gluconic, oxalic, and citric) can affect the solubilization of potassium minerals, in order to propose process strategies to improve their solubility. For this, evaluations were performed using the model minerals KRpolyhalite (sedimentary mineral), KRfeldspar (igneous mineral), and KCl (commercial fertilizer). For KCl and KRpolyhalite, complete solubilization was achieved using all the organic acids, while for KRfeldspar, the highest K+ solubilization (34.86 mg L-1) was achieved with oxalic acid. The solubility of KRfeldspar was further investigated under submerged cultivation with the filamentous fungus Aspergillus niger, as well as after a mechanochemical grinding treatment. The biotechnological route resulted in solubilized K up to 63.2 mg L-1. The mechanochemical route, on the other hand, increased the release of K by about 8.6 times (993 mg L-1) compared to the natural mineral, due to the greater fragmentation of the particles after the treatment (with a surface area about 2.5 times higher than for the in natura KRfeldspar). These findings demonstrated the potential of applying biotechnological and mechanochemical routes with organic acids to improve the solubilization of K present in low reactivity mineral rocks, indicating the possible use of these minerals in more sustainable agricultural practices.

Bio-based composite granules with simultaneous biocontrol and phosphorus fertilization roles: Outcomes from a lab-scale in vitro assessment.

The use of phosphate rocks as low-solubility phosphorus fertilizers has been promoted to reduce the environmental impacts of agriculture, but adequate nutrient uptake by plants depends on solubilization of the rock, driven by soil microorganisms. Here, investigation was made of the microbial solubilization of low-solubility phosphate rocks, together with simultaneous bioprotective action involving the biocontrol of microorganisms. The aim was to enhance function and value by delivering two effects using a single bio-based product, in accordance with the concept of a "bioreactor-in-a-granule" system. A composite structure was developed, based on a starch matrix, comprising a combination of Trichoderma asperelloides, as a biocontrol agent, and Aspergillus niger, as an acidulant. A significant increase of up to 150% in P solubilization was achieved, indicating the positive effect of the microorganism-composite interaction. In vitro assays showed that the ability of T. asperelloides to inhibit Fusarium oxysporum mycelial growth was maintained in the presence of A. niger. Moreover, the estimated cost of the composite granule (0.35 US$/kg of product on a dry basis) revealed competitive. The results indicated that the association of T. asperelloides and A. niger is an effective way to increase nutrient availability and to inhibit plant pathogens, opening up possibilities for the design of multifunctional bio-based fertilizer composites.

Asbestos cement waste treatment through mechanochemical process with KH2PO4 for its utilization in soil pH correction and nutrient delivery.

The manufacture of asbestos materials has been banished worldwide due to their toxicity, but discarding the existing wastes remains a challenge. We investigated an alternative mechanochemical method to treat asbestos-cement materials by loading them with potassium and phosphorus from KH2PO4 during the milling process to obtain a product used as liming and soil conditioner. The results showed total asbestos fibrous elimination after 7 to 8 h of milling. The materials showed a slow-release fertilizer profile. The liming property is maintained when the asbestos-cement weight proportion used is equal to or higher than KH2PO4. A comparative soil experiment with limestone also indicates that lower doses of the K- and P-enriched detoxified asbestos cement were required to reach similar liming effects. Maize cultivation (greenhouse) was used to evaluate its performance showing higher biomass production for the sample loaded with potassium and phosphorous.

Different Zn loading in Urea-Formaldehyde influences the N controlled release by structure modification.

Nitrogen fertilization has been a critical factor for high crop productivity, where urea is currently the most used N source due to its high concentration and affordability. Nevertheless, urea fast solubilization leads to frequent losses and lower agronomic efficiency. The modification of urea structure by condensation with formaldehyde has been proposed to improve nutrient uptake by plants and to reduce environmental losses. Herein we show that the co-formulation with Zn strongly modifies the N release (in lab conditions) and, more important, the Zn source-ZnSO4 or ZnO-has a critical role. Urea-formaldehyde (UF) served as a matrix for the zinc sources, and chemical characterizations revealed that Zn particles influenced the length of the polymeric chain formation. Release tests in an aqueous medium showed that the UF matrix favors ZnO release and, on the other hand, delays ZnSO4 delivery. Soil incubation with the fertilizer composites proved the slow-release of N from UF, is ideal for optimizing nutritional efficiency. Our results indicated that the ZnO-UF system has beneficial effects for both nutrients, i.e., reduces N volatilization and increases Zn release.

Synergy of Aspergillus niger and Components in Biofertilizer Composites Increases the Availability of Nutrients to Plants.

Intensive fertilization has been required to provide nutrients for plant growth under the current agricultural practices being applied to meet the global food demands. Micronutrients such as zinc, manganese, and copper are required in small quantities when compared to macronutrients (such as nitrogen, phosphorus and potassium), but they are essential for the plant growth cycle and consequently for increasing productivity. Mineral oxides such as ZnO, MnO, and CuO are used in agriculture as micronutrient sources, but their low solubility limits practical applications in plant nutrition. Similarly, elemental sulfur (S0) can provide a high-concentration source of sulfate, but its availability is limited by the ability of the soil to promote S0 oxidation. We propose here the integration of these nutrients in a composite based on a biodegradable starch matrix containing mineral oxides and S0 in a dispersion that allowed encapsulation of the acidifying agent Aspergillus niger, a native soil fungus. This strategy effectively improved the final nutrient solubility, with the composite starch/S0/oxidemixture multi-nutrient fertilizer showing remarkable results for solubilization of the oxides, hence confirming a synergic effect of S0 oxidation and microbial solubilization. This composite exhibited an extended shelf life and soil-plant experiments with Italian ryegrass (Lolium multiflorum Lam.) confirmed high efficiencies for dry matter production, nutrient uptake, and recovery. These findings can contribute to the development of environmentally friendly fertilizers towards a more sustainable agriculture and could open up new applications for formulations containing poorly soluble oxide sources.

Synergy of Phosphate-Controlled Release and Sulfur Oxidation in Novel Polysulfide Composites for Sustainable Fertilization.

The development of smart and eco-friendly fertilizers is pivotal to guarantee food security sustainably. Phosphate rock and struvite are promising alternatives for P fertilization; nevertheless, the solubility of these sources is a challenge for consistent use efficiency. Here, we propose using a polysulfide obtained via inverse vulcanization as a novel controlled-release fertilizer matrix in a system containing either Bayóvar rock (Bay) or struvite (Str). The polysulfide provides S for plants after being biologically oxidized to sulfate in soil, generating local acidity for P solubilization. After 15 days of soil incubation, the composites with 75 wt % Str and 75 wt % Bay achieved, respectively, 3 and 2 times the S oxidation from the elemental sulfur reference. Results indicated that P content stimulates the soil microorganisms' activity for S oxidation. The matrix had a physical role in improving Bay dissolution and regulating the rapid release from Str. Moreover, the available P in soil was 25-30 mg/dm3 for Bay composites, while for pure Bay, it was 9 mg/dm3.

Experimental Evidence of CO2 Photoreduction Activity of SnO2 Nanoparticles.

Tin dioxide (SnO2 ) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO2 photoreduction in the gas phase. The hydroxylation of the SnO2 surface played a role in the CO2 affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH4 ), carbon monoxide (CO), and ethylene (C2 H4 ) is related to different SnO2 hydrothermal annealing. The best performance was seen for SnO2 annealed at 150 °C, with a production of 20.4 µmol g-1 for CH4 and 16.45 µmol g-1 for CO, while for SnO2 at 200 °C the system produced more C2 H4 , probably due to a decrease of surface -OH groups.

Role of urea and melamine as synergic co-plasticizers for starch composites for fertilizer application.

Herein we describe the interaction of starch, urea, and melamine (C3N6H6) in composite materials for use as controlled-release plant fertilizer. Slow-release fertilizers are important in minimizing nutrient losses due to run-off, leaching, and other factors. Urea is an effective plasticizer for starch and is an important nitrogen fertilizer throughout the world. Melamine also has high nitrogen content and could be combined with urea-starch composites to provide enhanced controlled-release fertilizer. This study reports the structural interaction and the performance gain of melamine addition to starch-urea composites. Composites were characterized by spectroscopic techniques (FT-Raman and 13C NMR) detailing the interaction between melamine, urea, and starch. These interactions helped facilitate extrusion processing by lowering viscosity and processing temperatures suggesting an enhanced starch plasticizing effect of starch-urea-melamine composites. Further research into the co-plasticization of starch by urea and melamine could be exploited for improved controlled-release fertilizer products. Further research into the co-plasticization of starch by urea and melamine could be exploited for improved controlled-release fertilizer products.

Biodegradable oil-based polymeric coatings on urea fertilizer: N release kinetic transformations of urea in soil

Polymer coatings are used to control the rate of release of plant available nutrients from fertilizers as well as to reduce nutrient losses such as ammonia (NH3) volatilization. Although the literature presents several examples of materials used to coat urea, little is known about nitrogen (N) release properties such as the mechanism involved and phenomena (e.g., pore opening) in the polymer coating. Thus, this study investigated urea release from polyurethane (PU) derived from two renewable raw materials (castor oil and soybean oil), to explain how the oil structure and coating microstructure influence release and urea-N dynamics in soil. The results demonstrated that the profile of urea release and the urea-N mineralization in the soil could be controlled by altering the thickness of the coating on the urea granules. Coating by eco-friendly polymer was efficient in controlling urea release in soil to reduce volatilization of ammonia and increase the availability of N in the soil.

Analysis of NH3-N Slow Release systems for fiber digestibility of low-quality forage: in vitro approach

Urea is a common non-protein supplement used in ruminant feed; however, excessive consumption may lead to poisoning by NH3. Although the slow release of urea into the rumen has shown to be an essential aspect for ruminant feed, to date only a few studies have addressed this matter. In this study we examined the influence of five different NH3-N slow release systems based on clay-urea nanocomposites on the fiber digestibility of low-quality forage (sugarcane straw) in vitro. Physical properties of nanocomposites were evaluated and their effects on digestibility were tested in vitro using pristine urea as a positive control (level of 1 % of DM of sugarcane straw sample) and sugarcane (with no additives) as a negative control. Ammonia release and digestibility were evaluated at 12, 24, 36, 48, 72 and 96-h. Generally, all nanocomposites increased (p < 0.05) digestibility of fiber over control under all the conditions stipulated, but the samples with hydrogel content were more expressive. We concluded that an ideal release rate and optimum environment for microbial synthesis are necessary to maximize the digestion of sugarcane.