Promoting nonsymmetric C-C coupling to valuable oxygenates without metal catalysts in alkali aqueous medium.

Efficient conversion of C1 molecules into multicarbon oxygenates is a promising avenue for energy storage. Herein, we synthesize adjustable alkanoic acids/alcohols from formate C1 molecules via a hydrothermal reaction without any metal catalyst participation. This is achieved via HCO* and HCOO- nonsymmetric C-C coupling by alkali catalysis in aqueous medium.

Catalytic conversion of cellulosic biomass to harvest high-valued organic acids.

Catalytic conversion of biomass provides an alternative way for the production of organic acids from renewable feedstocks. The emerging process contains complex reactions and strategies to cut down those complex biogenic materials into target molecules. Here, we review the catalytic conversion of cellulosic biomass toward high-valued organic acids. This work has summarized the key controlling reactions which lead toward formic acid, glycolic acid, or sugar acids in oxidative conditions and the main pathways for lactic acid or levulinic acid in the anaerobic environment from cellulosic biomass and its derivatives. We evaluate and compare different strategies and methods such as one-pot and two-step conversion. Additionally, the optimization of catalytic reactions has been discussed to realize the design of C-C coupling reactions, the development of multifunctional materials, and new efficient system. In all, this article gives an insight guide to precisely convert cellulosic biomass into target organic acids.

Potential Application Performance of Hydrochar from Kitchen Waste: Effects of Salt, Oil, Moisture, and pH.

The surge in kitchen waste production is causing food-borne disease epidemics and is a public health threat worldwide. Additionally, the effectiveness of conventional treatment approaches may be hampered by KW's high moisture, salt, and oil content. Hydrothermal carbonization (HTC) is a promising new technology to convert waste biomass into environmentally beneficial derivatives. This study used simulated KW to determine the efficacy of hydrothermal derivatives (hydrochar) with different salt and oil content, pH value, and solid-liquid ratio for the removal of cadmium (Cd) from water and identify their high heating value (HHV). The findings revealed that the kitchen waste hydrochar (KWHC) yield decreased with increasing oil content. When the water content in the hydrothermal system increased by 90%, the yield of KWHC decreased by 65.85%. The adsorption capacity of KWHC remained stable at different salinities. The KWHC produced in the acidic environment increases the removal efficiency of KWHC for Cd. The raw material was effectively transformed into a maximum HHV (30.01 MJ/kg). HTC is an effective and secure method for the resource utilization of KW based on the adsorption capacity and combustion characteristic indices of KWHC.

One-Pot Chitin Conversion to High-Activity Antifungal N,N-Dimethyl Chitosan Oligosaccharides.

Invited for this month's cover is the group of Ning Yan at the National University of Singapore. The image shows the production of modified oligosaccharides from marine biomass as powerful antimicrobial 'weapon' through the 'booster' made of formaldehyde. The Research Article itself is available at 10.1002/cssc.202300591.

One-Pot Chitin Conversion to High-Activity Antifungal N,N-Dimethyl Chitosan Oligosaccharides.

Chitosan oligosaccharide and its derivatives are known for their diverse biological activities. In this study, we communicate a convenient one-pot synthesis of N,N-dimethyl chitosan oligosaccharide (DMCOS) from chitin via acid-catalyzed tandem depolymerization-deacetylation-N-methylation pathway using formaldehyde as the methylation reagent. The synthesis protocol offers 77 % DMCOS that features a high degree of deacetylation, a high degree of methylation, and a low average molecular weight. Compared to chitosan, DMCOS exhibits superior antifungal activity against Candida species. Mechanism study reveals a previously non-reported hydroxyl group-assisted effect that facilitates the reductive amination reaction under strong acidic conditions. Overall, our findings demonstrate the feasibility of direct synthesis of DMCOS from chitin, highlighting its potential use in anti-fungal applications.

Rhizosphere effect on the relationship between dissolved organic matter and functional genes in contaminated soil.

Arsenic contamination in a mining area is a potential threat to the local population. In the context of one-health, biological pollution in contaminated soil should be known and understandable. This study was conducted to clarify the effects of amendments on arsenic species and potential threat factors (e.g., arsenic-related genes (AMGs), antibiotic resistance genes (ARGs) and heavy-metal resistance genes (MRGs)). Ten groups (control (CK), T1, T2, T3, T4, T5, T6, T7, T8, and T9) were set up by adding different ratio of organic fertilizer, biochar, hydroxyapatite and plant ash. The maize crop was grown in each treatment. Compared with CK, the bioavailability of arsenic was reduced by 16.2%-71.8% in the rhizosphere soil treatments, and 22.4%-69.2% in the bulk soil treatments, except for T8. The component 2 (C2), component 3 (C3) and component 5 (C5) of dissolved organic matter (DOM) increased by 22.6%-72.6%, 16.8%-38.1%, 18.4%-37.1%, respectively, relative to CK in rhizosphere soil. A total of 17 AMGs, 713 AGRs and 492 MRGs were detected in remediated soil. The humidification of DOM might directly correlate with MRGs in both soils, while it was influenced directly on ARGs in bulk soil. This may be caused by the rhizosphere effect, which affects the interaction between microbial functional genes and DOM. These findings provide a theoretical basis for regulating soil ecosystem function from the perspective of arsenic contaminated soil.

Application of heavy metal immobilization in soil by biochar using machine learning.

Biochar application is a promising strategy for the immobilization of heavy metal (HM)-contaminated soil, while it is always time-consuming and labor-intensive to clarify key influenced factors of soil HM immobilization by biochar. In this study, four machine learning algorithms, namely random forest (RF), support vector machine (SVR), Gradient boosting decision trees (GBDT), and Linear regression (LR) are employed to predict the HMimmobilization ratio. The RF was the best-performance ML model (Training R2 = 0.90, Testing R2 = 0.85, RMSE = 4.4, MAE = 2.18). The experiment verification based on the optimal RF model showed that the experiment verification was successful, as the results were comparable to the RF modeling results with a prediction error<20%. Shapley additive explanation and partial least squares path model method were used to identify the critical factors and direct and indirect effects of these features on the immobilization ratio. Furthermore, independent models of four HM (Cd, Cu, Pb, and Zn) also achieved better model prediction performance. Feature importance and interactions relationship of influenced factors for individual HM immobilization ratio was clarified. This work can provide a new insight for HM immobilization in soils.

Application of life cycle assessment and machine learning for the production and environmental sustainability assessment of hydrothermal bio-oil.

The hydrothermal bio-oil (HBO) production from biomass conversion can achieve sustainable and low-carbon development. It is always time-consuming and labor-intensive to quantitative relationship between influential variables and bio-oil yield and environmental sustainability impact in the hydrothermal conditions. Machine learning was used to predict bio-oil yield. Life cycle assessment (LCA) is further conducted to assess its environmental sustainability effect. The results demonstrated that gradient boosting decision tree regression (GBDT) have the most optimal prediction performance for the HBO yield (Training R2 = 0.97, Testing R2 = 0.92, RMSE = 0.05, MAE = 0.03). Lipid content is the most significant influential factor for HBO yield. LCA result further suggested that 1 kg of bio-oil production can cause 0.02 kg ep of SO2, 2.05 kg ep of CO2, and 0.01 kg ep of NOx emission, and environmental sustainability assessment of HBO is exhibited. This study provides meaningful insights to ML model prediction performance improvement and carbon footprint of HBO.

Palladium nanoparticles on chitin-derived nitrogen-doped carbon materials for carbon dioxide hydrogenation into formic acid.

Utilizing waste carbon resources to produce chemicals and materials is beneficial to mitigate the fossil fuel consumption and the global warming. In this study, ocean-based chitin biomass and waste shrimp shell powders were employed as the feedstock to prepare Pd loaded nitrogen-doped carbon materials as the catalysts for carbon dioxide (CO2)/bicarbonate hydrogenation into formic acid, which simultaneously converts waste biomass into useful materials and CO2 into a valuable chemical. Three different preparation methods were examined, and the two-stage calcination was the most efficient one to obtain N-doped carbon material with good physicochemical properties as the best Pd support. The highest formic acid yield was achieved of ∼77% at 100 °C in water with KHCO3 substrate under optimal condition with a TON of 610. The nitrogen content and N functionalities of the as-synthesized carbon materials were crucial which could serve as anchor sites for the Pd precursor and assist the formation of well-dispersed and small-sized Pd NPs for boosted catalytic activity. The study puts forward a facile, inexpensive and environmentally benign way for simultaneous valorization of oceanic waste biomass and carbon dioxide into valuable products.

Exploration of the Interrelationship within Biomass Pyrolysis Liquid Composition Based on Multivariate Analysis.

The diverse utilization of pyrolysis liquid is closely related to its chemical compositions. Several factors affect PA compositions during the preparation. In this study, multivariate statistical analysis was conducted to assess PA compositions data obtained from published paper and experimental data. Results showed the chemical constituents were not significantly different in different feedstock materials. Acids and phenolics contents were 31.96% (CI: 25.30−38.62) and 26.50% (CI: 21.43−31.57), respectively, accounting for 58.46% (CI: 46.72−70.19) of the total relative contents. When pyrolysis temperatures range increased to above 350 °C, acids and ketones contents decreased by more than 5.2-fold and 1.53-fold, respectively, whereas phenolics content increased by more than 2.1-fold, and acetic acid content was the highest, reaching 34.16% (CI: 25.55−42.78). Correlation analysis demonstrated a significantly negative correlation between acids and phenolics (r2 = −0.43, p < 0.001) and significantly positive correlation between ketones and alcohols (r2 = 0.26, p < 0.05). The pyrolysis temperatures had a negative linear relationship with acids (slope = −0.07, r2 = 0.16, p < 0.001) and aldehydes (slope = −0.02, r2 = 0.09, p < 0.05) and positive linear relationship with phenolics (slope = 0.04, r2 = 0.07, p < 0.05). This study provides a theoretical reference of PA application.

Hydrothermal synthesis of similar mineral-sourced humic acid from food waste and the role of protein.

Food waste is a challenging biomass resource due to its high moisture content, low calorific value, and complex composition. Natural humification of animal and plant residues is highly related to microorganism activity, but natural hydrothermal conditions are also speculated to play a significant role. In this work, a novel method for the conversion of food waste into artificial humic acid (HAa) under hydrothermal conditions is proposed. The results revealed that an optimum HAa yield of 43.5% from food waste was successfully obtained at 215 °C for only 1 h. Detailed analyses, including elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), nuclear magnetic resonance (NMR), and Fourier transform infrared (FT-IR) spectroscopy, showed that the produced HAa had similar structures and compositions with natural HA extracted from minerals. Moreover, the proteins contained in the food waste significantly promoted HA formation through the reaction of saccharides with amino acids, in which Maillard-like reactions were the key steps. These results not only provide experimental evidence for verifying the role of hydrothermal reactions in transforming food waste into humic acid but also provide insight into effective resource utilization of food waste.

Hydrothermal synthesis of long-chain hydrocarbons up to C24 with NaHCO3-assisted stabilizing cobalt.

Abiotic CO2 reduction on transition metal minerals has been proposed to account for the synthesis of organic compounds in alkaline hydrothermal systems, but this reaction lacks experimental support, as only short-chain hydrocarbons (

Dissolved organic carbon drives nutrient cycling via microbial community in paddy soil.

Microbial mediated iron cycling drives the biogeochemical cycling of carbon, nitrogen, sulfur, and phosphorus. However, the fate of the microbial community and the relative metabolic pathways in paddy soil after the addition of biogas slurry are poorly understood. In this study, the response of functional genes was investigated by growing one-season rice in paddy soils in a pot experiment. Seven treatments were prepared: 1) control (CK); 2) organic carbon (OC); 3) fertilizer (F); 4) 5% of biogas slurry (B05); 5) 10% of biogas slurry (B10); 6) 15% of biogas slurry (B15); 7) 20% of biogas slurry (B20). In the biogas slurry treatments, Geobacter increased more than in the other treatments during rice growth, which were structured by TOC. Particularly, in the B10 treatment, the relative abundance of Geobacter was 1.6 and 14.8 times higher than that of CK at the heading and mature stages, respectively. At the heading stage, the addition of biogas slurry and OC shifted the microbial phosphorus-transformation communities differently. There were no significant differences in the carbon, nitrogen, and sulfur metabolic pathways between the two treatments. At the mature stage, the carbon: nitrogen: phosphorus balance was significantly influenced by the regulation of functional gene expression and metabolic activities. These findings provide insight into the key factors affecting carbon, nitrogen, sulfur, phosphorus, and iron during rice growth after carbon inputs.

Bifunctional electrocatalysts for oxygen reduction and oxygen evolution: a theoretical study on 2D metallic WO2-supported single atom (Fe, Co, or Ni) catalysts.

Catalysts play a critical role in the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) for energy storage, conversion, and utilization. Herein, first-principles density functional theory (DFT) calculations demonstrated that single-metal-atom (Fe, Co, or Ni) sites can bind to the surface of 2D WO2, enhancing the adsorption of intermediates involved in the OER/ORR. Furthermore, it was found that the single-metal-atom-doped 2D WO2 achieves the smallest OER and ORR overpotentials of 0.42 V and 0.40 V, respectively, which are comparable to those of IrO2 or Pt-based catalysts. This predicts the excellent OER/ORR catalytic activities of the single-metal-atom (Fe, Co, or Ni) doped 2D WO2, which would be a promising bifunctional catalyst for fuel cells, water splitting, and metal-air batteries.

The endosperm-specific transcription factor TaNAC019 regulates glutenin and starch accumulation and its elite allele improves wheat grain quality.

In wheat (Triticum aestivum L.), breeding efforts have focused intensively on improving grain yield and quality. For quality, the content and composition of seed storage proteins (SSPs) determine the elasticity of wheat dough and flour processing quality. Moreover, starch levels in seeds are associated with yield. However, little is known about the mechanisms that coordinate SSP and starch accumulation in wheat. In this study, we explored the role of the endosperm-specific NAC transcription factor TaNAC019 in coordinating SSP and starch accumulation. TaNAC019 binds to the promoters of TaGlu-1 loci, encoding high molecular weight glutenin (HMW-GS), and of starch metabolism genes. Triple knock-out mutants of all three TaNAC019 homoeologs exhibited reduced transcript levels for all SSP types and genes involved in starch metabolism, leading to lower gluten and starch contents, and in flour processing quality parameters. TaNAC019 directly activated the expression of HMW-GS genes by binding to a specific motif in their promoters and interacting with the TaGlu-1 regulator TaGAMyb. TaNAC019 also indirectly regulated the expression of TaSPA, an ortholog of maize Opaque2 that activates SSP accumulation. Therefore, TaNAC019 regulation of starch- and SSP-related genes has key roles in wheat grain quality. Finally, we identified an elite allele (TaNAC019-BI) associated with flour processing quality, providing a candidate gene for breeding wheat with improved quality.

Natural mineral bentonite as catalyst for efficient isomerization of biomass-derived glucose to fructose in water.

The development of inexpensive and efficient heterogeneous catalyst for the conversion of biomass including food and winery processing waste to value-added products is crucial in biorefinery. Glucose could be obtained via the hydrolysis of waste cellulose or starch-rich material, and the isomerization of glucose to fructose using either Lewis acid or Brønsted base catalysts is an important route in biorefinery. As a natural clay mineral, bentonite (Bt) is widely used as adsorption material and catalyst support, but how its intrinsic acid-base properties can impact the biomass conversion chemistry is still rarely reported. In this study, we investigated the influence of the textural and acid-base properties of Bt on the glucose isomerization reaction. The reaction kinetics and mechanism, and the effect of Al3+-exchange were explored. The results showed that the activation energy of Bt-catalyzed glucose conversion was 59.0 kJ mol-1, and the in-situ Fourier transform infrared spectrometer (FT-IR) characterization proved that Brønsted base was responsible for the isomerization. The highest fructose yield of 39.2% with 86.3% selectivity could be obtained at 110 °C for 60 min in water. Alkaline rinse and calcination can recover most of the catalytic activity of the spent catalyst.

Atomic-scale evidence for highly selective electrocatalytic N-N coupling on metallic MoS2.

Molybdenum sulfide (MoS2) is the most widely studied transition-metal dichalcogenide (TMDs) and phase engineering can markedly improve its electrocatalytic activity. However, the selectivity toward desired products remains poorly explored, limiting its application in complex chemical reactions. Here we report how phase engineering of MoS2 significantly improves the selectivity for nitrite reduction to nitrous oxide, a critical process in biological denitrification, using continuous-wave and pulsed electron paramagnetic resonance spectroscopy. We reveal that metallic 1T-MoS2 has a protonation site with a pKa of ∼5.5, where the proton is located ∼3.26 Šfrom redox-active Mo site. This protonation site is unique to 1T-MoS2 and induces sequential proton-electron transfer which inhibits ammonium formation while promoting nitrous oxide production, as confirmed by the pH-dependent selectivity and deuterium kinetic isotope effect. This is atomic-scale evidence of phase-dependent selectivity on MoS2, expanding the application of TMDs to selective electrocatalysis.

Enzyme Mimetic Active Intermediates for Nitrate Reduction in Neutral Aqueous Media.

Nitrate is a pervasive aquatic contaminant of global environmental concern. In nature, the most effective nitrate reduction reaction (NRR) is catalyzed by nitrate reductase enzymes at neutral pH, using a highly-conserved Mo center ligated mainly by oxo and thiolate groups. Mo-based NRR catalysts mostly function in organic solvents with a low water stability. Recently, an oxo-containing molybdenum sulfide nanoparticle that serves as an NRR catalyst at neutral pH was first reported. Herein, in a nanoparticle-catalyzed NRR system a pentavalent MoV (=O)S4 species, an enzyme mimetic, served as an active intermediate for the NRR. Potentiometric titration analysis revealed that a redox synergy among MoV -S, S radicals, and MoV (=O)S4 likely play a key role in stabilizing MoV (=O)S4 , showing the importance of secondary interactions in facilitating NRR. The first identification and characterization of an oxo- and thiolate-ligated Mo intermediates pave the way to the molecular design of efficient enzyme mimetic NRR catalysts in aqueous solution.

Ni and Zn/ZnO Synergistically Catalyzed Reduction of Bicarbonate into Formate with Water Splitting.

Conversion of CO2 into value-added chemicals with a facile hydrogen source such as water is always of great interest for sustainable development. In this work, a simple and efficient method of reduction of bicarbonate to formate on a simple Ni powder catalyst with water as the facile hydrogen source and Zn as the regenerable reductant is proposed. The Ni catalyst and in situ formed Zn/ZnO exhibited a synergetic catalytic activity in the conversion of bicarbonate into formate, and a good formate yield of 81% was obtained. Detailed studies revealed that the synergetic catalytic activity between Ni and the in situ formed Zn/ZnO was mainly attributed to (i) the inhibited oxidation of Zn by Ni, leading to more interface of Zn/ZnO; (ii) the decreased growth of ZnO crystal along the [0001] direction, and thus increasing the more polar (0001) Zn face and the (0001̅) O face, which have high activity; and (iii) the enhanced generation of more oxygen vacancies at the Zn/ZnO interface to promote the formate yield. This research demonstrates an efficient method of using a simple and nonprecious metal catalyst for the CO2 reduction into value-added chemicals and provides a better understanding of the synergistic catalytic mechanism of Ni and Zn/ZnO.

Reduction of CO2 with H2S in a simulated deep-sea hydrothermal vent system.

H2S is considered to be an important reductant in abiotic CO2 reduction to organics, however, almost no experimental support has been reported. Herein, the first observation of CO2 reduction to formate with H2S under alkaline hydrothermal conditions is reported, and water is found to act as a hydrogen donor.