ACS Sustainable Chemistry & Engineering最新文献

The hydrogenation of CO₂ to produce valuable chemicals through photocatalytic or photothermal technologies represents a viable path toward carbon neutrality. However, typical nanosemiconductor materials, such as TiO₂, often exhibit limited activity, necessitating the optimization of their performance as a key research priority. Here, we demonstrate that the size of anatase TiO₂ significantly influences its performance in the selective photocatalytic and photothermal reduction of CO₂ to CO. The small-sized TiO₂ (S-TiO₂, 15 nm) exhibits a low CO yield of 32.7 μmol g^–1 h^–1 and shows almost no photothermal synergy. In contrast, the large-sized TiO₂ (L-TiO₂, 160 nm) demonstrates a high CO yield of 185.3 μmol g^–1 h^–1 and significant photothermal synergy, with the CO yield reaching 438.7 μmol g^–1 h^–1. We reveal that L-TiO₂ is well-crystallized and has a higher conduction band position compared to the S-TiO₂. This results in a higher charge separation efficiency and more effective photoexcited electrons for CO₂ reduction. Additionally, the external heating primarily enhances the charge separation in L-TiO₂, significantly improving the conversion of CO₂ to CO. This work provides insights into the relationship between the structure and activity of TiO₂ in photocatalytic and photothermal CO₂ reduction.

Offshore carbon capture utilization and storage (CCUS) is essential for addressing greenhouse gas emissions in China’s emission-intensive, land-constrained coastal regions. This study combines a dynamic reservoir estimation model with a drilling economic model to develop a multiwell optimization scheme that efficiently balances cost efficiency and storage capacity. The cost of saline aquifer storage varies from $3.69 to $12.51/t_CO2. A multiphase offshore storage source-sink matching model underpinned by a multiwell optimization framework is proposed to minimize full-process costs by integrating emission sources, coastal hubs, transport pipelines, and storage sinks. The network is economically optimized over a 25 year planning horizon to identify the optimal matching schemes, pipeline development, and phased economic evaluations. The results suggest that a 4.59 Gt emission reduction from 154 stationary sources in Zhejiang Province is economically feasible at an expenditure of $236.03 billion. The optimal CCUS network incurs a unit cost of $51.22/t_CO2, dominated by capture cost at 84.23%. The Qiantang, Minjiang, and Fuzhou basins are progressively developed and utilized. Notably, as the learning rate of technological advancements increases from 0.02 to 0.08, the unit capture cost decreases by 50.12%. This study provides guidance for the green low-carbon transition of offshore storage in the coastal regions of China.

The hydroxylation of inert benzene through the activation of the C_sp2–H bond is a representative reaction involving the transformation of C–H bonds to C–O bonds. Despite its far-reaching guiding significance, this process remains a complex scientific challenge. This issue was effectively addressed by achieving the hydroxylation of benzene with H₂O₂ into phenol utilizing a phase transition type catalyst of the VO_x-WO₃ series. This catalyst proved to be an efficient and economical synthesis route and presented a phenol yield of 90.2% (conversion >91%). This represents the highest conversion, which is attributed to the unique properties of the VO_x-WO₃ catalyst. In summary, the reaction path was optimized via the phase transformation of the catalyst at 70 °C. Herein, the introduction of tungsten regulates the acidity of the catalyst and the valence state of vanadium. Furthermore, it protects vanadium and forms a more active V–O–W active site, promoting the efficient transformation of the reaction.

Crystallization plays a critical role in chemical manufacturing, and the production efficiency of many crystallization processes has been significantly improved through the transition from batch to continuous operation. However, due to the more stringent process requirements of reactive crystallization compared to other crystallization methods, there are almost no precedents for successfully implementing continuous reactive crystallization. This study used the 1-phenyl-3-methyl-5-pyrazolone (edaravone) reactive crystallization process as a case to explore detailed strategies for upgrading from batch to continuous operation and to evaluate the performance of the continuous process. The results demonstrate the successful implementation of continuous reactive crystallization for edaravone. Experimental data show that the crystallization efficiency of the continuous process is 916.7% higher than that of the batch process in reactors of the same volume. Compared with industrial-scale batch reactors, the continuous system can achieve an approximately 2308.2% improvement in crystallization efficiency. Additionally, the continuous process produces crystals with a higher uniformity, indicating superior product quality. This study provides actionable insights into continuous reactive crystallization, offering valuable guidance for the optimization and industrialization of the continuous reactive crystallization process.

An economical and eco-friendly food sweetener erythritol with abundant hydroxyl groups and suitable site resistance has been added to ZnSO₄ electrolytes in aqueous Zn ion batteries (AZIBs). Density functional theory (DFT) calculations demonstrate that the O atoms in erythritol molecules can supply electrons to Zn²⁺, thus mitigating an electron transfer from H₂O to Zn²⁺, resulting in erythritol entering the solvation structure of Zn[(H₂O)₆]²⁺ and replacing some water molecules. Spectroscopic analysis confirms the altered solvation structure of Zn²⁺ and the reconstructed hydrogen-bonding network of the ZnSO₄ and erythritol electrolytes. With an equilibrium between “network water” and “free water” induced by erythritol additives, the possibility of active water decomposition is degraded, which further inhibits water-splitting and corrosion side reactions. In addition, theoretical studies and experimental characterizations verify that erythritol additives preferentially adsorb on the surface of Zn anodes, thus effectively protecting Zn anodes and inhibiting the mad growth of dendrites. As a result, the cells with ZnSO₄ + erythritol electrolytes demonstrated significantly higher Coulombic efficiency values and longer lifetimes than those of pure ZnSO₄ electrolytes. This study could advance the research process of small-molecule polyol additives for AZIBs.

The growing reliance on pesticides for food sustainability has led to environmental pollution and food safety concerns. Herein, we present a chemodynamic strategy using a Fenton-type nanopesticide, referred to as metal-phenolic ROS-nanogenerator (nanoRSG), to enhance the control of two widely spreading plant pathogens (Pseudomonas syringae and Fusarium oxysporum). The nanoRSG is constructed by the supramolecular self-assembly of natural polyphenols and Cu²⁺ ions, followed by an in situ transition into phenolic-stabilized CuO₂ nanoclusters with the aid of hydroxide ions in the presence of H₂O₂. Subsequently, the nanoRSG decomposes in the pathogenic-relevant microenvironment into Fenton-catalyzed H₂O₂ and Cu²⁺ ions, followed by the highly efficient Fenton reactions for generating •O₂^– to damage pathogenic cell membranes. Regarding curative effects on tomato leaves against P. syringae and F. oxysporum, nanoRSG outperforms the commercial Kocide 3000 formulations with 94.7 and 86.9% increasing efficacy, respectively. Moreover, for curative activity on tomato roots, nanoRSG also has a better performance (87.8 and 78.9%) than Kocide 3000 (31.3 and 43.9%). Besides, the biosafety of nanoRSG is confirmed by toxicity tests in zebrafish and lettuce cultivation in a field test of hydroponics. Our findings demonstrate that the metal-phenolic nanoenabled strategy offers a promising formulation for innovating conventional pesticides and enhancing food sustainability.

Supramolecular hydrogels have broad application prospects in asymmetric catalysis due to their unique properties, and the water environment inside the hydrogels plays an important role in green catalysis. This paper reports a novel C2-symmetric proline derivative gelator (p-L-Phe-Pro-COOH) with a hydrophobic benzene ring in the center and hydrophilic groups on both sides. The C2-symmetric structure can provide the gelator with more catalytically active sites. p-L-Phe-Pro-COOH can self-assemble in H₂O or H₂O/dimethyl sulfoxide (DMSO) mixed solvents to form gels with a three-dimensional network of left-handed intertwined helical nanofibers, namely, L-Hyd and L-Hyd-DMSO. The L-Hyd and L-Hyd-DMSO gels are used as catalysts for the aldol and Mannich reactions, achieving high yields (>90%), diastereoselectivity (dr >90/10 (anti/syn)), and enantioselectivity (ee value of 99%) of the products without requiring additional additives. Results indicated that the L-Hyd and L-Hyd-DMSO gels exhibited higher catalytic activity compared to that of the gelator. Further, the Mannich reaction catalyzed by L-Hyd-DMSO revealed that introducing DMSO considerably enhanced the reaction yield while maintaining a high enantioselectivity. The L-Hyd-DMSO effectively addresses the issue of low yield in Mannich reactions conducted in aqueous systems. In addition, the L-Hyd and L-Hyd-DMSO gels acting as catalysts can be recovered by simple extraction and maintain good reactivity after five cycles. The findings of this study indicate that supramolecular hydrogels show potential in asymmetric catalytic reactions, which closely align with the principles of green chemistry.