ChemSusChem最新文献

In the pursuit of high-energy-density lithium metal batteries (LMBs), the development of stable solid electrolyte interphase (SEI) is critical to address issues such as lithium dendrite growth and low Coulombic efficiency. Herein, we propose a facile strategy for the in-situ fabrication of a LiCl-rich artificial SEI layer on Li surfaces through reaction of MoCl₅ with Li (Li@MoCl₅). The resulting artificial SEI significantly enhances the uniformity of Li deposition, effectively suppresses dendrite formation, and improves electrochemical performance. As a result, Li@MoCl₅ symmetric cells demonstrate remarkable stability, achieving continuous cycling of 4200 h under a high current density of 10 mA cm^-2 with an areal capacity of 1 mAh cm^-2. Full-cells employing Li@MoCl₅ exhibit superior cycling stability and rate capability, even at high cathode loading (17 mg cm^-2). These results highlight the potential of this interface engineering strategy for advanced practical application of LMBs.

Valorization of carbohydrate-rich biomass by conversion into industrially relevant products is at the forefront of research in sustainable chemistry. In this work, we studied the inulin conversion into 5-hydroxymethylfurfural, in deep eutectic solvents, in the presence of acidic task-specific ionic liquids as catalysts. We employed aliphatic and aromatic ionic liquids as catalysts, and choline chloride-based deep eutectic solvents bearing glycols or carboxylic acids, as solvents. The reactions were performed in a biphasic system, with acetone as a benign extracting solvent, enabling continuous extraction of 5-HMF. We aimed to find the best experimental conditions for this transformation, in terms of catalyst loading, solvent, reaction time and temperature to achieve an economical and energy efficient process. We also analyzed the results in terms of solvent viscosity and structural organization as well as catalysts acidity, to elucidate which structural features mostly favour the reaction. Under optimized conditions, we obtained a yield in 5-HMF of 71 %, at 80 °C in 3 h. Our system can be scaled up and recycled three times with no loss in yield. Finally, comparison with the literature shows that our system achieves a higher yield under milder conditions than most protocols so far reported for the same transformation.

Sluggish oxygen evolution reaction (OER) is a crucial part of water splitting and solar fuel generation, which limits their utilization. Ni3S2 is a promising OER catalyst, in which surface reconstruction is an important step to improve performance. In this study, DFT calculations were employed to investigate the effect of surface reconstruction on (001), (110), and (101) surfaces of Ni3S2 in alkaline OER. According to the Pourbaix diagram and surface free energy landscape, Ni3S2 is prone to transform into Ni oxides and (oxy) hydroxides under alkaline OER conditions. This process induces exposed S atoms to leach and O from the electrolyte to incorporate S sites, thereby lowering the Bader charge of *O and increasing [[EQUATION]], and then decrease [[EQUATION]], the free energy penalty of the potential determining step. In general, the surface reconstruction enhances the OER activity through S leaching and adjusting the coordination environment. We believe this work not only provides insights into the clarification of surface reconstruction, but also provides a valuable guideline for the further discovery of efficient TM-based sulfides.

The tightly connected structure of polybenzimidazole (PBI) membrane can be relaxed by solvent/nonsolvent solution to achieve a high proton conductivity for vanadium redox flow battery (VRFB). However, the nature behind the solvent/nonsolvent strategy is not unraveled. This work proposes a guideline to analyze the effect of PBI membrane relaxing formulas based on the interactions between different components in membranes. The supreme-efficient PBI membrane derived by the DMSO/formamide formula according to the guideline displays a marvelous performance for VRFB, with the proton conductivity boosted by 4300 % (from 1.93 to 83.33 mS cm^-1), and VRFB assembled with this membrane achieves an outstanding energy efficiency of 82.5 % under 200 mA cm^-2. Moreover, this work profoundly unravels the structure, property and performance relationship of PBI membrane, which is of great value for the development of membranes.

Electrochemically grown copper nanoclusters (CuNCs: < 3 nm) from single-atom catalysts have recently attracted intensive attention as electrocatalysts for CO2 and CO reduction reaction (CO2RR/CORR) because they exhibit distinct product selectivity compared with conventional Cu nanoparticles (typically larger than 10 nm). Herein, we conducted a detailed investigation into the size dependence of CuNCs on selectivity for multicarbon (C2+) production in CORR. These nanoclusters were electrochemically grown from single Cu atoms dispersed on covalent triazine frameworks (Cu-CTFs). Operando X-ray absorption fine structure analysis revealed that Cu-CTFs containing 1.21 wt% and 0.41 wt% Cu (Cu(h)-CTFs and Cu(l)-CTFs, respectively) formed CuNCs of 2.0 and 1.1 nm, respectively, at -1.0 V vs. RHE. The selectivity for CORR products was particularly dependent on the size of CuNCs, with the Faraday efficiencies of C2+ products being 52.3% and 32.7% at -1.0 V vs. RHE with Cu(h)-CTFs and Cu(l)-CTFs, respectively. Spherical CuNCs modeling revealed that larger cluster sizes led to a greater proportion of a surface coordination number (SCN) of 8 or 9. Density functional calculations revealed that the CO dimerization reaction was more likely to proceed at SCNs of 8 or 9 compared to SCN of 7 because of the stability of the *OCCO intermediate.

Capacitive deionization (CDI) is a novel, cost-effective and environmentally friendly desalination technology that has garnered significant attention in recent years. Carbon materials, owing to their excellent properties, have become the preferred electrode materials for CDI. Given the significant differences between different ions, ion-selective performance has emerged as a critical aspect of CDI applications. However, comprehensive reviews on the selective ion separation capabilities of carbon materials for CDI remain scarce. This review examines the progress in developing carbon materials for ion-selective separation in CDI, focusing on regulatory mechanisms and representative materials. It also discusses the applications of selective CDI carbon materials in areas such as heavy metal removal, nutrient recovery, seawater desalination resourcing, and water softening. Furthermore, the challenges and future prospects for advancing carbon materials in CDI are explored. This review aims to provide theoretical insights and practical guidance for utilising carbon materials in wastewater treatment and resource recovery.

Concentrated solar-driven CO2 reduction is a breakthrough approach to combat climate crisis. Harnessing the in-situ coupling of high photon flux density and high thermal energy flow initiates multiple energy conversion pathways, such as photothermal, photoelectric, and thermoelectric processes, thereby enhancing the efficient activation of CO2. This review systematically presents the fundamental principles of concentrated solar systems, the design and classification of solar-concentrating devices, and industrial application case studies. Meanwhile, key technological advances-from theoretical foundations to practical applications-are also discussed. At the microscopic level, a comprehensive analysis of multiscale reaction kinetics within the domain of photothermal synergistic catalysis has been conducted. This analysis elucidates the significance of catalyst design, further detailing the intricate regulatory mechanisms governing reaction pathways and active sites through nanostructured catalysts, single-atom catalysts, and metal-support interactions. However, the transition from laboratory research to industrial-scale application still faces challenges, including the complexity of system integration, energy density optimization, and economic feasibility. This review provides a theoretical framework and practical guidance through a complete investigation of current technological bottlenecks and future development directions, with the aim of driving key advances in concentrated solar-driven CO2 reduction catalysis.

Hole transport layer (HTL)-free carbon-based perovskite solar cells (C-PSCs) own outstanding potential for commercial applications due to their attractive advantages of low cost and superior stability. However, the abundant defects and mismatched energy levels at the interface of the perovskite/carbon electrode severely limit the device efficiency and stability. Constructing a 2D layer on the surface of 3D perovskite films to form 2D/3D heterojunctions has been demonstrated to be an effective method of passivating surface defects and optimizing the energy level alignment in almost all kinds of PSCs. Due to the unique structure of HTL-free C-PSCs, 2D/3D heterojunctions play especially important roles. This review article summarizes the reports of 2D/3D perovskite heterojunctions in HTL-free C-PSCs. It describes the contributions of 2D/3D heterojunctions in terms of their roles in defect passivation, energy level optimization, and stability improvement. Finally, challenges and prospects of 2D/3D heterojunction for further development of HTL-free C-PSCs are highlighted.

This work aims to recover rare earths from wind turbines NdFeB magnets through pyrometallurgical and hydrometallurgical techniques. First, a NdFeB hydride powder is obtained by decrepitation with hydrogen. Subsequently, this powder was subjected to a chlorination roasting process and successive leaching with water to bring the metals into solution. This was followed by a liquid-liquid extraction to remove the iron and purify the rare earth solution. For this purpose, Aliquat 336 diluted in Solvesso was selected as the iron selective extraction agent. As a single extraction was not enough for complete iron removal, a second Fe extraction step was carried out. This second extraction step was performed using the restored organic phase. This restoration was achieved by treating the organic phase with Na2SO3 and then washing it with a 3M HCl solution. In this way, the process was achieved more sustainably. Finally, the rare earths contained in the final solution were precipitated using oxalic acid to obtain mixed rare earth oxalates.

Layered double hydroxides (LDHs), which resemble hydrotalcite, are a type of materials with cationic layers and exchangeable interlayer anions. They have drawn lots of curiosity as a high-temperature CO2 adsorbent because of its quick desorption/sorption kinetics and renewability. Due to its extensive divalent or trivalent cationic metals, high anion exchange property, memory effect, adjustable behavior, bio-friendliness, easy to prepare and relatively low cost, the LDHs-based materials are becoming increasingly popular for photocatalytic CO2 reduction reaction (CO2RR). Fabrication and modification are good ways to move forward the advancement of LDHs-based catalysts, which will help chemistry and materials science make great progress. In this review we discussed structural characteristics and the methods for preparation and modification of LDHs-based photocatalysts. We also highlighted and discussed the major developments and applications in photocatalytic CO2RR as well as the photocatalytic mechanism. The goal of the present review is to give a broad summary of the various LDHs-based photocatalysts and the corresponding design strategies, which could motivate more excellent research works to explore this kind of CO2RR photocatalysts to further increase CO2 conversion yield and selectivity.