ACS Sustainable Chemistry & Engineering最新文献

Surge in lithium-ion battery (LIB) production predicts that massive spent LIBs will be produced in the future. Hence, rational utilization of spent LIBs is a win-win strategy to protect the environment, recycle resources, and reverse the dilemma of the current energy challenges. In this work, different decommissioned layered oxide cathodes were recovered and converted into a novel NiCoMn phosphides–nickel foam (NCM-P) electrode for the OER using acid leaching to extract valuable metals and then carrying out a hydrothermal process and phosphating. The enhanced inherent catalytic activity can be achieved by regulating intermetallic interactions with adjusting the stoichiometric ratio of transition metal. Additionally, the NCM 111-P catalyst obtained from the spent LiNi_0.33Co_0.33Mn_0.33O₂ cathode has a special nanosheet–nanoneedle hierarchical structure, resulting in abundant active sites and stimulative detachment of gases in the OER course. Consequently, the NCM 111-P exhibits competitive catalytic performance (overpotential of 277 mV at 10 mA cm^–2, electrolytic durability of 246 h). The research furnishes a positive way to recycle spent LIBs and promotes the development of electrolytic water.

The widespread use of plastic mulch has caused serious environmental problems and poses a potential threat to human health. However, biomass-based films as the most commonly used alternative still exhibit unsatisfactory characteristics, including low wet mechanical stability, high processing costs, and harsh biodegradable conditions. Here, a high moisture retention capability (38 °C, 90 ± 2% RH) corn stover mulch film (CCP-PMF) with outstanding mechanical stability in both wet and dry environments is prepared by intrinsic lignin structural rearrangement and multimolecular-scale interfacial regulation synergy strategy. The elaborated composite films exhibited superior tensile index (68.9 N m g^–1), effective moisture retention (259.8 cc m^–2/24 h), and excellent biodegradability (28 days) compared to conventional mulches. Notably, the improved moisture resistance of CCP-PMF films allows for the integration of herbicides, resulting in CCP-PMF-based weed control films (AE-CCP-PMF) that provide a multifunctional solution for corn stover-based mulch films, broadening their potential for agricultural applications with lower environmental impacts (e.g., weed control film). This work demonstrates the potential of corn stover-based films as a sustainable alternative in agricultural practices, in line with the growing demand for environmentally friendly agricultural solutions (e.g., moisturized and biodegradable).

To address increasing climate deterioration, it is of great value to prepare highly permselective separation membranes for CO₂ enrichment and separation. In this study, zirconium-based metal-organic frameworks (Zr-MOFs) containing defective structures (defected-UiO-66-NH₂, D-UN) with a high volume yield (12 g L^–1 in a single batch) were prepared at room temperature for the first time using a simple green-synthesis strategy. After the modification with pentafluorobenzaldehyde, the fluorine-containing D-UN (named F-g-UN) nanoparticles showed the characteristics of local and dense distribution of fluorine elements. Due to the optimized CO₂ affinity and improved dispersion of fluorination modification, the prepared mixed-matrix membrane (MMM) F-g-UN@AO-PIM-1 achieved synergistic improvement in CO₂ permeability and selectivity, exceeding the 2008 Robeson upper bound (CO₂ 664.1 Barrer and CO₂/CH₄ 34.2) and the 2018 binary CO₂/CH₄ mixed-gas upper bound (CO₂/CH₄ 28.7). The substantial cause was the introduction of fluorine species, verified by relevant experiments and mechanism analyses such as CO₂ adsorption. This work proves the feasibility of using crystal defect engineering and post-treatment strategies to enhance separation functions and offers new insights into designing efficient and low-cost MMMs for gas separation, promoting their application in separation membranes including but not limited to gas separation.

Catalytic transfer hydrogenation (CTH) of nitrobenzene (NB) to value-added azobenzene has been a long-standing challenge. Here, we report that constructing magnetic iron-based catalysts enriched with oxygen-vacancy defects and appropriate Fe⁰ can enhance the catalytic activity and selectivity for the CTH of NB to azobenzene. The concentrations of oxygen-vacancy defects and Fe⁰ can be precisely tuned by altering the reduction temperature of iron-based catalysts. FeO_x-600 catalyst with the richest oxygen-vacancy defects and appropriate Fe⁰ sites shows full conversion of NB with 98.6% azobenzene selectivity in 12 h at 80 °C. Glycerol is used as the hydrogen donor, and lactic acid is selectively obtained (91.6%) during the CTH of NB. FeO_x-600 shows catalytic performance comparable to that of the state-of-art Au-based catalysts for the direct production of azobenzene from NB. FeO_x-600 also shows good stability during the 6 catalytic recycles. This is the first report of an iron-based catalytic system that can selectively convert NB to azobenzene from glycerol; in this regard, it is an exciting discovery that has the potential for large-scale industrial applications.

Li–N₂ is a subset of Li–air batteries, without a testing protocol. Porous graphene was employed as the cathode to study the cycling of Li–N₂. The nitrogen reduction mechanism was revised to an electrochemical interaction between lithium and nitrogen. The role of the Li₃N interface during cycling was discovered. Using in situ electrochemical impedance, the study discerns the instability of the interface formed during the initial cycles. An abnormal phenomenon that the discharge voltage platform rose after cycling prompts a detailed characterization of the interface evolution during the initial and subsequent cycles. In the later stage of the Li–N₂ battery, it seems that N₂ fixation no longer occurs due to the occurrence of side reactions. Finally, the study proposes preforming the cathode interface to improve cycling performance. The article sheds light on the challenges and opportunities for metal–N₂ batteries.

Thermosensitive polymer solutions and hydrogels show great potential for thermochromic windows. However, current research often overlooks two critical factors: thermal stability under heating and processability, which are typically contradictory. This study develops a physically cross-linked hydrogel specifically for thermochromic smart windows, aiming to achieve an optimal balance between these two factors. The hydrogel is made from low-cost, environmentally friendly materials, using commercial block polyether (L62) combined with a poly(vinyl alcohol)-borosilicate network. By optimizing PVA and borax concentrations at 2 and 0.3%, the hydrogel demonstrates good thermal stability, showing no significant changes after repeated heating to 60 °C for 9 h. Additionally, it exhibits excellent processability, allowing it to flow and fill gaps between glass slides when heated. The transition temperature for transmittance and solar modulation can be easily adjusted by varying the concentration of L62. The resulting hydrogel achieves tunable transition temperature, high luminous transmittance (71.2%), solar modulation efficiency (72.2%), and excellent durability. Compared to air-sandwiched windows, these thermochromic smart windows exhibit a significant cooling effect, with temperature responsiveness contributing up to 50%, depending on hydrogel thickness. This work addresses key issues that will advance the industrial application of hydrogel-derived thermochromic smart windows.

In this study, alkali-activated granulated blast furnace slag (AAS) was selected as a low-carbon precursor for fabricating an inorganic radiative cooler via accelerated carbonation and BaSO₄ nanoparticles (NPs) modification. The influence of the accelerated carbonation and BaSO₄ dosages on the solar reflectance and thermal emittance were experimentally investigated, along with multiple analytical characterizations that provide insights into the correlation between phase/microstructure transformation and optical properties. Additionally, small-scale field tests were conducted to validate the cooling performance of the as-fabricated sample in outdoor environments. An energy balance analysis was subsequently performed to calculate the corresponding net cooling power. The results revealed that the synergy of carbonation and BaSO₄ NPs significantly improved the solar reflectance from 10.3 to 83.9% while having negligible impact on the thermal emittance. Mechanism analysis indicated that the whitening effect of BaSO₄ NPs and its capability to promote the formation of calcite and capillary pore were responsible for the improved solar reflectance. Outdoor measurements demonstrated an excellent passive cooling performance compared to the plain sample, with an average temperature drop of ∼10 °C in the midday, corresponding to a net cooling power of 59 W/m². This work paves the way for upcycling waste slag into a high-performance passive cooling material while also capturing CO₂ for energy-efficient buildings.

The electrochemical CO₂ reduction reaction (eCO₂RR) is a sustainable approach for converting CO₂ into high-value-added products to promote carbon neutrality but is limited by low reaction selectivity and activity. Multinuclear Cu(I) cluster complexes are considered to be one of the most promising catalysts due to abundant copper sites, high atom utilization, and excellent stability. Herein, we synthesized two tetranuclear Cu(I) complexes [{Cu₂(μ-dppm)₂}₂(μ₃-η²(N,N),η¹(N),η¹(N)-pytz)₂](ClO₄)₂ (1) and [{Cu₂(μ-dppm)₂}₂(μ₃-η²(N,N),η¹(N),η¹(N)-mpytz)₂](ClO₄)₂ (2) and investigated their performance for eCO₂RR. X-ray structural analysis revealed that 1 and 2 were two Cu(I) clusters with similar planar Cu₄N₈ units, but 2 showed worse planarity than 1 due to the steric hindrance of the methyl into the 3-position on the pyridyl ring. Complex 1 achieved an optimal CH₄ Faradaic efficiency (FE_CH4) of 43% with a partial current density (j_CH4) of 70.85 mA·cm^–2 at −1.1 V, which was superior to that of methylated derivative 2. Mechanistic investigations demonstrated that stronger π-conjugation in complex 1 upshifted the d-band center, enhancing the adsorption and activation of the Cu site to the key reaction intermediate. And the highest occupied molecular orbital–lowest-unoccupied molecular orbital (HOMO–LUMO) gap was decreased, which facilitated electron transfer between active sites and CO₂. Moreover, π-conjugation enhanced the electropositive properties of the Cu site, thereby forming an acidic local microenvironment to promote the hydrogenation of intermediates toward CH₄. This study provides new insights into the design of efficient multinuclear Cu(I) catalysts for the electrocatalytic reduction of CO₂ to CH₄ by modulating conjugation effects.

The application of zero-emission passive radiative coolers is a crucial step toward global carbon neutrality. However, a single radiative cooling function cannot meet the thermal requirements under various weather conditions. We present a dual-mode thermal management film that integrates passive radiative cooling and heating functions through its porous polymer surface for cooling and a light-to-heat conversion surface enabled by graphene and carbon nanotubes for heating. The surfaces of the dual-mode film were physically flipped, positioning the corresponding surface toward solar radiation to obtain the desired functionality. In the cooling surface, the film achieves sub-ambient cooling of ≈13.3 °C under 853.88 W m^–2 of sunlight, thanks to its high solar reflectance (0.92) and mid-infrared emissivity (0.95). In the heating surface, it uses high solar absorption (0.90) to increase the temperature by 11.4 °C and generates Joule heating at various voltage levels. According to EnergyPlus software estimates, buildings with roofs covered in the film could reduce CO₂ emissions by 1.109 billion metric tons, equivalent to 3% of current global CO₂ emissions. This study offers a promising solution to climate challenges and holds great potential for energy savings and carbon reduction.