ACS Sustainable Chemistry & Engineering最新文献

Developing efficient and robust electrocatalysts for overall water splitting is vital for sustainable green hydrogen production, yet it remains a formidable challenge. In this work, a robust Mo-doped FeNNi₃ antiperovskite catalyst (Mo-FeNNi₃) is fabricated via a facile two-step strategy involving hydrothermal reaction and subsequent nitrogen treatment. The designed hydrangea-like structure not only endows the electrocatalyst with a robust framework but also exposes abundant available active sites, thereby facilitating efficient mass transport and accelerating reaction kinetics. The as-prepared Mo-FeNNi₃ electrocatalyst delivers exceptional catalytic performance, requiring very low overpotentials of 17, 36, and 77 mV to achieve a current density of 10 mA cm^–2 for the hydrogen evolution reaction in alkaline, acidic, and neutral media, respectively, alongside an outstanding oxygen evolution reaction overpotential of 223 mV in alkaline solution. Remarkably, when employed in an alkaline electrolyzer (Mo-FeNNi₃||Mo-FeNNi₃), it delivers a current density of 10 mA cm^–2 at a remarkably low cell voltage of 1.472 V, significantly outperforming the commercial RuO₂||Pt/C benchmark (1.536 V). The theoretical studies provide evidence that the electronic structure regulation in Mo-FeNNi₃ accelerates water dissociation kinetics and optimizes the adsorption/desorption energies of reaction intermediates, thereby dramatically enhancing the hydrogen production efficiency.

Developing Pd-based catalysts for formic acid (HCOOH) dehydrogenation is of great significance to the advancement of renewable hydrogen utilization. However, traditional Pd surfaces typically display symmetrical electronic and geometrical configurations that suffer from both selectivity issues and CO poisoning phenomena, deteriorating their long-term HCOOH dehydrogenation performance. In this study, we report a bismuth–palladium (BiPd) alloy catalyst with asymmetric electronic and geometric Pd sites that achieved an exceptional H₂-evolving turnover frequency (5893.7 h^–1) of HCOOH dehydrogenation while maintaining over 96% catalytic activities spanning consecutive 15-round experiments. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and synchrotron X-ray absorption spectroscopy (XAS) characterizations verified the successful construction of BiPd alloys and that Bi components desymmetrized the electronic configuration of Pd sites toward the thermodynamically favored HCOOH dehydrogenation pathway for H₂ evolution. On the other hand, in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) and kinetic isotope effect experiments combined with density functional theory (DFT) calculations collectively demonstrated that Bi also diluted Pd ensembles, and the resulting asymmetric Pd architectures reduced the diversity of *CO adsorption configurations on the surface of BiPd alloys, effectively mitigating CO poisoning. This work underscores the critical role of alloying engineering in designing Pd-based catalysts for practically implementing sustainable hydrogen release from liquid organic hydrogen carriers.

The hydrodeoxygenation (HDO) of guaiacol demonstrates significant potential for the efficient conversion of biomass into biofuels and fine chemicals. In this work, a Ni/CeO₂ catalyst was synthesized via a combined hydrothermal and pyrolysis method; the catalytic performance of the material was evaluated, with a water-glycerol mixture employed as the in situ hydrogen donor. Under the optimal conditions of 280 °C and 6 h, the guaiacol conversion reached 56.71%, and the catalyst maintained a conversion rate close to 50% after four consecutive uses, showing excellent reusability. Combined with product distribution and characterization results, the HDO reaction pathways and mechanisms of guaiacol over Ni/CeO₂ were proposed. Metallic Ni active sites, oxygen vacancies, and surface acid sites exerted a synergistic effect to modulate the cleavage of C–O bonds and product selectivity. This study provides a feasible strategy for the selective conversion of guaiacol into high-value phenols.

The growing environmental concern over petroleum-based plastics has intensified the demand for sustainable alternatives with high performance and reliable processability. Bio-based plastics have attracted considerable attention as sustainable alternatives to petroleum-derived plastics. However, despite their environmental advantages, their development and application are severely constrained by the necessity for tedious chemical modification and complex processing. Herein, we propose a covalent adaptable network strategy to transform chitosan (CS) into a thermally processable bioplastic through simple and efficient dynamic covalent enamine cross-linking. The enamine bonds enable network rearrangement upon heating, imparting hot-press processability, thermal repairability, and closed-loop recyclability to the material. The resulting bioplastic exhibits a high flexural strength of 189.8 MPa, excellent moisture and solvent resistance, favorable recyclability, high thermal stability, a low thermal expansion coefficient of 1.05 ppm k⁻¹, superior quantitative green chemistry metrics, and rapid soil-burial disintegration. With these advantageous features, the developed bioplastic represents a promising sustainable substitute for conventional petroleum-based plastics.

Recycling spent graphite anodes is essential for the sustainable development of the lithium-ion battery (LIB) industry. Conventional recycling technologies are often constrained by inherent drawbacks, including high energy consumption, severe secondary pollution, and inadequate structural restoration. Herein, we report a simple room-temperature NH₃ plasma treatment strategy for regenerating spent graphite into high-performance anodes. Through precise control of the plasma treatment conditions, three key functions are achieved simultaneously: effective removal of residual passivating solid electrolyte interphase (SEI) species, restoration of the graphitic structural ordering and in situ nitrogen doping. The optimal regenerated anode (denoted N-Gr-20), obtained by 20 min plasma treatment, delivers a high reversible specific capacity of 412 mAh g^–1 at 0.5 C. It also exhibits excellent rate capability (296 mAh g^–1 at 3.0 C) and exceptional long-cycle stability, retaining a capacity of 286 mAh g^–1 after 350 cycles at 2.0 C. Electrochemical kinetic analyses indicate that the restored graphitic framework promotes solid-state Li⁺ diffusion, while nitrogen-induced surface defects provide additional active sites for surface-controlled lithium storage. Overall, this work establishes a green and sustainable closed-loop strategy for spent LIB recycling and verifies the promising application potential of plasma engineering in the regeneration of spent battery anodes.

Sodium-ion batteries (SIBs) have garnered widespread attention as a highly promising alternative technology to lithium-ion batteries (LIBs). Based on life cycle assessment and supply risk evaluation methods, this study establishes an evaluation framework to compare the resource–environment impacts of two SIBs and four LIBs. Results indicate that layered oxide SIBs reduce toxicity and human health impacts by more than 50% compared to LiCo_xNi_yMn_1–x–yO₂ (NCM) batteries, primarily due to their avoidance of copper and cobalt. Among LIBs, LiFePO₄ (LFP) exhibits the lowest greenhouse gas emissions, endpoint environmental impacts, and supply risks. The environmental burden of NCM batteries alleviates with increasing nickel content, but emissions from cathode materials remain above 37% of the total. Due to the geographical concentration and geopolitical instability of lithium, cobalt, and nickel in LIBs, their supply risk (208–815 × 10⁷) is higher than that of SIBs (18–26 × 10⁷). Competitiveness evaluation indicates that layered oxide SIBs exhibit superior sustainability (0.393–0.489) compared to high-nickel NCM (0.959). Moreover, optimizing production layout can reduce the carbon footprint by 15%, and increasing energy density can lower environmental burden and resource demand by 66%. This study provides a quantitative decision-making basis for battery technology selection, supply chain risk management, and global low-carbon layouts, holding significant importance for advancing the energy transition.

Catechol (1,2-benzenediol) is a critical platform chemical with a growing global market, currently produced primarily through the fossil-based Hock process to produce phenol from benzene, followed by its hydroxylation to catechol. As the transition toward a bio-based economy intensifies, identifying sustainable production routes from renewable resources like lignocellulosic biomass is essential. To that end, different biomass-to-catechol strategies have been developed, such as (i) lignin depolymerization, followed by catalytic conversion of their alkylated/methoxylated phenol monomers, or (ii) glucose fermentation to catechol. Yet both approaches face specific challenges that hamper strong market integration. As an alternative, this present study reports an interesting, yet long-neglected alternative, catechol synthesis in subcritical water from 2-acetylfuran, a biomass-derived furan obtained from, e.g., sorbitol dehydration or acylation of furan. Since the subcritical reaction of 2-acetylfuran to catechol essentially entails a rearrangement, a higher atom economy can be persued, compared to lignin and fermentation-based routes. After initial exploration, a systematic optimization of the reaction temperature, time, and Lewis catalyst concentration (ZnCl₂) through response surface modeling, a catechol yield of 52% was achieved (i.e., a 10-fold increase over what was previously achieved) at a conversion of 82% and a selectivity of 61% (applying catalyst concentration of 2.4 mol % ZnCl₂, 310 °C reaction temperature and 366 min reaction time). Mass balance closures reached 92–93%, identifying acetic acid as the primary side product formed through competing α-dicarbonyl cleavage, with virtually no catechol degradation under these reaction conditions. These findings establish 2-acetylfuran as a high-potential feedstock for sustainable aromatic production, offering a robust pathway for integrating green catechol into industrial biorefinery schemes.