ChemSusChem最新文献

Generating hydrogen directly from seawater is an attractive feature for realizing large-scale solar fuel production. Here, we present an effective photocatalyst design that not only considers solar light activity but also long-term durability and optimized manufacturing costs. A series of stabilized bimetallic Au–Ag plasmonic “rainbow” nanoparticles were synthesized and grafted at low loadings onto TiO₂ substrates, yielding strong visible-light absorption and enhanced photocatalytic activity. To address the intrinsic instability of (plasmonic) metal nanoparticles in saline environments, two encapsulation strategies were investigated: insulating layer-by-layer (LbL) polyelectrolyte shells and conductive polyaniline (PANI) shells formed via in situ polymerization. In simulated seawater, a maximum H₂ evolution rate of 348 ± 108 µmol g⁻¹ h⁻¹ was achieved for TiO₂ + 2 wt% “rainbow” PANI-stabilized nanoparticles. PANI-stabilized plasmonic catalysts outperformed both bare and LbL-coated samples while maintaining full activity even after 1 month of storage in the dark in simulated seawater. These results demonstrate that conductive polymer encapsulation effectively preserves plasmonic activity even in harsh media, offering a prospect toward durable and economically viable solar hydrogen production from simulated seawater.

Plastic upcycling into iso-alkenes offers a sustainable route to mitigate plastic pollution and reduce the carbon footprint relative to petroleum-derived routes. However, selective C─C bond cleavage remains challenging, often resulting in broad product distributions and limited yields. Here, we report a tandem decomposition-catalysis strategy employing ternary-active ZnAlO catalysts for the selective conversion of polypropylene (PP) into narrow-range iso-alkenes. Zn₁₀AlO (10 wt% Zn proportion) achieved a liquid yield of 77.75 wt% with 83.71% selectivity toward C₈–C₁₂ iso-alkenes. The catalyst maintained liquid yield above 77 wt% and selectivity of ~84% toward narrow-range iso-alkenes over 10 successive cycles without catalyst regeneration. Furthermore, Zn₁₀AlO exhibited strong tolerance toward real-world PP waste, delivering product distributions comparable to those obtained from virgin PP. Structural and catalytic investigations revealed that the ternary-active ZnO─ZnAl₂O₄─Al₂O₃ nanocomposite, featuring balanced acidity and abundant oxygen vacancies, promoted controlled β-scission and isomerization while suppressing excessive cracking. Simply put, this work established a catalyst design strategy that integrated ternary-active nanocomposites and tailored acidity to overcome the yield-selectivity trade-off in PP upcycling and enabled the efficient production of value-added narrow-range iso-alkenes.

Electrocatalytic CO₂ reduction (CO₂RR) converts CO₂ into high-value chemicals and fuels using renewable electricity, serving as a core technology for recycling of carbon resources and supporting the carbon neutrality goal. Nevertheless, multiple bottlenecks hinder its transition toward industrial-scale application. These include poor catalyst stability under industrial-level high current density, uneven mass transfer and limited durability of key components during electrolyzer scale-up, high energy consumption together with difficult product separation and purification, mismatches between intermittent renewable energy supply and continuous electrolysis operation, as well as insufficient synergy between fundamental research and engineering applications. Economic factors also constrain industrialization, such as weak cost competitiveness, long investment-return periods, and imperfect carbon-pricing mechanisms. Aiming at the full-chain industrial implementation of CO₂RR, this paper systematically analyzes the challenges and underlying mechanisms of four core modules: catalysts, electrolysis systems, product separation, and system integration. It reviews the latest technological breakthroughs and feasible solutions, emphasizing the importance of fundamental research-engineering synergy, policy support, and interdisciplinary integration. This work provides a systematic reference and rational development direction for scientific research breakthroughs and industrial transformation of CO₂RR technology.

Alkali-metal amino acid solutions are attractive liquid sorbents for carbon capture. Potassium glycinate shows more favorable CO₂ capture behavior than sodium and lithium analogues despite sharing the same reactive amine motif. However, the molecular origin of this countercation effect remains unresolved. Here, we use molecular dynamics simulations to examine how K⁺, Na⁺, and Li⁺ regulate CO₂ accessibility and transport in aqueous glycinate solutions. We treat CO₂ uptake as a multistep process in which interfacial accessibility and transport precede chemical conversion, and we isolate this pre-reactive stage. Li⁺ forms a compact coordination environment with glycinate and water, restricting molecular mobility and reducing CO₂ access to glycinate-centered regions. In contrast, K⁺ maintains a more diffuse solvation environment, supporting higher diffusivities, larger interfacial CO₂ populations, and more frequent vapor-to-liquid transfer events. Collectively, these results identify interfacial gating, defined as cation-dependent control of CO₂ population and exchange frequency at the vapor–liquid boundary, as the interfacial manifestation of a cation-controlled CO₂ accessibility mechanism around glycinate.

Electrochemical nitrate reduction (NO₃RR) provides a sustainable route for ammonia (NH₃) synthesis while also enabling the treatment of nitrogen-containing wastewater. Herein, Bi nanoparticles were anchored on Ti₃C₂T_x MXene through an in situ reduction strategy to form Bi–NP/MXene. Compared with pristine MXene, Bi–NP/MXene exhibits markedly improved NO₃RR activity and NH₃ selectivity, achieving a Faradaic efficiency of 93.2% at −1.2 V versus reversible hydrogen electrode (RHE) and an NH₃ yield rate of 195.3 μmol h⁻¹ cm⁻² at −1.4 V versus RHE. The catalyst retains stable performance over six consecutive cycles and 1200 min of continuous electrolysis. Density functional theory calculations reveal that Bi incorporation regulates nitrate-derived intermediate adsorption, suppresses H* binding, and reduces the energy barrier of the potential-determining step from 1.36 to 0.74 eV. Moreover, a Zn–NO₃⁻ battery employing Bi–NP/MXene enables simultaneous NH₃ production and electricity generation.

Proton exchange membrane water electrolysis (PEMWE) is a promising route to low-carbon hydrogen production, but its sustainability remains incomplete unless the electrolyzer itself is designed for circularity. Repeated stack replacement can impose substantial lifecycle burdens because PEMWE relies on resource-intensive components such as iridium-based anodes, fluorinated polymer membranes, and titanium-based stack materials. Here, we investigate the significance of introducing remanufacturing into PEMWE systems from the perspective of design for remanufacturing and resource circulation. Repeated new-manufacturing and repeated remanufacturing scenarios are compared using the Sustainability Benefit Ratio (SBR), a lifecycle-oriented indicator that integrates greenhouse-gas burdens, avoided burdens, and valuation-weighted lifecycle factors into a unified circular-economy metric. The results show that remanufacturing consistently improves the cumulative environmental–economic balance relative to repeated new manufacturing, reduces carbon-footprint-based burdens, and enables repeated circulation of valuable stack-related resources while maintaining comparable hydrogen output. Cost decomposition and sensitivity analysis further reveal that the OER electrode governs the circular value of PEMWE remanufacturing and that its contribution can be translated into practical design targets in terms of catalyst cost, remanufacturing cost, recovery ratio, and electrochemical performance. These findings demonstrate that SBR can serve as a practical design-support tool for quantifying circular-economy value and guiding remanufacturing-oriented PEMWE development.

Rechargeable zinc–air batteries are highly promising next-generation electrochemical energy storage devices because of their advantages, such as high theoretical energy density, enhanced safety, and environmental friendliness. The development of efficient and stable bifunctional oxygen electrocatalysts is crucial for improving the performance of zinc–air batteries. This review systematically summarizes recent design strategies and research progress in composite catalysts developed to address this challenge. First, the working principles of zinc–air batteries and the key challenges faced by oxygen electrode catalysis are outlined, including the large voltage gap, the difficulty of single active sites in simultaneously meeting the requirements for both the OER and ORR, and conflicts between material hydrophilicity and hydrophobicity. On this basis, the design principles of composite catalysts are discussed, with a focus on optimizing the electronic structure through synergistic effects between components, achieving high dispersion of active sites, and constructing heterointerfaces to enhance charge transfer and intermediate adsorption/desorption capabilities. Finally, prospects and future directions for composite catalysts in zinc–air batteries are presented. Ongoing efforts are needed in areas such as precise regulation of active sites, elucidation of multicomponent synergistic mechanisms, and improvement of durability under practical operating conditions to advance the practical application of high-performance and low-cost zinc–air batteries.

Poly(ionic liquid)s (PIL) are a class of highly designable functional polymers that integrate the high ionic conductivity, a wide electrochemical stability window, and intrinsic flame retardancy of ionic liquids, positioning them as leading candidates to overcome the safety bottlenecks of conventional lithium batteries. This review systematically summarizes recent advances in PIL across three critical application areas: homogeneous solid electrolytes, composite solid electrolytes, and multifunctional electrode binders. It highlights PIL molecular design strategies, compositing approaches with flexible polymers, nanoparticle composites, and porous framework composites, as well as the performance advantages of bifunctional binders in both cathodes and anodes. Furthermore, this review provides an in-depth analysis of key challenges, including the inherent trade-off between ionic conductivity and mechanical strength, interfacial degradation over prolonged cycling, and high costs associated with large-scale manufacturing. Future directions are outlined with a focus on precise molecular engineering and in situ interfacial engineering, offering a forward-looking reference for the design of high-safety, high-performance solid-state lithium batteries.

Aqueous zinc-ion batteries (ZIBs) are promising candidates for large-scale energy storage. However, their practical application is severely hindered by Zn anode instability caused by water-induced side reactions and dendritic growth. Herein, a multifunctional TiN─TiO₂ (TNO) heterostructure is constructed on the Zn anode, effectively suppressing parasitic side reactions and regulating Zn deposition behavior to achieve dendrite-free anodes. Combined experimental characterizations and density functional theory (DFT) calculations reveal that the TNO layer modulates the local coordination environment of hydrated Zn²⁺ at the electrode–electrolyte interface, accelerating interfacial desolvation kinetics and inhibiting the hydrogen evolution reaction. Simultaneously, its strong chemical affinity toward the Zn (002) plane guides horizontal, dense, and highly textured Zn deposition. As a result, the TNO-coated Zn anode (TNO@Zn) exhibits outstanding electrochemical stability, enabling stable cycling for over 3000 h at 1 mA cm⁻² and 1.0 mAh cm⁻². Moreover, TNO@Zn//NH₄V₄O₁₀ cell retains a high specific capacity of 152 mAh g⁻¹ after 4000 cycles. The work provides mechanistic insights into interfacial heterostructure engineering and presents a viable strategy for the development of durable aqueous Zn metal batteries.

Chemical recycling of polystyrene (PS) by high-temperature pyrolysis can recover styrene monomer, but conventional processes require substantial energy input and generate complex, nonrecyclable byproducts. Here, we report an additive-free continuous-flow depolymerization of PS using localized microwave (MW) heating. A toluene solution of PS was passed through a quartz cartridge packed with spherical activated carbon beads (CBs), which concentrate MW energy and create a confined high-temperature reaction zone. Using a temperature-controlled single-mode MW reactor, the effects of backpressure and feed delivery were examined with reagent-grade PS and postconsumer PS products, including takeout trays and containers. Backpressure was found to be essential for stable styrene production. Without backpressure, channel occlusion occurred and the styrene yield reached only 19% after 4 h, whereas 0.5 MPa backpressure enabled 70%–76% styrene yield after 24 h. Postconsumer PS feeds also afforded 67%–76% styrene yield, comparable to reagent-grade PS. The coproducts were mainly limited to dimers and trimers, supporting distillative styrene recovery. This cartridge-based MW-flow system provides a simple route for direct styrene recovery from diverse PS waste streams under low-power, localized heating conditions.