ChemSusChem最新文献

The Front Cover shows a newly developed method that uses a simple undivided electrochemical cell to perform oxidative functionalization of renewable furfural by using an indirect Baeyer–Villiger-type oxidation. In this method, bromine gets electrochemically generated from bromide salt followed by the formation of hypobromous acid, which acts as an oxidant. The immediate consumption of hazardous bromine as it is generated allows its concentration to be kept very low. The obtained yields are comparable to those of existing thermochemical methods and allow (renewable) electricity to be used as a driving force. More information can be found in the Research Article by J. H. Bitter and co-workers (DOI: 10.1002/cssc.202501861).

Despite its potential as a renewable feedstock, lignin, a major component of plant cell walls and a by-product of the pulp and paper industry, has long been underutilized. Historically, pulp mills employed ozonolysis, a powerful oxidative process, to delignify cellulosic fibers and break down lignin. The ability of this technique to modify lignin structures has attracted attention in recent years, creating opportunities for the development of novel lignin-based materials with improved functions. This review revisits the use of ozone as a bleaching agent and bridges its historical role in pulp processing with its emerging potential as a selective oxidative tool for lignin modification in materials chemistry. We discuss the fundamental chemical processes, significant developments in ozonolysis technology, and its potential to functionalize sustainable biomaterials. We also give our perspectives on the present obstacles and potential opportunities for ozonolysis optimization in lignin valorization.

The solar-driven photoelectrochemical (PEC) oxidation of glycerol to value-added C₃ products faces challenges due to the rapid charge recombination and unfavorable CC bond cleavage. This study presents a novel strategy through the rational design of a core–shell TiO₂@CuFe-cMOF photoanode, where caffeic acid (CA) serves as a bifunctional molecular bridge to engineer a conformal, atomically coherent heterojunction interface. The unique architecture significantly enhances interfacial charge transport, suppresses carrier recombination, and promotes the selective generation of hydroxyl radicals (·OH) as the primary oxidant. Under AM 1.5 G illumination , the optimized photoanode achieves remarkable performance metrics: a photocurrent density of 1.67 mA cm⁻² at 1.0 V_RHE (~3.2-fold higher than pristine TiO₂), together with glyceraldehyde (GLD) and 1,3-dihydroxyacetone (DHA) yields of 108 and 35.3 mmol m⁻² h⁻¹, representing ~3.0 times and ~2.3 times improvements over bare TiO₂, respectively. The results reveal that the reaction proceeds dominantly via ·OH-mediated CH activation, with the CA-bridged core–shell structure effectively steering the reaction pathway toward valuable C₃ products while suppressing over-oxidation to C₁ byproducts. This study demonstrates the critical role of ligand-mediated interfacial engineering in designing efficient heterostructured photoanodes and establishes a sustainable paradigm for valorizing biomass-derived feedstocks through solar energy conversion.

Ammonia decomposition is a key route for CO_x-free hydrogen production and nitrogen recycling, which requires efficient and durable catalysts. Non-noble metal catalysts are attractive because of their low cost and availability. However, low activity and poor stability caused by particle sintering hinder practical applications. Constructing an efficient ternary metal-promoter-support interface offers a viable strategy to overcome these limitations. Herein, an in situ exsolution method was employed to fabricate Co-Ba/La₂O₃ catalyst from high-purity perovskite precursor La_0.95Ba_0.05CoO₃ under reaction conditions. The efficient Co-BaO-La₂O₃ interface was constructed via Ba-promoted in situ exsolution process, outperforming that prepared by traditional methods and enhancing catalytic performance. The optimized catalyst achieves a high hydrogen production rate of 98.5 mmol H₂ g_cat⁻¹ h⁻¹ at 500°C, surpassing most reported Co-based catalysts, and exhibits excellent catalytic stability during the 200 h test. The superior performance originates from the unique interfacial structure with dispersed and anchored Co nanoparticles, which thereby strengthen metal–support interactions. The Ba promoter enhances interfacial charge transfer efficiency and catalyst basicity. This synergistic interface effectively facilitates nitrogen associative desorption and suppresses hydrogen poisoning. This work demonstrates that constructing an efficient exsolved interface can alleviate the activity-stability conflict, offering a new strategy for designing advanced non-noble metal catalysts.

Polyurethane (PU) adhesives are extensively employed in flexible packaging owing to their strong adhesion and excellent wettability. However, most conventional PU adhesives are petroleum-based, which has driven growing interest in biobased alternatives. In this article, we synthesized biobased PU adhesives for flexible packaging applications using 2,5-furandicarboxylic acid (FDCA) and carbon dioxide (CO₂). FDCA-based polyols (FPs) (2500–3500 g mol⁻¹) with processable viscosities were prepared from FDCA, succinic acid, and 1,3-propanediol. To further enhance adhesion by increasing hydrogen-bond density, the diol and triol containing urethane moieties were synthesized via CO₂-utilization technology. In T-peel tests, the adhesives crosslinked with CO₂-based triols exhibited the highest adhesion strength (986 gf/25 mm) and were compared with those crosslinked using petroleum-derived trimethylolpropane (TMP). The prepared adhesives exhibited low glass transition temperature (from −28  to −18°C), ensuring flexibility at room temperature. In addition, the synthesized adhesives could be degraded through base-catalyzed transesterification in ethanol/ethyl acetate, enabling clean substrate recovery. These sustainable FDCA/CO₂-based PU adhesives demonstrate strong potential as alternatives to petroleum-derived adhesives for flexible packaging.

Due to lower energy consumption, great separation performance, and simple operation process, membrane technology plays an important role in gas separation. However, separation membranes often face a trade-off between permeance and selectivity. For instance, the pure layered double hydroxide (LDH) or metal organic framework (MOF) membranes exhibit high gas permeance but suffer from low selectivity. However, conventional Pd membranes typically have a thickness exceeding 50 μm, resulting in high costs and limited permeance. This article develops a novel strategy to fabricate a CoAl LDH/zeolitic imidazolate framework (ZIF)-67 heterostructure on a polydopamine-modified substrate, following by the infiltration of Pd nanoparticles (Pd NPs) into the LDH/ZIF framework via magnetron sputtering, resulting in a well-integrated LDH/ZIF@Pd membrane for highly efficient H₂/CH₄ separation. In this architecture, the LDH sheets not only create nanocorridors for gas permeation but also provide the nucleation sites for ZIF grains. The incorporated Pd NPs and LDH/ZIF network form a well-integrated heterostructure, which endows the LDH/ZIF@Pd hybrid membrane with exceptional comprehensive performance, achieving H₂/CH₄ selectivity of 48.3 and ultrahigh H₂ permeance of 8.4 $$ 10⁵ GPU (75°C, 1 bar). This result sets a new benchmark for membrane-based gas separation, demonstrating outstanding potential for advanced hydrogen purification and sustainable energy applications.

Valorising crude glycerol, a major by-product of biodiesel production, is essential for advancing a circular chemical economy. Traditional methods of oxidising crude glycerol to produce value-added chemicals such as glycolic acid (GcA) and dihydroxyacetone (DHA) typically require noble metal catalysts and energy-intensive conditions. Herein, we present a catalyst-free, non-thermal plasma (NTP) process that operates in the liquid phase at ambient temperature and pressure. This novel approach enables the selective oxidation of glycerol into GcA and DHA without the need for added reagents or catalysts. With a deposited power of 9.6 W and short residence time, 100% selectivity towards GcA was achieved with 7% glycerol conversion. Extending the treatment time to 60 min increased glycerol conversion to 35%, with selectivities of 58% for GcA and 36% for DHA. These results highlight the potential of liquid-phase NTP as a sustainable and efficient method for upgrading crude glycerol under mild conditions.

Ammonia (NH₃), the world's second most produced chemical, is indispensable to modern society, with widespread applications in agriculture, chemical manufacturing, refrigeration, and energy storage. However, the conventional Haber–Bosch process for NH₃ synthesis is characterized by lengthy process flows, harsh operating conditions, and significant carbon emissions, rendering it increasingly misaligned with global carbon peaking and neutrality objectives. Consequently, there is an urgent need to develop new NH₃ synthesis technologies that are both energy-efficient and environmentally benign. This review specifically examines three promising gas–solid phase NH₃ synthesis routes driven by external fields: photocatalysis, plasma catalysis, and the emerging technique of alternating magnetic field (AMF) catalysis. We summarize recent progress in this area, discuss catalyst design strategies tailored to each approach, and identify persistent challenges at the level of catalytic materials, reaction mechanisms, and reactor engineering. Finally, we outline future research directions, emphasizing the importance of multi-scale collaborative design to advance toward the ultimate goal of green and low-carbon NH₃ production.

Organic cathode materials (OCMs), with their inherent structural diversity, elemental sustainability, and environmental compatibility, present a promising pathway to overcome the energy density and resource limitations of conventional inorganic cathodes. As such, they are regarded as highly promising candidates for next-generation rechargeable batteries. Nevertheless, the simultaneous achievement of high-energy density and robust stability in OCMs remains a significant challenge. High energy density depends on the high capacity and high voltage of the material, while robust stability relies on the low solubility of the material. In this review, we begin by systematically examining the fundamental causes of the low capacity, low voltage, and strong solubility in OCMs. On this basis, we summarize recent advances in enhancing the energy density of OCMs, including molecular-level material design, electrode-level engineering, and electrolyte-level optimization. Meanwhile, we offer forward-looking perspectives on the future development of organic electrodes for next-generation battery technologies.

An electrochemical platform enabling condition-dependent chemoselective reduction of alkynes was developed. Modulation of electrochemical parameters allowed selective formation of alkenes or alkanes via proton transfer or nickel hydride formation pathways, as supported by potentiodynamic analyses and detailed isotope-labeling studies. The reactions proceed under mild conditions without the use of molecular hydrogen, featuring broad scope and high functional-group tolerance, thus providing a practical and sustainable approach to chemoselective alkyne reduction.