ChemSusChem最新文献

The Cover Feature depicts a dynamic superhero who embodies the elements of carbon, phosphorus, oxygen and nitrogen, thus symbolizing the metal-free catalyst central to our research. Armed with scissors, the superhero is shown cleaving lignin model dimers into valuable monomers. The scene is set on a road that transitions from a lush forest on the left, representing the natural source of lignin, to a modern industry on the right, illustrating the sustainable transformation of lignin into industrially valuable compounds such as phenol. This image highlights the innovative approach of using a P,N co-doped carbon catalyst to achieve efficient lignin valorization, offering an eco-friendly solution for producing industrial chemicals and fuels. More information can be found in the Research Article by R. Srivastava and co-workers.

Plasma-induced methane pyrolysis is a promising hydrogen production method. However, few studies have focused the decomposition of pure methane as a discharge gas. Herein, a rotating gliding arc reactor was used for the conversion of methane (discharge gas and feedstock) into hydrogen and solid carbon. Methane conversion, gaseous product selectivity, and energy usage efficiency(specific energy requirement for hydrogen production(SER)) were investigated as functions of operating parameters, e.g., specific energy input(SEI), residence time, and reactor design. SEI was positively(almost linearly) correlated with methane conversion and hydrogen yield and negatively correlated with SER. Conversion and efficiency of energy usage increased when reactor designs providing higher thermal densities were used. With the increasing flow rate of methane at constant SEI, the reaction volume and, hence, the residence time of the gas inside the reaction zone increased, which resulted in methane conversion and hydrogen selectivity enhancement. The solid carbon featured four distinct domains, namely graphitic carbon, turbostratic carbon, few-layer graphene, and amorphous carbon, which indicated a nonuniform temperature distribution in the reaction zone. But it seems that graphitic carbon dominates amorhphous one. This study highlights the potential of rotating gliding arc plasma systems for efficient methane conversion into hydrogen and valuable solid carbon products.

The Cover Feature shows plasticware for biomarker measurement, which constitutes a notable portion of the plastic waste stream from medical consumables. We have developed a portable vortex fluidic device (P-VFD) with a membrane array to initiate fast reaction, detection and analysis of a clinically relevant protein biomarker, p75ECD. It shows significant potential to replace traditional assay plates with a membrane, providing a greener and more sustainable alternative in biofluid biomarker measurement. More information can be found in the Research Article by X. Luo, M.-L. Rogers, C. L. Raston and co-workers.

The Cover Feature shows the efforts to prepare active and N₂-selective catalysts for NH₃-SCR-DeNO_x for automotive applications. Systematic studies of Cu-containing SSZ-13, including micro-/mesoporous variants by in-situ FTIR and EPR as well as in-situ DR UV-Vis together with SSITKA for the investigation of the reaction mechanism provide new insights into and show new aspects of this highly relevant class of catalysts. More information can be found in the Research Article by M. Jabłońska and co-workers.

We explored the electrochemical behavior of antimony-doped tin oxide (ATO) and perylene diimide (PDI)-sensitized ATO (ATO-PDI) for the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) mediated conversion of 5-hydroxymethyl furfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a value-added substrate for alternative polymer synthesis. We first showed that ATO displayed good electrocatalytic properties towards TEMPO, affording a quasi-reversible response with a heterogeneous rate constant on the order of 2×10^-4 cm s^-1. We then evaluated the performance of ATO under exhaustive electrolysis of HMF in basic aqueous electrolyte, reaching 80 % Faradaic Efficiency (FE) for FDCA production. Interestingly, a significantly enhanced current (up to 2.5 mA cm^-2) was recorded over time when ATO-PDI was exposed to prolonged visible illumination in a Dye-Sensitized Photoelectrochemical Cell (DSPEC) configuration, which we ascribed to the photoinduced doping of ATO resulting from the oxidative quenching of PDI excited states. The proposed system enabled the production of FDCA with ca. 75 % FE in <2 h reaction time, and an almost quantitative HMF conversion when both the mono- and di-acid products were considered. To the best of our knowledge, this is the first example of a molecular dye-sensitized interface used for the TEMPO-mediated oxidation of HMF.

Perovskite oxides have been extensively investigated as active electrocatalysts for the oxygen evolution reaction (OER) in alkaline solution. While the OER activity of some perovskite oxides is positively influenced by Fe ions in the electrolyte, the impact of other transition metal ions in the electrolyte remains unclear. In this study, we compared the influence of Co ions intentionally added to the electrolyte on the OER activities of two Fe-based perovskite oxides (Ba0.5Sr0.5FeO3-δ and LaFeO3). While the OER activity of Ba0.5Sr0.5FeO3-δ is significantly enhanced by adding Co ions to the electrolyte, LaFeO3 showed little difference in the OER behavior between the Co-free and Co-containing electrolytes. In the case of Ba0.5Sr0.5FeO3-δ, an amorphous layer was formed, and the Co ions from the electrolyte were incorporated on the surface as a result of OER cycling. On the other hand, Co ions were also detected on the surface of LaFeO3, but its crystalline structure remains unchanged during the OER. Our study suggests that synergistic interplay between the perovskite oxides undergoing a structural transformation at the surface and transition metal ions in the electrolyte can improve the OER activity.

The most influential technological innovations and societal progress lie at the intersection of scientific disciplines. Today, more than ever, biology assumes a more central and participatory role at this confluence. Within the context of this scientific inter-disciplinarity, the current effort was undertaken to explore the ecology of invasive tunicates, marine invertebrates increasingly considered a nuisance to the ecology of coastal ecosystems, yet potentially a resource for diverse applications in materials chemistry, construction, composites, and engineering. The intention of this perspective is to stimulate conversation and discussion with respect to benthic tunicates, a valuable yet underappreciated biological resource, which can be converted to cellulose nanocrystals, one of the most important bio-based materials sourced today. It will also attempt to consolidate current understandings of the ecology of tunicates and how potential material exploitation can be mutually compatible and compliant with efforts to protect coastal ecosystems and aquaculture which are currently inundated or threatened by invasive tunicates.

Useful monophosphorus products are obtained from both white and red phosphorus via a simple strategy involving initial oxidation by aryl disulfides followed by quenching with nucleophiles. Direct transformations of elemental phosphorus are usually very challenging, forcing chemists to instead rely on inefficient and hazardous multi-step methods. However, here they are achieved using inexpensive and easy-to-handle reagents, providing access to diverse P-C, P-N and P-O bonded products in good yields. By isolating the thiolate byproducts of these reactions, a simple, closed loop can be achieved that produces only minimal, benign waste byproducts, in contrast to other direct methods. This closed loop can even be elaborated into a true (electro)catalytic cycle, which is extremely rare in the field of elemental phosphorus functionalization.

With the aim of transforming sewage sludge into a P-fertiliser material in a single combustion step, the chemical processes underlying sewage sludge combustion were analysed using powder X-ray diffraction (P-XRD), infrared spectroscopy (IR), thermogravimetric (TGA) as well as elemental analyses (EA). In addition to the combustion of sewage sludge on its own ("mono-combustion"), additions of different additives prior to the combustion step were also carried out. Based on the very positive effects of the additives sodium and potassium carbonate on the obtained ashes concerning their phosphate solubilities in neutral ammonium citrate (NAC) solution, sewage sludge combustions after additions of Na2CO3 or K2CO3 were investigated in detail. We found that these additions altered the main phosphate-containing product found in the ashes from whitlockite (Ca9(Mg,Fe)(PO3OH)(PO4)6), a hardly plant-accessible species, to other phosphate containing compounds such as buchwaldite (CaNaPO4), which is known for a long time as a very good P‑source for plants. Consecutive greenhouse experiments with maize (Zea mays L.) as test plant confirmed the results of the chemical analyses and demonstrated that Na- or K-ashes obtained from a "co-combustion" of sewage sludge mixed with alkali carbonates exhibit relative P-fertilising efficiencies of up to ~80 % in comparison to commercial superphosphate.

Integrating oxygen redox reactions with transition metal redox reactions offers a promising strategy to double or triple the energy density for large-capacity battery cathodes. In this study, we have introduced intrinsic oxygen vacancies (V_O) into a P3 layered cathode to modulate the electronic structure of O atoms and enhance oxygen redox activity. Rietveld-refined X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy confirm the successful creation of V_O in Na_0.66Mn_0.66Mg_0.33O_1.93 (OV-NMM). Density functional theory (DFT) calculations reveal that V_O in OV-NMM positively enhances the antibonding interaction between Mn and O, directing excess electrons from O holes toward adjacent Mn t_2g and O 2p orbitals. This modification significantly improves the reversibility and accelerates Na⁺ transport kinetics for O2^-/O^- redox reactions. Ex situ synchrotron-based XRD demonstrates that V_O effectively eliminates the O3 phase, reduces Mg²⁺ migration, and suppresses irreversible structural changes. XAS of Mn K-edge and O K-edge further illustrate the advantageous role of oxygen vacancies in facilitating oxygen redox reactions. These findings highlight the potential of defect engineering, particularly V_O, to boost anionic redox activity for high-capacity energy storage applications.