Liquid organic hydrogen carriers (LOHCs) based on cycloalkane/aromatic pairs are promising for safe hydrogen storage and transportation, but their practical implementation is limited by sluggish dehydrogenation kinetics and catalyst deactivation under working conditions. Herein, we report a rationally designed platinum catalyst supported on curved graphene-coated nanodiamond (ND@G), in which fully exposed subnanometric Pt clusters (Ptn) and three-dimensional Pt clusters (Ptc) are integrated in close proximity on the support (Ptn+c/ND@G), which delivers remarkably enhanced hydrogen production in the solvent-free dehydrogenation of bicyclohexyl and other representative cycloalkanes, outperforming either single-counterpart catalysts or their physical mixtures while maintaining good recyclability. Mechanistic investigations combined with density functional theory calculations demonstrate that this synergistic effect originates from the cooperation between these respective Pt ensembles: Ptc sites possess higher intrinsic activity for C-H bond activation than Ptn clusters, yet are more susceptible to poisoning. By contrast, Ptn clusters, although less active for substrate activation, remain operative in the presence of aromatic adsorbates. Hydrogen generated on Ptn clusters can weaken product binding on adjacent Ptc sites via support-mediated spillover. As a result, poisoning is mitigated, active Ptc sites are continuously regenerated, and overall dehydrogenation performance is enhanced. These findings provide a general design principle for developing high-performance LOHC dehydrogenation catalysts through Pt ensemble engineering and support-mediated hydrogen management.

The electrocarboxylation of butadiene (BD) offers a sustainable route to hexenedioate synthesis through CO2 utilization. Hexenedioate can be converted into adipic acid, the main precursor to Nylon, which is currently produced from fossil-based feedstocks. However, key aspects of BD electrocarboxylation remain unclear, particularly the involvement of surface-bound intermediates and competing interfacial reactions, such as the CO2 reduction reaction (CO2RR). Herein, we employ in situ Attenuated Total Reflectance Surface Enhanced Infrared Absorption Spectroscopy (ATR-SEIRAS), electrolysis experiments with product analysis and density functional theory (DFT) to investigate BD electrocarboxylation on Au, Cu, and Pt. ATR-SEIRAS tracks the evolution of interfacial species and shows that BD suppresses the CO adsorption band on Cu but remains unchanged on Pt, consistent with DFT predictions that result from its preferential binding and the destabilization of BD chemisorption at increasingly cathodic potentials. Electrolysis experiments reveal higher hexenedioate Faradaic efficiency on Au, followed by Cu and Pt, while CO selectivity shows the opposite trend (Pt > Cu > Au), providing complementary evidence for metal-dependent trends observed in the spectroscopic measurements. Although CO still forms in the presence of BD, part of the CO2•- is consumed by BD to generate electrocarboxylation products, and the CO that is produced does not adsorb on Cu because BD or BD-derived species outcompete and displace it. These findings highlight the effect of BD adsorption and potential-dependent radical competition in shaping electrocarboxylation reactions, emphasizing the importance of considering interfacial contributions in the electrochemical process.

Protein and enzyme film electrochemistry is a powerful technique which enables the energetics and kinetics of biological electron transfer processes to be quantified. One of the major challenges is finding a suitable electrode surface upon which a redox active protein or enzyme can be adsorbed in an electroactive configuration. Multi-walled carbon nanotubes (MWCNTs) have been a useful class of electrode modifiers which facilitate electroactive protein adsorption and provide a substantial increase in electrode surface area. MWCNTs are therefore commonly used in bioelectrochemical studies, with applications in analytical electrochemistry and electrochemical sensing. Herein, we report the effect of electrochemical oxidation on a MWCNT-functionalised glassy carbon electrode in the presence of adsorbed protein. Previously uncharacterised redox functionalities are introduced by sweeping to oxidising potentials (> 0.8 V vs. SHE), with two reversible electron transfer signals subsequently appearing with midpoints of 80 and 390 mV at pH 7.0. This redox activity is hypothesised to be a result of the irreversible oxidation of the MWCNT-protein system resulting in the introduction of species capable of performing fast, reversible electron transfer.

There is great interest in systems where enzymes are adsorbed on and act at electrode surfaces, including enzymatic biofuel cells, bioreactors, and biosensors. Although studied extensively since the 1960s, progress is hindered by a lack of molecular-level understanding of enzyme adsorption and the associated electron transfer processes. Herein, we present a multiscale approach combining molecular dynamics (MD) simulation to elucidate the former and density functional theory (DFT) for the latter. The demonstration focuses on a system involving microperoxidase-11 (MP-11), a microenzyme made up of a Fe-containing heme ring attached to an 11-residue scaffold, a graphene electrode, and a neutral-pH saline solution. Adsorbed MP-11 was found to adopt six possible heme configurations, defined by the iron-to-graphene distance and the angle between the heme and graphene normals. The electron transfer rate constants, evaluated by combining MD and DFT results, and their variation with overpotential are comparable to the limited experimental data. The results also illustrate how the new multiscale approach can suggest experimental strategies, from targeted protein engineering to changes in substrate conditions, for improving the electrocatalytic performance of MP-11/graphene and, more broadly, of other microenzyme/electrode systems of interest across bioelectrocatalysis, biosensing, and bioenergy.

This study compares activated carbons prepared from normal (AC-FN) and insect-infested (AC-FI) Ferula stem biomass for Methylene Blue (MB) and Congo Red (CR) adsorption. Insect-induced structural modification was evaluated for its effect on pore development and adsorption performance after chemical activation. Among the tested conditions, H2SO4 activation produced the most efficient carbons. AC-FI exhibited superior textural properties with a BET surface area of 993.79 m[2]/g and micropore surface area of 770.82 m[2]/g, compared to 617.08 m[2]/g and 324.27 m[2]/g for AC-FN, respectively. The pHpzc values (6.81 for AC-FI, 6.34 for AC-FN) explained the pH-dependent adsorption: CR removal was favored under acidic conditions, and MB was enhanced near neutral to slightly basic pH. Equilibrium data fitted the Freundlich model, indicating heterogeneous surfaces. Langmuir maximum capacities were 78.60 mg/g (MB) and 71.20 mg/g (CR) on AC-FI. Kinetics followed the pseudo-second-order model, suggesting surface interactions dominate the process. Thermodynamic parameters revealed an endothermic process with positive entropy changes. Overall, insect-infested Ferula biomass is a promising biologically pre-modified precursor for producing efficient activated carbon with enhanced microporosity, favorable surface chemistry, and improved dye adsorption performance.

The separation of aromatic compounds from cyclic aliphatics has drawn decades of attention from researchers. Adsorption-based separation, an energy-saving recovery technology, can be efficiently carried out on various adsorbents. Developing cost-effective adsorbents with good selectivity and batch preparation capability is an inevitable trend. Carbon molecular sieves (CMSs) are promising, but controlling the pore size distribution is a major limitation. In this work, a series of phenolic resin-based fibrous CMSs with a concentrated distribution of ultramicropores and conjugated sp[2] carbon structures was synthesized by regulating electrospinning and heat treatment. Experimental and computational studies indicate that SCF2-1000 exhibits an adsorption amount ratio of 6.8 in static adsorption, comparable to those of reported framework materials and zeolites. In equimolar benzene/cyclohexane breakthrough experiments, it achieves a high adsorption amount ratio of 11.4 and a long separation window of 2000 min g[-1]. FCF-1H demonstrates a dynamic adsorption selectivity factor of 30.14 and a long separation window of 8300 min g[-1] in a 1:9 toluene/methylcyclohexane separation experiment. The short-range and concentrated ultramicropores allow rapid, selective adsorption and easy regeneration without decline. This work offers a feasible pathway toward separating and purifying mixed gases containing aromatics and their hydrogenation products in industrial processes.

As an emerging adsorbent， biochar has shown a broad application prospect in the field of environmental remediation. However， in recent years， many studies have confirmed that their own pollutants have potential environmental risks in practical application. This paper summarizes the source of biochar endogenous inorganic pollutants （heavy metals， metalloid， etc.） and organic pollutants （PAHs， EPFRs， etc.）， occurrence characteristics， and potential environmental application risk and further explores the environmental release mechanism of biochar endogenous pollutants （physical release， chemical release， and biological-mediated release）. The study shows that the endogenous pollutants of biochar showed the dynamic migration characteristics in different environmental media （soil， water， and atmosphere）， and their migration behavior was influenced by many factors. Meanwhile， the ecotoxicological effects of endogenous pollutants of biochar were also summarized. Finally， this paper prospects the future research direction， pointing out that the key to reduce the risk of endogenous pollutant release of biochar is to consider the control of reaction process parameters and planning the application site of biochar.

Area-selective atomic layer deposition (AS-ALD) is a promising approach for precise thin film deposition and nanoscale patterning in 2D and 3D architectures. Since ALD growth is strongly dependent on surface chemistry, area-selective deposition (ASD) can be achieved either through intrinsic differences in surface reactivity or through deliberate surface functionalization via chemisorption of molecules called inhibitors that suppress thin film formation on targeted surfaces or via promoters that favor thin film formation on desired surfaces. Therefore, understanding the selective adsorption of these molecules as well as their interactions with ALD precursors and reactants is crucial for determining growth versus non-growth surfaces and the extent of surface passivation. In this study, two organosulfide inhibitors, dipropyl sulfide (DPS) and isopropyl sulfide (IPS), have been utilized for AS-ALD on Cu, SiO2, and TiN surfaces. Despite sharing the same chemical composition, DPS and IPS exhibit distinct adsorption behaviors. Both DPS and IPS selectively adsorbed on Cu, whereas only DPS adsorbed on SiO2, while both inhibitors remained unreactive toward TiN. Density functional theory (DFT) calculations suggest that the inhibitors can dissociate into fragments whose adsorption geometries differ between substrates, enabling DPS to achieve multi-surface passivation while IPS remains surface selective.

The corrosion inhibition performance of two newly synthesized pyrazole-based derivatives, P6 (bis-pyrazole) and P8 (pyrazolyl-thiadiazine), toward carbon steel in 1.0 M HCl was systematically investigated using combined experimental and theoretical approaches. Electrochemical and gravimetric results revealed high inhibition efficiencies exceeding 95% at 5 × 10[-4] M, with P6 exhibiting superior performance. This enhanced performance is attributed to its stronger adsorption affinity and more stable interaction with the steel surface. Polarization measurements revealed predominantly anodic inhibition behavior, although both anodic and cathodic reactions were affected, while impedance analysis confirmed the formation of a protective adsorbed film. Surface characterization (SEM, EDX, and AFM) further supported the development of a compact and homogeneous protective layer. Thermodynamic analysis suggested a mixed adsorption mechanism involving electrostatic and chemical interactions. Computational studies (DFT and Monte Carlo simulations) corroborated the experimental findings, demonstrating strong adsorption on the Fe (110) surface.

Metal-doped biochar is a promising phosphate adsorbent for mitigating phosphate-driven eutrophication and valorizing biomass, but its adsorption performance, selectivity and stability are strongly governed by the biochar-metal structure. Herein, the biochar was embedded into carbon nanofiber' networks to construct a self-supporting biochar-carbon nanofiber framework (C-ACF). The C-ACF was first functionalized with an amine-rich HCCP-PEI polymer layer to obtain PCP@C-ACF, which was then used to anchor highly dispersed La species, yielding the performant La-loaded adsorbent PCP-La@C-ACF. Expectantly, PCP-La@C-ACF exhibited outstanding phosphate adsorption kinetics and selectivity, achieving phosphate uptake of 63.5 mg P·g[-1] within 1 min (9.3-fold that of La(OH)3) and an equilibrium capacity of 93.9 mg P·g[-1], along with broad pH tolerance and marked reusability. Under fixed-bed operation, PCP-La@C-ACF maintained the effluent phosphate concentration below 0.2 mg P·L[-1] (removal rate > 99.4%). Owing to the loaded La species, markedly improved phosphate selectivity under high concentrations of Cl[-], NO3[-], and SO4[2-] was achieved, with selectivity coefficients against NO3[-] and SO4[2-] being 14- and 32-fold higher than La-free PCP@C-ACF. Molecular dynamics simulations rationalize that such dispersed La species enhance adsorption selectivity/rate by promoting phosphate dehydration and improving interfacial diffusion efficiency.

Wastewater generated from industrial and marine activities is considered one of the most pressing global environmental challenges due to the presence of hazardous contaminants, including heavy metals, organic pollutants (such as dyes, phenolic compounds, and pharmaceuticals), and oil-in-water emulsions. At the same time, marine industries generate substantial amounts of crustacean waste that can harm the environment when improperly disposed of. From this valuable marine waste, chitosan, the second most abundant biopolymer after cellulose, can be chemically extracted from crustacean shells such as shrimp, fish, lobster, crab, krill, and squid. The term "extracted, environmentally friendly chitosan" refers to chitosan obtained from marine waste via chemical extraction, which is the primary focus of this review. The biomass-derived chitosan can become a source of several applications, including wastewater treatment, specifically oil-in-water separation, heavy-metal removal, organic contaminant adsorption, and desalination. This review covers marine sources of chitosan, chemical extraction methods, and the application of marine-derived chitosan-based materials in wastewater treatment. Focusing on research published from 2020 to 2025, this review examines marine-derived chitosan-based materials, adsorbents, membranes, and hydrogels, and highlights their application in water treatment. This review not only promotes cleaner water technologies but also fosters the transition towards sustainable valorization of marine waste through chitosan. Overall, this review highlights the significant potential of marine-derived chitosan-based materials as sustainable and efficient solutions for advanced wastewater treatment and marine waste valorization.

Chitin, an abundant marine biomass resource, holds great potential for the sustainable preparation of high-valued nitrogen-containing chemicals to reduce the environmental footprint associated with the Haber-Bosch process. However, current synthetic methods for converting chitin into the organonitrogen platform chemical 3A5AF typically suffer from harsh reaction conditions and poor environmental benignity. Herein, we develop a new ternary composite catalyst AlCl3-5TBAC-WO3 to efficiently convert chitin into 3A5AF in one-step in γ-valerolactone (GVL) under mild conditions. The composite catalyst was characterized by FT-IR, XRD, SEM, and pyridine-adsorbed IR to elaborate its superior catalytic performance. After a series of optimization experiments, the highest 3A5AF yield achieved from H2SO4 aged-ball milled-chitin was 32% under mild conditions. Moreover, the reaction was scaled up to 1 g scale, achieving an isolated yield of 16%. This study offers a low-cost, efficient, and eco-friendly route for the sustainable valorization of chitin biomass into valuable organonitrogen chemicals.

Perfluoroalkyl substances (PFAS) pollution has been a worldwide environmental challenge. Inspired by the semipermeable function of cell membranes, we constructed a millimeter-sized capsule adsorbent with specific molecular recognition capability to capture a broad spectrum of PFAS. This novel capsule consists of a core with a regulated nanoscale amine-rich network powder (ANP) and a porous polyvinylidene fluoride (PVDF) shell. Adsorption experiments and molecular simulations revealed that the PVDF shell acted as a semipermeable membrane, allowing only PFAS to pass through while repelling the coexisting environmental matrices, whereas the ANP core could provide the driving force for PFAS to enter the interior of the capsule adsorbent. Moreover, by regulating the hydrophilic functional structure of ANP, the driving force for short-chain PFAS to enter the capsule interior was enhanced, enabling the efficient capture of a wide range of PFAS (C-F number: 3-9). Further mechanistic studies demonstrated that the dual driving forces based on fluorophilicity and hydrogen bonding were key to capturing broad-spectrum PFAS. The fixed-bed experiments further demonstrated that the aminated organic fluorine capsule (AFC) column could treat approximately 18,000 bed volumes of effluent from synthetic PFOA-polluted water, with the effluent PFOA concentration remaining below 40 ng/L from an initial influent concentration of 1 μg/L (compared with the World Health Organization's drinking-water standard of 100 ng/L). Overall, this work not only provides a promising approach to treat PFAS-containing water but also sheds light on the design of functional remediation materials based on molecular properties and confined structures.

Building on our previous investigations of chalcone-based functional materials, the present work reports a synergistic experimental and theoretical investigation of the designed bis-chalcone derivatives, namely 3-(4-(dimethylamino)benzylidene)pentane-2,4-dione (DBPD) and 3-(3-(4-dimethylamino)phenylallylidene)pentane-2,4-dione (DPAPD), as highly efficient corrosion inhibitors for carbon steel in 1.0 M HCl solution. The inhibition performance and adsorption behavior were evaluated using weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy, surface characterization techniques (SEM/EDX), density functional theory, and Monte Carlo simulations. Both compounds exhibited excellent concentration-dependent corrosion inhibition efficiency. Potentiodynamic polarization measurements confirmed that both compounds behave as mixed-type corrosion inhibitors, significantly reducing the corrosion current density (Icorr) from 217.59 to 27.61 and 21.18 μA cm[-2], while electrochemical impedance spectroscopy (EIS) revealed a marked increase in the charge-transfer resistance (Rct) from 19.7 to 219.05 and 244.78 Ω cm[2] in the presence of 10 × 10[-5] M DBPD and DPAPD, respectively, confirming the formation of a protective adsorbed film on the steel surface. Adsorption followed the Langmuir isotherm model (R[2] > 0.994), indicating spontaneous adsorption and nearly homogeneous surface coverage. SEM and EDX analyses confirmed the formation of a compact protective film and a substantial reduction in corrosion damage. DFT calculations and MC simulations revealed strong adsorption of the inhibitor molecules on the Fe(110) surface, with DPAPD exhibiting higher adsorption affinity, in excellent agreement with experimental observations. The enhanced inhibition performance was attributed to the electron-donating dimethylamino group, extended π-conjugation, and multiple adsorption centers. These findings provide molecular-level insight into the inhibition mechanism and highlight bis-chalcone derivatives as promising, structurally tunable corrosion inhibitors for acidic industrial applications.

Microplastics (MPs) can act as both carriers of intrinsic additive metals and scavengers of ambient contaminants, yet information regarding metal-associated atmospheric MPs remains limited. This study investigated the spatial and seasonal characteristics of suspended MPs and associated metals in science park, urban, and rural regions of Hsinchu, Taiwan. Total suspended particulate samples were collected, and MPs were characterized using fluorescence microscopy and μFTIR. Additive and adsorbed metals associated with MPs were operationally separated through density fractionation and acid digestion and quantified using ICP-MS. Science park areas exhibited the highest MP concentrations, particularly during the cold season. Polyethylene (PE), polystyrene (PS), polypropylene (PP), and rayon were the dominant polymers across sites, but their relative distributions varied spatially. Suspended MPs contained approximately 3-50% of the corresponding metal concentrations measured in TSP, with elevated enrichment factors observed for anthropogenic metals including Cr, Cu, Zn, As, Cd, Sb, and Pb. Seasonal differences were evident, as adsorbed metals dominated during the cold season whereas additive-derived metals contributed more prominently during the warm season. Multivariate analyses identified resuspended dust as a common source connecting the MPs and their metals. Comparisons with locally collected plastic products suggested that packaging materials and consumer plastics contributed substantially to intrinsic metal signatures in suspended MPs. These findings demonstrate that atmospheric MPs function as sources and sinks of hazardous metals and highlight the importance of considering both additive and adsorption processes when evaluating the environmental and health risks of airborne MPs.