Adsorption Sites Research Articles

Visible‐Light‐Driven Oxidation of Benzene to Phenol with O2 over Photoinduced Oxygen‐Vacancy‐Rich WO3

AbstractDirect photocatalytic conversion of benzene to phenol with molecular oxygen (O2) is a green alternative to the traditional synthesis. The key is to find an effective photocatalyst to do the trick. Defect engineering of semiconductors with oxygen vacancies (OVs) is an emerging strategy for catalyst fabrication. OVs can trap electrons to promote charge separation and serving as adsorption sites for O2 activation. However, the randomly distribution of OVs on the semiconductor surface often results in mismatching the charge carrier dynamics under irradiation, thus failing to fulfill the unique advantages of OVs for photoredox functions. Herein, we demonstrate that abundant OVs can be facilely generated and precisely located adjacent to the reductive sites on reducible oxide semiconductors such as tungsten oxide (WO3) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O2 as they readily capture photogenerated electrons from the reductive sites of WO3 to activate adsorbed O2. The oxygen‐isotope‐labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O2 into phenol, revealing in detail the pathway for photocatalytic benzene hydroxylation. This study demonstrates that the photochemistry approach is an appealing strategy for the synthesis of high‐performance OVs‐rich photocatalysts for solar‐induced chemical conversion.

Effect of background ions and physicochemical factors on the cotransport of microplastics with Cu2+ in saturated porous media

Microplastics (MPs) in subsurface environments are migratory and can carry heavy metals, increasing the extent of MP and heavy metal pollution. This study used quartz sand-filled column experiments to investigate the adsorption and cotransport behaviours of PS-MPs, O3, UV-aged PS-MPs, and Cu2+ at different MP concentrations, ionic strengths, and ionic valences in a saturated porous medium. The results showed that when MPs migrate alone in the absence of an ionic background, higher concentrations have increased mobility. In contrast, an increase in the background ion concentration or ion valence inhibits the individual transport capacity of PS-MPs. An increase in the concentration of background ions or elevation in the valence state promotes Cu2+ transport because of the action of the double electric layer on the surface of the colloid and the electrostatic repulsive forces combined with the background ions. The adsorption capacity of aged PS-MPs was stronger than that of PS-MPs because of the binding of the aged PS-MPs to Cu2+ through complexation and electrostatic attraction. In the binary system of PS-MPs/Cu2+, PS-MPs promoted Cu2+ transport and the mobility of Cu2+ loaded by PS-MPs decreased with increasing background ion concentration. The cotransport results showed that MPs promote Cu2+ transport in the following order: O3-aged Ps > UV-aged Ps > Ps, as the increasing cation concentration in the MPs and Cu2+ occupies the PS surface adsorption sites. Overall, PS is an effective carrier for Cu2+. These findings offer fresh exploration concepts for the joint migration of MPs and heavy metals in underground settings.

Synergistic N/F Dual-Doped MoC/C Catalyst Synthesized via Liquid Phase Plasma for Sustainable Ammonia Production.

NH3 is a versatile solution for the storage and distribution of sustainable energy, offering high energy density and promising applications as a renewable hydrogen carrier. However, electrochemical NH3 synthesis under ambient conditions remains challenging, such as low selectivity and efficiency, owing to the inertness of N≡N and competing reactions. In this study, a catalyst (MoC/NFC) comprising molybdenum carbide evenly dispersed on carbon doped with N and F heteroatoms was successfully synthesized using liquid-phase plasma. The MoC/NFC catalyst exhibited a maximum NH3 yield of 115 μg h-1 mg-1cat. with a faradaic efficiency of 1.15% at -0.7 V vs reversible hydrogen electrode in 0.1 M KOH electrolyte. Pyridinic- and pyrrolic-N atoms adjacent to the carbon pores served as active sites for N2 adsorption and enabled N2 triple bond cleavage. In addition, F doping contributed to N2 activation owing to the high electronegativity of 3.98, resulting in the attraction of more electrons. These findings demonstrate a significant advancement in the development of efficient catalysts for electrochemical ammonia synthesis, potentially paving the way for scalable and sustainable NH3 production methods that can support the growing demand for renewable energy storage solutions.

Engineering Dual-Defective 0D/2D VN-CNQDs/VBi-Bi4O5Br2 S-Scheme Heterostructure for Boosting CO2 Photoreduction in Air.

The direct photocatalytic reduction of CO2 in air is the future trend of photocatalyst application. Herein, the 0D carbon nitride quantum dots with nitrogen vacancies (VN-CNQDs) and 2D bismuth-deficient Bi4O5Br2 (VBi-Bi4O5Br2) are integrated by hydrothermal method. The S-scheme heterostructure of VN-CNQDs/VBi-Bi4O5Br2 composite promotes the separation rate of photogenerated carriers and enhances the redox capacity. The dual defects provide a large number of adsorption and catalytic sites that enhance the ability to capture and reduce CO2. The synergistic effect of S-scheme heterostructure and defect engineering enables the efficiency of CO2 photoreduction to CO with VN-CNQDs/VBi-Bi4O5Br2 to reach 16.89µmolg-1h-1 in air and 55.69µmolg-1h-1 in VCO2: VAir = 3:1 condition, which is 17 and 21 times higher than that of Bi4O5Br2, respectively. The dual-defective VN-CNQDs/VBi-Bi4O5Br2 exhibits more lower energy barrier for forming *CO2, *COOH, and *CO and is easier to release CO gas. And it exhibits excellent cycling stability for photocatalytic CO2 reduction to CO. The photocatalytic reduction mechanism of CO2 to CO in the VN-CNQDs/VBi-Bi4O5Br2 S-scheme heterostructure is further analyzed. This work provides new perspectives for the design of the photocatalysts with defect engineering for efficient photoconversion at low CO2 concentrations.

Constructing an Active Sulfur-Vacancy-Rich Surface for Selective *CH3-CH3 Coupling in CO2-to-C2H6 Conversion With 92% Selectivity.

To achieve high selectivity in photocatalytic CO2 reduction to C2+ products, increasing the number of CO2 adsorption sites and lowering the energy barriers for key intermediates are critical. A ZnIn2S4 (ZIS)/MoO3-x (Z-M) photocatalyst is presented, in which plasmonic MoO3-x generates hot electrons, creating a multielectron environment in ZIS that facilitates efficient C─C coupling reactions. Density functional theory (DFT) calculations reveal that MoO3-x reduces the formation energy of sulfur vacancies (SV) in ZIS, thereby enhancing CO2 adsorption and activation. The SV-rich surface lowers the energy barrier for forming HCOO* to -0.33 eV whereas the energy barrier for forming *COOH is 0.77 eV. Successive hydrogenation of HCOO* leads to *CH2, which converts to *CH3 with an energy barrier of -0.63 eV. The energy barrier for *CH3-CH3 coupling is 0.54 eV, which is lower than the 0.73 eV for *CH2-CH2 coupling to form *C2H4. Thus, Z-M preferentially produces C2H6 over C2H4. Under visible light, Z-M achieves a CO2-to-C2H6 conversion rate of 467.3 µmol g-1 h-1 with 92.0% selectivity. This work highlights the dual role of plasmonic photocatalysts in enhancing CO2 adsorption and improving C2+ production in CO2 reduction.

Polarized electric field-mediated graphitic carbon nitride-based S-scheme heterostructure for efficient photocatalytic removal of bisphenol A

Tuning interface charge transfer is considered as a feasible way to promote electron migration and separation in heterojunction system, but the role of in-plane electron behavior in single phase has received little attention. Here, a carboxyl functionalized graphitic carbon nitride (CCN) coupled PbBiO2Br (PBOB) S-scheme heterostructure is elaborately designed for investigation. Compared with pristine CN/PBOB, although the existence of carboxyl group weakens the built-in electric field strength of CCN/PBOB (ΔΦ = 0.44 eV), the formed polarized electric field (µ = 3.18 Debye) is conducive to the pre-separation of photogenerated electrons and holes in CCN, thereby improving interface charge transfer. In addition, the introduced carboxyl group can also serve as an O2 adsorption site to enhance its activation, and generate reactive oxygen species (ROS) through a two-step single-electron O2 reduction route. Thus, the optimized CCN/PBOB exhibits excellent photocatalytic ROS generation ability, which can remove 88.7 % of bisphenol A and significantly reduce the acute toxicity of the formed intermediates. This work provides a new perspective for the development of advanced heterojunction photocatalyst by regulating in-plane/interface charge dynamics, and helps to fully understand the pollutant detoxification/degradation process initiated by molecular oxygen activation.

Cascade Reactions for Enhanced CO2 Capture: Concurrent Optimization of Porosity and N‐Doping

AbstractCarbon capture emerges as a pivotal decarbonization technology for addressing global warming challenges. Porous carbons, despite their cost‐effectiveness and ease of regeneration for CO2 capture, typically exhibit limited capacity owing to insufficient adsorption sites. Here, nitrogen‐doped porous carbons (NPCs) are introduced that overcome the prevalent trade‐offs between specific surface area and N‐doped content in NPCs fabrication through cascade reactions. The optimized NPC, which features hierarchical porosity ranging from ultra‐micropores to macropores, shows a superior CO2 capture capacity of 4.46 mmol g−1, ranking in the top 10% of the reported NPCs. This capacity exceeds that of the NPC fabricated with the conventional method by 58% and surpasses the control porous carbon by 106%. Langmuir adsorption modeling and mathematic correlation analysis revealed that this enhanced capacity is attributed to significantly improved ultra‐micropores volume and nitrogen‐species content. Moreover, this optimized NPC demonstrates exceptional stability, preserving its adsorption performance over 110 adsorption–desorption cycles under simulated flue gas conditions. This research not only highlights the integration of templating and N‐doping within NPCs fabrication but also offers an effective strategy to optimize porosity and nitrogen functionality in carbon materials, advancing beyond conventional methodologies.

The new fate of MCLR revealed by dialysis equilibrium and theoretical calculations: Influence from DOM and Fe(II)/Mn(II)

Microcystin-LR (MCLR) is a highly toxic pollutant widely distributed in eutrophic waters. The interplay between dissolved organic matter (DOM) and metal ions has been extensively reported; however, the impact of DOM-metal complexes on MCLR remains to be thoroughly studied. In this research, equilibrium dialysis was employed to study the kinetics and isotherms of MCLR adsorption by DOM, meanwhile the Density functional theory (DFT) calculations provided insights into the theoretical mechanisms of Fe(II)/Mn(II) involvement in the adsorption process. The adsorption kinetics revealed that the process is physicochemical, with chemisorption being the critical factor controlling the adsorption rate. The adsorption isotherms confirmed that Fe(II) alters the spatial arrangement of adsorption sites on the superficies of DOM, with the complexes of Fe(II) and DOM from the macrophyte-dominated regions of Lake Taihu (MDR-Fe(II)) showing the uppermost adsorption capacity of 6193.965 µg/g among all combinations. The influence of different cations (K+, Ca2+, Na+, Mg2+) on the adsorption of MCLR to DOM is divergent, with metals either reducing MCLR adsorption through competition for adsorption sites or increasing it by forming ternary complexes. The pH decrease reduced the affinity of DOM to metal ions while simultaneously enhancing MCLR adsorption through changes in its ionization state. DFT calculations demonstrated that Fe(II)/Mn(II) reduces the resistance to interaction between functional groups on DOM and MCLR, with carboxyl-Fe(II)-carboxyl interactions showing the highest binding energy (ΔG = −7.253 eV). Overall, Fe(II)/Mn(II) enhances the adsorption of MCLR via altering the structure and surface electrostatic potential distribution of DOM. This research indicates that the ultimate fate of MCLR in aquatic ecosystems is affected by DOM and metal ions.

Oxygen Defect Site Filling Strategy Induced Moderate Enrichment of Reactants for Efficient Electrocatalytic Biomass Upgrading.

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) provides a feasible approach for the efficient utilization of biomass. Defect regulation is an effective strategy in the field of biomass upgrading to enhance the adsorption capacity of reactants and thus increase the activity. However, how to select appropriate strategies to regulate the over-enrichment of reactants induced by excessive oxygen vacancy is still a huge challenge. In this work, the defect-filling strategy to design and construct an element-filled oxygen vacancy site layered double hydroxide (S─Ov─LDH) is adopted, which achieves a significant reduction in the electrolysis potential of biomass platform molecule HMF oxidation reaction and a significant increase in current density. Physical characterizations, electrochemical measurements, and theoretical calculations prove that the formation of metal─S bond in the second shell effectively regulates the electronic structure of the material, thus weakening the over-strong adsorption of HMF and OH- induced by excessive oxygen vacancy, promoting the formation of high-valence Co3+ during the reaction, and forming new adsorption sites. This work discusses the catalytic enhancement mechanism of defect filling in detail, fills the gap of defect filling in the field of biomass upgrading, and provides favorable guidance for the further development of defect regulation strategies.

Cyanogel-Transformed Porous Palladium and Iron Framework Intermixed with rGO for Wearable Hydrogen Sensing.

Wearable hydrogen (H2) sensing is necessary to monitor the H2 leakage in its transportation and storage, of which ppm-concentration detection limit and fast response at room temperature are highly desired. Here, a wearable H2 sensing working at room temperature is developed with palladium and iron framework intermixed with reduced graphene oxide (rGO//Pd-Fe FW), which is synthesized by combined Pd-Fe cyanogel immobilized with graphene oxide as precursor and in situ reduction. As-prepared rGO//Pd-Fe FW is observed with porous FW structure composed of interconnected Pd-Fe nanoparticles, in which rGO is evenly intermixed. Beneficially, rGO//Pd-Fe FW exhibits 2ppm low detection limit and 2 s fast response (1 v/v% H2) at room temperature. Such excellent H2 sensing performance may be attributed to the synergistic effect of the optimized Pd-Fe FW's catalytic activity, boosted electron transfers between Pd hydride and rGO, and enriched adsorption sites over porous FW's surface. Practically, the perceptron learning algorithm combined with principal component analysis is conducted to identify the H2 leakage, and the wearable H2 sensing devices are built by integrating rGO//Pd-Fe FW over the paper and flexible printed circuit board with reliable sensing responses.

One-Pot Synthesis of Mixed-Phase MoVTeNbOx Catalysts for Selective Oxidation of Propane to Acrylic Acid.

One-pot hydrothermal synthesis assisted by sodium citrate and citric acid is developed to fabricate mixed-phased MoVTeNbOx catalysts with different phase compositions for selective oxidation of propane to acrylic acid. Structures of various catalysts are comprehensively characterized. Interfacial interactions occur among the M1 and M2 phases of mixed-phase MoVTeNbOx catalysts to exert synergistic effects on the selective production of acrylic acid. Various mixed-phase MoVTeNbOx catalysts exhibit the same type of active site on the M1-phase component, with a significantly enhanced ability to adsorb and activate propane. The propane conversion increases linearly with the density of surface site for propane adsorption, while the propene selectivity increases linearly with the density of surface site for propene adsorption. Among the synthesized catalysts, a MoVTeNbOx catalyst composed of 35.3 wt % M1 phase, 19.2 wt % M2 phase, and 45.7 wt % amorphous phase exhibits the largest density of active site and consequently the best catalytic performance with 38.9% propane conversion and 71.2% acrylic acid selectivity at 380 °C.

Cooperative S-S coupling and H2 production from photocatalytic dehydrogenation of thiols over ReSe2/ZnIn2S4 heterostructure

Photocatalytic anaerobic dehydrogenation provides a new avenue to cooperatively produce clean fuels and fine chemicals, while minimizing waste discharge and reducing environmental impact. Here, we demonstrate an efficient co-production of disulfides and H2 via photocatalytic S-S dehydrogenation of thiols using a two-dimensional (2D) heterostructure of ultrathin ZnIn2S4 (ZIS) nanosheets decorated with dispersed (1T phase) ReSe2 nanoparticles. Experimental characterizations and DFT calculations reveal that integrating ReSe2 with ZIS leads to the formation of a robust internal electric field (IEF) within the ReSe2/ZIS heterostructure. The distorted 1T phase ReSe2 with abundant active Se sites and a high Fermi level induces downward band bending of ZIS at the interface, which promotes charge separation and expedites H2 evolution. Moreover, the introduction of ReSe2 provides more adsorptive sites, increasing the concentration of reactants on the catalyst surface. This enhancement fosters surface interactions between the catalyst and p-toluenethiol (PTT), ultimately accelerating the reaction rate. The optimal H2 and S-S coupling p-tolyl disulfide (PTD) production rates of the 5 wt% ReSe2/ZIS composite reach 2275 and 2303 µmol g−1h−1, respectively, approximately 5 times greater than those of blank ZIS. Importantly, the selectivity of PTD reaches 98.4 %. This visible-light-driven dehydrogenation process aligns with the principles and objectives of green chemistry, realizing high atom economy without generating byproducts. It is anticipated to open new possibilities for sustainable and environmentally friendly routes for synthesizing high-value chemicals and producing clean energy.

Constructing SDBS-intercalated MoS2 nanosheets confined and near-vertically grown on network biochar adsorbent: Insights into highly efficient co-adsorption of ciprofloxacin and lead ions

To overcome the problems of the weak adsorption ability of biochar to heavy metal ions (HMIs) and competitive adsorption between HMIs and antibiotics during co-adsorption, the adsorbent material in which 2D sodium dodecylbenzenesulfonate-intercalated molybdenum disulfide nanosheets confined and growing near-vertically on 3D network biochar (SDBS-MoS2/BC) was synthesized. The SDBS-MoS2/BC demonstrated good adsorption ability for ciprofloxacin (CIP) and lead ions (Pb2+). Notably, the adsorption capacity of SDBS-MoS2/BC for the target in the binary system remains higher than in the single system, even at elevated concentrations of the competing target (Qmax,CIP = 393.701 mg g−1, Pb2+: 100 mg/L; Qmax,Pb = 264.550 mg g−1, CIP: 100 mg/L). This may be due to the improvement in the utilization of edge/interlayer adsorption sites by the near-vertical SDBS interlayer expansion of MoS2 as a heavy metal ion anchor. Furthermore, the spatial difference between the upper edge site of near-vertical SDBS-MoS2 and the BC plane, that is, the “longitudinal steric effect”, can separate the CIP and Pb2+ adsorptions in a different horizontal plane to avoid competitive adsorption. The underlying adsorption mechanism was elucidated through a series of experiments and the analysis of characterization results. Furthermore, the load of the SDBS-MoS2/BC sponge-packed column can continuously remove contaminants from water. The rapid, anti-interference, multifunctional and reusable properties make SDBS-MoS2/BC promising for excellent environmental treatment.

Synthesis and carbon monoxide purification performance of ZSM-5 molecular sieve Co-doped Mn/V catalytic material

Trackless, rubber-tired, diesel-powered vehicles are widely used in the mining industry. In recent years, the use of high-performance catalysts to remove carbon monoxide (CO) from diesel vehicle exhaust has attracted much attention. In this paper, a series of manganese-vanadium doped ZSM-5 molecular sieve catalysts were prepared by an impregnation method. The structures of the catalysts were characterized and experiments were conducted to evaluate their performance. The CO catalytic oxidation performance experiments revealed that Mn0.6-V0.4-ZSM-5 had the best performance, with a conversion rate of 97.5 % at 300 °C. The catalyst was also tested for water resistance and stability. Kinetic measurements were performed and the fitted activation energy was 22.68 kJ/mol. Characterization studies revealed that the surface defects formed by Mn and V doping provided a large number of active sites and oxygen vacancies for CO oxidation, increased the number of adsorbed oxygen species on the surface, and enhanced the redox capacity through the interaction of Mn4+ and V5+ to improve the catalytic oxidation performance of the catalyst. The adsorption configurations, adsorption energy (Ebin), and formation energy of oxygen vacancies of CO at different adsorption sites and different active fractions were calculated with density functional theory. The Ebin of CO on Mn2V2O7, the active fraction of Mn0.6-V0.4-ZSM-5, was −1.29 eV, which was the most stable adsorption configuration. This configuration had good oxygen mobility, and was conducive to CO catalysis, confirming the characterization and performance experiments.

Eco-friendly micro-mesoporous carbon from sucrose and sodium metasilicate template for ciprofloxacin adsorption: Effect of molecules self-association over diffusion mechanisms

A green synthesis route of ordered mesoporous carbon by nanocasting of sucrose/sodium metasilicate with template removal only by hot water (70 °C) is proposed. The metasilicate-sucrose mesoporous carbon (MSMC) was characterized by structural, textural, surface chemistry properties and their effect on ciprofloxacin (CIP) adsorption. Phenomenological modeling was applied, including two surface-reaction models: adsorption on adsorbent sites (AAS) and on heterogeneous surface (AHS), and two mass transfer models: external film (EFD) and intraparticle homogeneous (IHD) diffusion. A controlled porous structure containing mesopores (3.8 nm) with micropores (1.8 and 0.87 nm) allowed the “pore filling effect” mechanism and strongly favorable kinetics. A highly oxygenated carbon material (C: 81.84 % O: 15.04 % Si: 1.72 % Na: 1.29 %) with efficient template removal was obtained. Unusual behavior of the rate-limiting step (AAS or IHD) as a function of CIP concentrations was observed, with mechanism changes due to self-aggregation of CIP molecules (dimers, trimers and tetramers).

A distinct role of microstructure on hot corrosion behaviour of additively manufactured IN718

The effect of LPBF-IN718 microstructure on hot corrosion behavior was studied at 650 °C. H-IN718 with <001> oriented grains demonstrate more weight changes than V-IN718 with <110> oriented grains. Detailed characterization analysis corroborates that Rapp-Goto fluxing and sulphidation mechanisms are operating in LPBF-IN718 with 3SM. Further, GDOES confirms the sulphur gradient existence between Air/3SM and 3SM/H-IN718 interfaces. It suggests that <001> oriented grains serve as preferred sites for ion adsorption and reactions, which might facilitate the sulfur diffusion more effectively than other grain orientations. As a result, oxy-anions generated during sulfidation enhance the fluxing mechanism, increasing weight gain in H-IN718.

Novel N-doped carbon nanotubes impregnated Mn spheres with polydopamine coating as an efficient polysulfide immobilizer for Li-S batteries

Lithium-sulfur (Li-S) batteries are one of the most promising energy storage and conversion devices due to the high theoretical capacity and cost-effectiveness of sulfur. However, they still suffer from sluggish redox kinetics and the shuttle effect caused by complex polysulfides. In this work, graphitic carbon nitride (g-C3N4) is utilized as a template and further hydrothermally treated with an Mn source and glucose. The pyrolysis of g-C3N4 gives rise to N-doped carbon nanotubes, producing abundant sites for physical confinement and chemical adsorption of polysulfides, while glucose carbonization brings forth amorphous carbon and Mn source produces metal spheres. Afterward, polydopamine (PDA) induces N-doped carbon coating and promotes interface connection as well as electron immigration. This synergistic design possesses a high surface area of micropores and mesopores to aggregate sulfur and accelerate redox kinetics. As a result, the N-doped carbon nanotube with Mn spheres and PDA coating@sulfur (CN/Mn-PDA@S) exhibits a high reversible capacity of 813.5 mAh g−1 at 1 C with a decay rate of 0.064% per cycle and remarkable capacity retention at 2 C with rate performance up to 4 C. Therefore, the novel design of N-doped carbon nanotubes with Mn spheres and PDA coating serves as an efficient polysulfide immobilizer for Li-S batteries.

Enhancing carbamazepine degradation in electrochemical systems: The interplay of sulfur vacancies and absorbed peroxydisulfate in molybdenite electrodes

Achieving high reaction efficiency with low energy input is crucial for electrochemical water remediation processes, yet remains a significant challenge. This study reported a practicable method, utilizing natural molybdenite as particle electrodes in an electro-activated peroxydisulfate (PDS) process (3D system) to develop a cost-efficient electrocatalytic oxidation system. Molybdenite’s unique ability to generate sulfur vacancies during electrocatalysis significantly enhances system efficiency. The 3D system enhanced the rate constant of carbamazepine (CBZ) abatement sixfold compared to the system without molybdenite. Additionally, a substantial decrease in electrical energy per order (EE/O) from 7.13 kWh/m3 to 0.326 kWh/m3 indicates a near 22-fold increase in energy efficiency. Characterizations involving electron microscopies, electrochemical experiments and density functional theory calculations confirm that hydroxyl radicals (•OH) and adsorbed PDS(PDS*) are the main active species. Molybdenite’s surface with plenty of edge-S, released S vacancy during electrocatalytic oxidation, providing adsorption and activation sites for PDS and H2O. This led to more active sites and facilitating the generation of PDS*, lowering the energy barrier for •OH formation and boosting the oxidation performance of the 3D system. The results underscore the constructed 3D system is a robust and energy-efficient method for practical water treatment.

Single nickel atoms anchored on porous N-doped nanocarbon with dual reaction sites for highly-efficient transfer hydrogenation of furfural to furfuryl alcohol

The non-precious metal single-atom catalysts (SACs) supported on carbon materials for the catalytic transfer hydrogenation (CTH) of α,β-unsaturated aldehydes (UAL) still suffer from the problems of harsh reaction conditions and low activity. In this work, nickel SACs anchored on porous N-doped nanocarbon (Ni1/NC900) with dual reaction sites were synthesized using the high internal-phase emulsion (HIPE) template method combined with impregnation. The Ni1/NC900 catalyst exhibited remarkable catalytic activity for the CTH of furfural (FF) to furfuryl alcohol (FFA), achieving >99.0 % conversion and selectivity at 100 °C for 60 min, with a turnover frequency (TOF) of 2908.1 h−1, surpassing other reported nickel-based catalysts by 1–3 orders of magnitude. The excellent catalytic performance of Ni1/NC900 was attributed to the high mass transfer efficiency (HMTE) of the support and the dual reaction sites of Ni–N4 and pyridinic N, where Ni–N4 as Lewis acidic site for adsorption of FF and isopropanol (i-PrOH), while the adjacent pyridinic N as Lewis basic site for the deprotonation of i-PrOH. The isotope labeling experiments revealed that the hydrogenation of FF was accomplished by proton transfer with i-PrOH, in agreement with the intermolecular hydride transfer mechanism. Furthermore, Ni1/NC900 demonstrated excellent stability and well general applicability, demonstrating its potential for industrial applications. This work provides a reference for the application of carbon-based non-precious metal SACs in the CTH reaction of UAL.

Dual-functional adsorptive membranes for PFAS removal: Mechanism, CFD simulation, and selective enrichment

The remediation of emerging water contaminants, particularly per- and polyfluoroalkyl substances (PFAS), presents challenges due to their refractory nature and the presence of competing substances. Dual-functional adsorptive membranes, with hydrophobic backbone and quaternary ammonium moieties, were thereby designed to selectively intercept organic competitors while enrich PFAS. A 96.8 % removal of perfluorooctanoic acid (PFOA) was achieved and this effective removal (>90 %) maintained across five reuse cycles with a total treatment capacity of 650 L m−2. Rather than the rejection mechanism of nanofiltration process, these adsorptive membranes utilize synergistic electrostatic attraction and hydrophobic interactions, leading to a greater enrichment factor of 18.5 (PFOA over humic acid) and a permeability of 34.6 L m-2h−1 bar−1 (1.9- and 4.5-fold higher than reported NF 270 membranes, respectively). Furthermore, computational fluid dynamics (CFD) modeling revealed that the sponge-like matrix effectively prevents channeling flow and enhance access to adsorption sites. Sensitivity analysis and the high Damkohler number indicated that the adsorption process is mass transfer-controlled, with the key parameters ranked in order of significance: residence time > fluid viscosity > intrinsic adsorption rate. With consistent removal performance with co-existing competitors, efficient regeneration, and reusability, the dual-functional adsorptive membranes offer promising practical efficacy for PFAS remediation.