Short Diffusion Research Articles

Specifically Targeting Capture and Photoinactivation of Viruses through Phosphatidylcholine-Ganglioside Vesicles with Photosensitizer.

Herein, we performed a simple virus capture and photoinactivation procedure using visible light on phosphatidylcholine vesicles. l-α-Phosphatidylcholine vesicles were enriched by viral receptors, GT1b gangliosides, and the nonpolar photosensitizer 5,10,15,20-tetraphenylporphyrin. These vesicles absorb in the blue region of visible light with a high quantum yield of antiviral singlet oxygen, O2 (1Δg). Through the successful incorporation of gangliosides into the structure of vesicles and the encapsulation of photosensitizers in their photoactive and monomeric state, the photogeneration of O2(1Δg) was achieved with high efficiency on demand; this process was triggered by light, and specifically targeting/inactivating viruses were captured on ganglioside receptors due to the short lifetime (3.3 μs) and diffusion pathway (approximately 100 nm) of O2(1Δg). Time-resolved and steady-state luminescence as well as absorption spectroscopy were used to monitor the photoactivity of the photosensitizer and the photogeneration of O2(1Δg) on the surface of the vesicles. The capture of model mouse polyomavirus and its inactivation were achieved using immunofluorescence methods, and loss of infectivity toward mouse fibroblast 3T6 cells was detected.

Ionic conductivity and dielectric characteristics of a Li incorporated PVA electrolyte membrane and a study of a fully solid-state electrochromic device based on it

The construction and study of a fully solid state electrochromic (EC) device with cathodic coloration exhibiting very fast response times (< 1s) is reported using a WO3 EC layer and a poly (vinyl alcohol) (PVA)- Lithium acetate membrane electrolyte. Broadband dielectric studies on the polymer membranes with different Li concentrations show multiple relaxation mechanisms out of which a segmental relaxation prominent beyond a certain composition is strongly correlated with Li-ion conduction yielding better ionic conductivity and reversible coloration in the EC device. The relatively high Li conductivity in PVA has a direct correspondence with the lowering of the crystallinity of PVA and a decrease of the glass transition temperature, Tg with increasing Li addition. A simple model of the coloration process suggests that the short electrolyte diffusion length coupled with a high electric field and an interfacial emf that varies as ≈t−0.6 results in the swift current response of the film with an optimal performance at 20 wt.% Li in PVA, exceeding which irreversible coloration can occur on the surface. The transient current is crucial for the observed swift switching characteristics. Ageing studies for almost a month indicate potential stability of the EC device for over 150 cycles.

Synthesis, characterization and photoelectrochemical performance of Bi2Fe4O9 thin films

Mullite-type Bi2Fe4O9 has been little explored in thin film form as a photoanode for photoelectrochemical water splitting. In this study, Bi2Fe4O9 thin films have been prepared using the sol-gel technique from a simple precursor solution based on the corresponding metal salts, acetic acid, and polyvinyl alcohol. The films were deposited by dip-coating onto fluorine-doped tin oxide substrates and dried at 350 °C, repeating the dipping-drying cycle six times, and finally sintered at 600 °C. The films were characterized by GIXRD, revealing the formation of the material in its orthorhombic phase. Raman spectroscopy showed the Ag and B1g vibrational modes, validating the formation of the bismuth iron oxide. UV–Vis transmittance measurements revealed that the material exhibits two optical transitions: a direct band gap of 2.86 eV and an indirect band gap of 1.98 eV. FESEM micrographs and AFM images showed a uniform nanostructured surface morphology. The photoelectrochemical properties of the Bi2Fe4O9 films were studied using cyclic voltammetry and chronoamperometry with front side illumination, demonstrating the stability of the material in aqueous media and the generation of photocurrent in the presence of H2O2. Furthermore, results from intensity-modulated photocurrent spectroscopy (IMPS) revealed that the photocurrent is limited by both bulk and surface recombination and a short hole diffusion length.

Microstructural evolution of Fe-25 W powder beds during CO2-H2 redox cycling at 800 °C

Fixed powder beds of Fe-25 W at% powders show excellent resistance to degradation during CO2-H2 redox cycling at 800 °C, releasing CO and H2O, respectively, with 100 % metal utilization. During cycling up to 165 full redox cycles (∼500 h), the reaction kinetics improve with cycle number and a stable, hierarchically-porous microstructure forms that shows neither sintering nor densification. The sintering inhibition provided by W addition to Fe stems from the formation of Fe-W mixed phases: as an intermetallic compound (Fe2W) in the reduced state and as a ternary oxide (FeWO4) in the oxidized state. In addition to the large channels running between coarse (100 µm) powder agglomerates, each agglomerate in the powder bed shows both microporosity due to sintering inhibition, and submicron porosity due to a chemical vapor transport reduction mechanism that is active when FeWO4 is reduced by H2 at high temperature. This hierarchical porosity enables fast reactions due to the short diffusion distance to free surfaces, and non-tortuous gas flow through the powder bed. As a result, under high CO2 flow, the CO2:CO ratio is sufficiently high to oxidize Fe3O4 to Fe2O3, improving the CO conversion capability on a per-mole basis.

Sulfur-doped pomegranate-like carbon microclusters designed via facile spray-drying process: A novel anode material for potassium-ion batteries

Recent research has demonstrated increasing inclination toward employing hollow carbons featuring nanoscale amorphous structures as anodes in potassium-ion batteries. However, these amorphous structures detrimentally impact the electrode’s electron and ion conductivities, leading to subpar rate performance. Additionally, integrating nanoparticles into electrodes typically yields an uneven distribution, owing to the propensity of nanomaterials to readily aggregate. To address these challenges, S-doped pomegranate-like carbon microclusters (S-PCMs) comprising S-doped primary hollow carbon spheres (HCSs) were synthesized via spray drying. The effects of self-assembly and S doping on the morphological structure and potassium storage performance of the HCS materials were systematically investigated through comprehensive analyses. PCMs mitigated volume expansion and imparted high conductivity and charge/discharge rates owing to short potassium-ion diffusion distances, while the self-assembled nanospheres improved slurry flow properties. Additionally, sulfur doping increased the pore size, interlayer spacing, and number of defect sites in the carbon lattice, improving electron mobility. The resulting S-PCMs exhibited exceptional potassium storage properties, particularly cycling performance (224 mA h g−1 at the 1000th cycle). Furthermore, various electrochemical tests attributed S-PCM’s enhanced potassium storage performance to the numerous active sites and increased resistance to charge transfer, improving the potassium diffusion coefficient.

(Invited) 3D Carbon-Based Hierarchical Electrodes for Energy Storage

: Carbon-based 3D hierarchical electrodes with appropriate spatial distributions of pores are expected to empower rapid and controllable electrochemical reactions. The ability to fabricate such an electrode, with tunable geometries comprised of continuous nano- and micro-conduits, allows simultaneous optimization of conversion capacity as well as reaction rate. Such manufacturability holds great potential to redefine the future of energy storage, electrocatalysis and chemical production for a sustainable future.In this presentation, I will outline two convergent strategies that involve the integration of additive manufacturing with several decades of advancements in nanomaterials synthesis, coupled with conventional pyrolysis – for creating such electrodes. The primary structure of 3D carbon-based electrodes was fabricated by either direct 3D writing, or the transition metal assisted pyrolysis of 3D-printed polymer templates. The secondary structure was established by employing bottom-up synthesis approaches: (a) SiO2 nanoparticle templates to create nanoscopic porous structures or (b) nanochannels formed through direct growth of carbon nanotubes. We have demonstrated that the primary and secondary structures can be formed by a single step. After monolithic integration of a tertiary structure to reveal sites for electrochemical conversion, these 3D architected electrodes offer impressive charge storage capacities while maintain excellent rate capability.By exploiting the short mass diffusion lengths, we have demonstrated that the new energy storage devices can operate at temperatures as low as -70°C without the requirement of a heater. Furthermore, the incorporation of a high loading of active materials in our 3D electrodes allows for concurrent enhancement of both energy density and power density. These scalable fabrication protocols address two critical challenges – sluggish mass transfer in 3D and the lack of accessible active sites, thereby offering a pathway to harness electrochemical reactions in 3D. This work offers an adaptable solution across a broad spectrum of industries.

Porous Bismuth Vanadate Photoelectrodes for Solar Water Oxidation Reaction

Bismuth vanadate (BiVO4), a material known for its high visible light activity and good stability, is a promising candidate as a photoanode for overall water splitting [1]. Its performance is limited by its relatively short charge carrier diffusion length, which has recently been estimated to be ~15 nm [2]. For these kinds of photo-absorbers, commercial flat transparent conducting oxide (TCO) substrates are unsuitable since the thickness needed to absorb a sufficient amount of light far exceeds the carrier diffusion length. With this in mind, deposition of very thin semiconductor film onto the internal structure of (micro)porous, conducting substrates can ensure sufficient light absorption [3], whilst ensuring the individual film thickness is uniformly lower than the carrier diffusion length. Nanostructured TCO substrates can be fabricated using a convenient template-free technique called glancing angle deposition (GLAD). The glancing angle deposition method can be used to synthesize different variations of highly oriented submicron-sized pillars, ranging from vertical and tilted columns to zig-zag and helical structures with the help of shadowing effects and substrate rotation [4]. The optical and electrical properties of nanostructured TCO’s were found to depend on the type of material and the substrate temperature during deposition. We find that pillars made from tin-doped indium oxide show good conductivity (79 Ohm/sq) and are promising for the fabrication of nanostructured substrates for bismuth vanadate. A recently developed alternative approach is the use of transparent, porous, conducting substrates (TPCS) made from quartz felt, in which the quartz fibers are coated with F-doped SnO2 [5]. We found that a BiVO4 film thickness of 50 nm within these porous substrates is enough to absorb the same amount of light as a compact 400 nm bismuth vanadate film. We will discuss the deposition of BiVO4 into the TPCS substrates and the photoelectrochemical performance of these porous photoanodes.[1] K. Sivula and R. van de Krol, Nat. Rev. Mater. 1, 15010 (2016)[2] M. Schleuning, M. Kölbach, F. F. Abdi, K. Schwarzburg, M. Stolterfoht, R. Eichberger, R. van de Krol, D. Friedrich, H. Hempel, PRX Energy 1, 023008 (2022)[3] U. Björksten, J. Moser and M. Grätzel, Chem. Mater. 6, 858 (1994)[4] M. M. Hawkeye, M. T. Taschuk and M. J. Brett, “Glancing Angle Deposition of Thin Films”, John Wiley & Sons, Ltd., Chichester, UK (2014).[5] M. Caretti, E. Mensi, R.-A. Kessler, L. Lazouni, B. Goldman, L. Carbone, S. Nussbaum, R. A. Wells, H. Johnson, E. Rideau, J.-h. Yum, K. Sivula, Adv. Mater. 35, 2208740 (2023)

(Invited) Nanowire Catalysts and Adsorbents

The unique properties of nanowire materials like fast charge transport, short diffusion length, controlled surface sites and single crystal nature make them ideal for designing high performance catalysts, adsorbents and electrocatalysts by design. To realize any of these applications, one would need either large quantities of nanowire powders or nanowire arrays on large areas. In this presentation, we will highlight our group’s efforts with scalable methods for continuous manufacturing of nanowire powders and arrays for oxides1 and III-nitride materials.2 The process for producing metal oxide nanowires has been scaled up to ton-scale. The resulting nanowire powders can be used to formulate unique catalyst and adsorbent products.Zinc oxide nanowires alloyed with catalytically active metals and have been formulated into ultra-deep desulfurization catalytic adsorbents.3,4 These materials exhibited ultra-deep desulfurization with sulfur removal down to 1 ppm or below for liquid hydrocarbons (diesel, gasoline and naphthalene) and to less than 1 ppb for natural gas. The desulfurization mechanism does not involve formation of H2S species unlike that typically observed with hydro-desulfurization process involving sulfided catalysts.Titania nanowires supported with nickel and molybdenum clusters have also shown to exhibit high activity and durability as hydro-desulfurization catalysts for removal of sulfur from hydrocarbons by forming H2S.5 The synergistic activity with MoS2 and titania are expected to contribute to enhanced activity with desulfurization.Alloying of nanowires with other elements is also studied to produce compound and alloyed nanowires. Fundamental studies have shown that alloying process occurs at much lower temperatures than decomposition temperatures for precursors used. Alloying studies have clearly shown that the solubility in nanowires to be much more than that expected for bulk materials systems. This presentation will provide several examples in which nanowires were alloyed with elements at compositions more than that expected for thermodynamic solubility.In the case of CO2 sorbents, alkali metal oxide nanowires have shown high capacity for CO2 sorption as high as 75% by wt. The alkali metal oxide nanowires have been alloyed with alkali hydroxides to produce alkali metal oxide compound nanowires. These solid sorbents showed selective CO2 sorption from a variety of streams including air, exhausts containing CO2 at various concentrations. Nanowire geometry for these nanowires allow for non-sinterability, and smaller length scales for rapid diffusion of alkali ions allow for fast kinetics and regenerability. 6,7 Acknowledgements: Authors also acknowledge contributions from Drs. Juan He, Sivakumar Vasireddy, Vivekanand Kumar, Veerendra Atla and Tu Nguyen. Partial support from National Science Foundation (NSF) and US Department of Energy (DOE) EPSCOR programs and full support from NSF and DOE SBIR programs and Kentucky Cabinet for Economic Development for Advanced Energy Materials, LLC are highly appreciated.

Influence of Microstructure on Defect Chemistry - Transport - Chemical Strain Coupling of (Pr,Ce)O2-δ Nanoparticles

Solid oxide fuel/electrolysis cells (SOFC/SOECs) are promising and environmentally-friendly technologies for meeting ever-increasing electricity and energy storage demands. Nanostructuring of SOFC/SOEC electrodes can enable improvement of the reaction kinetics and reduction of the operating temperature, owing to factors including the enlarged surface area, short diffusion lengths, and unique surface & interface properties. While the kinetic benefit is apparent, the effect of nanostructuring on other device-relevant physico-chemical properties cannot be neglected. Especially, the coefficients of chemical expansion (CCEs) are an important metric for mixed ionic-electronic conductors that can undergo changes in oxygen stoichiometry with variations in the surrounding atmosphere, temperature, and voltages during processing/operation. Chemical strains can cause cracking of monolithic parts during fabrication and delamination of electrodes from electrolytes in operation. CCEs are typically measured on bulk, polycrystalline materials with large particle or grain sizes. Therefore, it is important to understand the coupled transport and chemical expansion behavior in nano-ionic materials with large interface/surface density. This work aims to uncover the role of microstructure and nanoscale effects on the chemical strain and transport properties, through the lens of defect chemistry, with the goal of ultimately developing design principles for zero-strain materials with improved device lifetime and performance.Pr0.2Ce0.8O2- δ (PCO20) was selected as a model system and prepared as nanoparticles by a surfactant-free, low temperature co-precipitation method. (Pr,Ce)O2-δ compositions are valuable model oxide ion conductors to study, since both Pr and Ce can undergo changes of valence states under different temperature and pO2 regimes to accommodate oxygen stoichiometry excursions. Prepared nanoparticle samples were first in-situ sintered in the dilatometer at three different temperatures (600 ⁰C, 725 ⁰C, 850 ⁰C) to induce and evaluate microstructure evolution. The chemical strain and electronic/ionic conductivity were then studied on stable microstructures with different average particle sizes at lower temperatures by simultaneous in-situ dilatometry and electrochemical impedance measurement (EIS) upon changing pO2 at different isotherms (550 to 400 ⁰C). At each isotherm, all the samples expand as pO2 decreases. From the conductivity vs. pO2 measurements, the maxima at certain pO2 indicate the dominant polaron mechanism of the electronic transport, consistent with the measured conductivity activation energy. However, samples with lower sintering temperatures exhibit less pO2 dependence of the conductivity, which implies a transition in the mixed ionic/electronic conduction behavior toward higher ionic transference numbers as particle size decreases. Correspondingly, the chemical strains associated with losing oxygen monotonically decrease with the decrease of the sintering temperature, and hence the particle size. The chemical strain vs. oxygen stoichiometry dependence and corresponding CCEs were quantified as function of particle size and temperature by combining thermogravimetric analysis (TGA) with the dilatometry results and in-situ X-ray diffraction. The particle size, chemical composition, valence states, and morphology of samples after CCEs measurements were also compared using XRD, SEM, and S/TEM-EELS, with the latter indicating the expected differences between bulk and surface defect chemistry. Implications of the results for size-dependent defect chemistry and its influence on chemical strains and redox CCEs will be further discussed. Keywords: redox, chemical expansion, defect chemistry, mixed ionic electronic conduction, ceria, chemo-mechanics, nanoparticle, thermogravimetric analysis, dilatometry, impedance

Nanohybrid-Based Redox Homeostasis Perturbators Escaped from Early Lysosomes toward Amplified Sensitization of Tumor Cells and Photothermally Maneuvered Pyroptosis Therapy.

Reactive oxygen species (ROS) hold great potential in tumor pyroptosis therapy, yet they are still limited by short species lifespan and limited diffusion distance. Inducing cells into a metastable state and then applying external energy can effectively trigger pyroptosis, but systemic sensitization still faces challenges, such as limited ROS content, rapid decay, and short treatment windows. Herein, a nanohybrid-based redox homeostasis-perturbator system was designed that synergistically induce early lysosomal escape, autophagy inhibition, and redox perturbation functions to effectively sensitize cells to address these challenges. Specifically, weakly alkaline layered double hydroxide nanosheets (LDH NSs) with pH-responsive degradation properties enabled early lysosomal escape within 4 h, releasing poly(L-dopa) nanoparticles for inducing catechol-quinone redox cycling in the cytoplasm. The intracellular ROS levels were systematically rebounded by 3-4 times in tumor cells and lasted for over 4 h. Subsequently induced lysosomal stress and Ca2+ signaling activation resulted in severe mitochondrial dysfunction, as well as a perilous metastable state. Thereby, sequential near-infrared light was applied to trigger amplified stress through a local photothermal conversion. This led to sufficiently high levels of cleaved caspase-1 and GSDMD activation (2.5-2.8-fold increment) and subsequent pyroptosis response. In addition, OH- released by LDH elevated pH to alleviate the limitation of glutathione depletion by quinones at acidic pH and inhibit protective autophagy. Largely secreted inflammatory factors (2.5-5.6-fold increment), efficient maturation of dendritic cells, and further immune stimulation were boosted for tumor inhibition as a consequence. This study offers a new paradigm and insights into the synergy of internal systematic cellular sensitization and sequential external energy treatment to achieve tumor suppression through pyroptosis.

Thermal Exfoliation and Phosphorus Doping in Graphitic Carbon Nitride for Efficient Photocatalytic Hydrogen Production.

Photocatalytic H2 evolution has been regarded as a promising technology to alleviate the energy crisis. Designing graphitic carbon nitride materials with a large surface area, short diffusion paths for electrons, and more exposed reactive sites are beneficial for hydrogen evolution. In this study, a facile method was proposed to dope P into a graphitic carbon nitride framework by calcining melamine with 2-aminoethylphosphonic acid. Meanwhile, PCN nanosheets (PCNSs) were obtained through a thermal exfoliation strategy. Under visible light, the PCNS sample displayed a hydrogen evolution rate of 700 μmol·g-1·h-1, which was 43.8-fold higher than that of pure g-C3N4. In addition, the PCNS photocatalyst also displayed good photostability for four consecutive cycles, with a total reaction time of 12 h. Its outstanding photocatalytic performance was attributed to the higher surface area exposing more reactive sites and the enlarged band edge for photoreduction potentials. This work provides a facile strategy to regulate catalytic structures, which may attract great research interest in the field of catalysis.

Effect of annulus ratio on the residence time distribution and Péclet number in micro/milli‐scale reactors

AbstractMicro/milli‐scale annular reactor with straight and helical forms has excellent heat and mass transfer performance due to the short molecular diffusion distance and dual‐wall surface transport. The annular gap spacing is scalable by adjusting the inner and outer tube diameter. The influence of diffusion and convection effects on axial dispersion as expanding the flow scale requires further elucidation with the help of residence time distribution (RTD) curves and Péclet (Pe) numbers. The correlation of RTD characteristics with annulus ratio γ = Dh/D (ratio of annulus characteristic size to outer diameter) is investigated using computational fluid dynamics. Results show that with enlarging the straight annular gap from micro‐scale to milli‐scale, RTD characteristics exhibit opposing patterns. This can be attributed to the transition from diffusion‐dominated to convection‐dominated on momentum transfer, and the transition interval is 0.167 &lt; γ &lt; 0.250. Correlation equations of Pe number with Reynolds (Re) number and γ are established under diffusion‐dominated and convection‐dominated states. The symmetrically distributed secondary flow in the helical annular gap effectively elevates the Pe (Pemax &gt; 100). Correlation equations of Pe with Re and γ are established in helical annular gaps with 0.083 &lt; γ &lt; 0.208 and 0.167 &lt; γ &lt; 0.500. The above results contribute to understanding the annular flow RTD characteristics for better applications of tube‐in‐tube reactors.

Macromolecular Nano-Assemblies for Enhancing the Effect of Oxygen-Dependent Photodynamic Therapy Against Hypoxic Tumors.

In oxygen (O2)-dependent photodynamic therapy (PDT), photosensitizers absorb light energy, which is then transferred to ambient O2 and subsequently generates cytotoxic singlet oxygen (1O2). Therefore, the availability of O2 and the utilization efficiency of generated 1O2 are two significant factors that influence the effectiveness of PDT. However, tumor microenvironments (TMEs) characterized by hypoxia and limited utilization efficiency of 1O2 resulting from its short half-life and short diffusion distance significantly restrict the applicability of PDT for hypoxic tumors. To address these challenges, numerous macromolecular nano-assemblies (MNAs) have been designed to relieve hypoxia, utilize hypoxia or enhance the utilization efficiency of 1O2. Herein, we provide a comprehensive review on recent advancements achieved with MNAs in enhancing the effectiveness of O2-dependent PDT against hypoxic tumors.

γ-aminobutyric acid-assisted fabrication of plate-like ZSM-5 zeolite for efficient propylene production from methanol conversion

Plate-like ZSM-5 zeolites offering a short diffusion pathway along the b-axis are highly desirable catalyst for methanol to propylene (MTP) reaction. Herein, we successfully developed a simple synthetic strategy toward reducing the thickness along b-axis of ZSM-5 zeolite by combing a preliminary aging process and the addition of γ-aminobutyric acid. In particular, γ-aminobutyric acid adopted as a zeolite growth modifier was firstly proposed to prepare plate-like ZSM-5 zeolite with a short thickness of b-axis, and the minimum thickness can reach ∼50 nm. The shortened diffusion length in plate-like ZSM-5 zeolites could significantly improve the transport efficiency of molecules to and away from the active sites and finally leads to a better catalytic performance in the MTP reaction. Particularly, the plate-like ZSM-5 zeolite with an impressively shortened diffusion length (P-ZSM-5–0.3#0.3) displayed greatly improved catalytic performances (higher propylene selectivity and longer lifetime) than conventional ZSM-5 with a thicker dimension along the b-axis.

Lysine-assisted synthesis of plate-like TS-1 zeolite for 1-hexene epoxidation

Plate-like TS-1 zeolites offering a short diffusion pathway along the b-axis are highly desirable catalysts in the reaction of alkene epoxidation. Herein, we successfully developed a simple synthetic strategy toward reducing the thickness along the b-axis of TS-1 zeolite crystals, l-lysine adopted as a zeolite growth modifier was firstly proposed to prepare plate-like TS-1 zeolite. Meanwhile, through tuning the preliminary aging time, plate-like TS-1 zeolites with thickness in the range of 80–1000 nm can be controllable obtained. In this work, the synthesis parameters controlling the formation of plate-like TS-1 zeolites are studied, and the factors controlling the zeolite growth were well elucidated. Compared with the conventional TS-1 zeolite as well as the plate-like TS-1 synthesized in the fluoride-containing medium, the obtained plate-like TS-1 shows improved catalytic performances in catalyzing epoxidation of 1-hexene.

Hydrogen Sulfide Delivery System Based on Salting-Out Effect for Enhancing Synergistic Photothermal and Photodynamic Cancer Therapies.

The simultaneous application of photothermal therapy (PTT) and photodynamic therapy (PDT) offers substantial advantages in cancer treatment. However, their synergistic anticancer efficacy is often limited by tumor hypoxia, and thermotolerance induced by high expression of heat shock proteins (HSP). Fortunately, hydrogen sulfide (H2S), known for its direct cytotoxic effect on tumor cells, has been recognized for its ability to enhance PTT and PDT. The effectiveness of H2S in these therapies is challenged by its low loading efficiency, poor stability, and short diffusion distance. To address these issues, a nanoscale emulsion drop template created through the salting-out effect is employed to construct a robust H2S delivery system. Polydopamine (PDA), chosen for its interfacial polymerization tendency and excellent photothermal conversion rate, is utilized as a carrier for the H2S donor (ADT) and Zinc phthalocyanine (ZnPc) to fabricate a novel nanomedicine termed APZ NPs. The temperature-responsive APZ NPs are designed to release H2S during the PTT process. Elevated H2S levels promoted vasodilation, thereby enhancing the enhanced permeability and retention effect (EPR) of APZ NPs within solid tumors. This strategy effectively alleviated tumor hypoxia by disrupting the mitochondrial respiratory chain and mitigated tumor cell heat tolerance by inhibiting HSP expression.

Hierarchical metal–organic framework nanoarchitectures for catalysis

Metal–organic frameworks (MOFs) have garnered significant attention in the field of catalysis due to their unique advantages such as diverse coordination geometry, variable metal nodes, and organic linkers, facilitating precise structural and compositional control for achieving programmable catalytic functionalities. Although their inherent microporous structure could provide excellent shape selectivity during catalysis, it typically impedes the mass transfer process, thereby reducing the use of internal active sites and overall catalytic efficiency. Additionally, employing single MOFs as catalysts presents challenges in achieving complex catalytic reactions that require multifunctional active sites. In recent years, considerable research efforts have focused on designing and constructing hierarchical nanostructured MOFs to alleviate substrate diffusion limitations by introducing secondary nanopores, shortening diffusion distances via the construction of low-dimensional nanoarchitectures, and constructing multifunctional catalysts by integrating distinct MOFs with suitable functions. This review provides a comprehensive overview of the design, synthesis methods, and formation mechanisms of MOF-based hierarchical nanostructures in recent years. Subsequently, it further highlights their applications in thermal catalysis, electrocatalysis, and photocatalysis, along with the relationship between their hierarchical nanostructures and catalytic performances. Finally, it provides an outlook on the challenges and potential development directions of hierarchically structured MOF nanocatalysts.

Using PFG‐NMR and iGC to Study Diffusion and Adsorption in Heterogeneous Catalysts

AbstractMass transport in porous systems is inherently complex, but at the same also of utmost importance for large‐scale industrial processes such as heterogeneous catalysis. For each of the different length scales of diffusive motion potentially involved or relevant, specific characterization techniques have been developed and successfully applied over the years – including, but not limited to pulsed field gradient nuclear magnetic resonance (PFG‐NMR) spectroscopy, zero length column (ZLC) measurements and inverse gas chromatography (iGC). While each of these methods can deliver detailed information on certain types of diffusion, none of them are capable of delivering a full picture of mass transport across multiple length scales alone. In this context, the goal of the present work was to evaluate the technical feasibility and characterization potential of the hyphenated combination of PFG‐NMR and iGC in a coupled experimental setup. Challenges, advantages, and limitations of this approach are discussed using the example of propane adsorption and diffusion in two different zeolite catalysts (Mg(H)‐ZSM‐5 and Silicalite‐1). It is shown that the simultaneous detection of self‐diffusion on short length scales (as probed by PFG‐NMR) and transport diffusion covering longer distances (detectable by iGC) cannot be realized under the used conditions, essentially due to the lack of kinetic control at higher reactant loadings. The key advantage of the developed coupled setup is the ability of the iGC instrument to provide defined and readily variable levels of catalyst loading, which enables advanced pore connectivity studies by PFG‐NMR and yields thermodynamic data on reactant adsorption at the same time.

Interlayer-confined strategy to modulate alkaline reaction microenvironment for in-situ degradation of ofloxacin

In advanced oxidation processes designed for the mineralization of organic contaminants, the acidic microenvironment in the peroxymonosulfate (PMS) activation system poses a major threat to the stability of active species. In this study, we developed a low-cost Co-Mg–layered double hydroxide (LDH) structure with an OH−-enriched, interlayer-confined alkaline microenvironment around Co sites. This structure exhibited enhanced surface availability and a short reactant diffusion path, which accelerated proton migration and regulated local pH at the slipping plane. Theoretical calculations revealed that CoMg-LDH exhibited high catalytic activity for PMS cleavage and generated high-valence Co-oxo (Co(IV)=O) species in this specific microenvironment. At a natural pH, the optimized system achieved 100 % removal efficiency of the target pollutant (ofloxacin), with negligible Co leaching. It also demonstrated stability in long-term experiments and effectively purified hospital wastewater. Overall, this study provides valuable insights into the in-situ degradation of contaminants through self-regulating catalytic systems.

Encapsulating Antimony metal nanoparticles in hierarchical porous carbon skeleton as high-performance potassium- and lithium-ion batteries anodes

Metallic antimony (Sb) as alkaline metal battery anode material, being thoroughly researched for its high theoretical specific capacity, but there is still a huge expansion problem with repeated insertion/de-insertion., We reported a unique composite material that encapsulates Sb nanoparticles in hierarchical porous carbon skeletons (Sb@HPCs) in this work, to explore the effect of the hierarchical porous carbon structure on the electrochemical performance of the Sb@HPCs as potassium-ion batteries (KIBs) and lithium-ion batteries (LIBs) anode materials. The macropores could promote the penetration of electrolyte, thus reducing the internal impedance of the battery. The mesopores provide a short ion diffusion path and a large diffusion region, which plays a crucial role in facilitating rapid ionic migration in both KIBs and LIBs. The micropores in the electrode material contribute to a larger specific surface area, which provides more surface area for charge storage, thus enhancing the energy density of the material. Importantly, when the Sb@HPCs composite material is applied as anode material of KIBs, it exhibits an outstanding specific capacity of 360 mAh g−1 after 100 cycles at 100 mA g−1. In the LIBs, the specific capacity of the composite material is 595.2mAh g−1 after 100 cycles at a current density of 0.1 A g−1; even at a high current density of 1.0 A g−1, the specific capacity still maintains at 320.4 mAh g−1 after 800 cycles, indicating an excellent cycling stability. The development of hierarchical porous three-dimensional structure offers a practical solution to the capacity degradation issues of metal anode in KIBs/LIBs.