RESUMEN

Nanocatalysts with photodynamic therapy (PDT) and chemodynamic therapy (CDT) are excellent for tumor therapy. However, it is still challenging to achieve complete tumor eradication due to the drawbacks of limited penetration depth of intratumoural tissues, hypoxia and complexity of the tumor microenvironment (TME). Herein, we fabricated an integrated multifunctional nanoreactor (LuAG:Tb/Ce-RB@ZIF-8-Au2Pt-HA, LRZAPH) combining scintillating nanoparticles (SCNPs, LuAG:Tb/Ce), a metal-organic framework (ZIF-8), and bimetallic Au2Pt for X-ray-triggered PDT and dual noble-metal nanozyme catalyzed CDT. Such a nanoreactor not only significantly enhanced the PDT effect under X-ray irradiation through full resonance energy transfer from LuAG:Tb/Ce scintillator to Ross Bengal (RB), but also facilitated the reactive oxygen species (ROS) and oxygen (O2) production through the excellent peroxidase-like (POD-like) and catalase-like (CAT-like) catalytic properties of Au2Pt nanozymes. O2 also alleviates hypoxia in intratumoural tissues during coordinated PDT. In addition, the dissociation behavior of ZIF-8 with pH-responsive and targeted of hyaluronic acid (HA) in acidic TME significantly enhanced the therapeutic efficacy of LRZAPH nanocatalysts. Significantly, the high tumor growth inhibition rate of 93 % was revealed due to radiotherapy (RT)/PDT/CDT synergetic therapy in vivo, which minimized the toxic and side effects of conventional clinical radiotherapy/chemotherapy on human. The synergistic effect of LRZAPH nanocatalysts on PDT and catalytically induced CDT is expected to provide new pathways for effective treatment of deep tumors.

RESUMEN

This study presents a novel approach for the fabrication of a Co,Ni/MoS2-derived nanohybrid material using wheat straw extract. The facile synthesis method involves a sol-gel process, followed by calcination, showcasing the potential of agricultural waste as a sustainable reducing and chelating reagent. The as-prepared nanohybrid has been characterized using different techniques to analyse its physicochemical properties. X-ray diffraction analysis confirmed the successful synthesis of the nanohybrid material, identifying the presence of NiMoO4, CoSO4 and Mo17O47 as its components. Fourier-transform infrared spectroscopy differentiated the functional groups present in the wheat straw biomass and those in the nanohybrid material, highlighting the formation of metal-oxide and sulphide bonds. Scanning electron microscopy revealed a heterogeneous morphology with agglomerated structures and a grain size of around 70 nm in the nanohybrid. Energy-dispersive X-ray spectroscopy analysis shows the composition of elements with weight percentages of (Mo) 9.17%, (S) 6.21%, (Co) 12.48%, (Ni) 12.18% and (O) 50.46% contributing to its composition. Electrochemical analysis performed through cyclic voltammetry showcased the exceptional performance of the nanohybrid material as compared with MoS2, suggesting its possible applications for designing biosensors and related technologies. Thus, the research study presented herein underscores the efficient utilization of natural resources for the development of functional nanomaterials with promising applications in various fields. This study paves a way for manufacturing innovation along with advancement of novel synthesis method for sustainable nanomaterial for future technological developments.

Asunto(s)

RESUMEN

In this investigation, we explored the kinetics of Cr(VI) reduction to Cr(III) on carbon nanotube decorated with palladium (Pd-CNTs) nanocatalyst, using formic acid as the reducing agent. This study has been bone utilizing kinetic Monte Carlo simulation and experimental design methods. The mechanism and kinetic parameters of this reaction are provided. The effect various factors such as reaction time, pH level, dichromate (Cr2O72-) concentration, and formic acid concentration on Cr(VI) reduction was studied. Concentrations of HCOOH and Cr2O72- were identified as the crucial variables, while the HCOOH concentration has the most significant impact. Positive influences on Cr(VI) reduction were observed with increasing pH level and HCOOH concentration. Reaction time positively affects on Cr(VI) reduction efficiency. However, the concentration of Cr2O72- showed an increasing effect up to a threshold, negatively impacting the efficiency. The optimal conditions (Reaction time = 60 min, pH = 4.5, [Cr2O72-] = 5.05 × 10-3 M, and [HCOOH] = 0.95 M) for Cr(VI) reduction. At optimal conditions, the Cr(VI) reduction efficiency was obtained to be 100%.

RESUMEN

Energy dispersive X-ray (EDX) spectroscopy in the transmission electron microscope is a key tool for nanomaterials analysis, providing a direct link between spatial and chemical information. However, using it for precisely determining chemical compositions presents challenges of noisy data from low X-ray yields and mixed signals from phases that overlap along the electron beam trajectory. Here, we introduce a novel method, non-negative matrix factorization based pan-sharpening (PSNMF), to address these limitations. Leveraging the Poisson nature of EDX spectral noise and binning operations, PSNMF retrieves high-quality phase spectral and spatial signatures via consecutive factorizations. After validating PSNMF with synthetic data sets of different noise levels, we illustrate its effectiveness on two distinct experimental cases: a nanomineralogical lamella, and supported catalytic nanoparticles. Not only does PSNMF obtain accurate phase signatures, but data sets reconstructed from the outputs have demonstrably lower noise and better fidelity than from the benchmark denoising method of principle component analysis.

RESUMEN

The present work deals with developing a method for revalorizing steel residues to create sunlight-active photocatalysts based on iron oxides. Commercial-grade steel leftovers are oxidized under different combinations of pH and temperature (50-90 °C and 3 ≥ pH ≤ 5) in a low energy-intensive setup. The material with the highest production efficiency (yield > 12%) and magnetic susceptibility (χm = 387 × 10-6 m3/kg) was further explored and modified by diffusion of M2+ (Zn and Co) ions within the structure of the oxide using a hydrothermal method to create ZnFe2O4, CoFe2O4 and combined Co-Zn ferrite. (Co-Zn)Fe2O4 displayed a bandgap of 2.02 eV and can be activated under sunlight irradiation. Electron microscopy studies show that (Co-Zn)Fe2O4 consists of particles with diameters between 400 and 700 nm, homogeneous size, even distribution, and good dispersibility. Application of the developed materials in the sunlight catalysis of black liquors from cellulose extraction resulted in a reduction of the Chemical Oxygen Demand (- 15% on average) and an enhancement in biodegradability (> 0.57 BOD/COD) after 180 min of reaction. Since the presented process employs direct solar light, it opens the possibility to large-scale water treatment and chemical upgrading applications.

RESUMEN

Given that tumor microenvironment (TME) exerts adverse impact on the therapeutic response and clinical outcome, robust TME modulators may significantly improve the curative effect and increase survival benefits of cancer patients. Here, Au nanodots-anchored CoFe2O4 nanoflowers with PEGylation (CFAP) are developed to respond to TME cues, aiming to exacerbate redox dyshomeostasis for efficacious antineoplastic therapy under ultrasound (US) irradiation. After uptake by tumor cells, CFAP with glucose oxidase (GOx)-like activity can facilitate glucose depletion and promote the production of H2O2. Multivalent elements of Co(II)/Co(III) and Fe(II)/Fe(III) in CFAP display strong Fenton-like activity for·OH production from H2O2. On the other hand, energy band structure CFAP is superior for US-actuated 1O2 generation, relying on the enhanced separation and retarded recombination of e-/h+ pairs. In addition, catalase-mimic CFAP can react with cytosolic H2O2 to generate molecular oxygen, which may increase the product yields from O2-consuming reactions, such as glucose oxidation and sonosensitization processes. Besides the massive production of reactive oxygen species, CFAP is also capable of exhausting glutathione to devastate intracellular redox balance. Severe immunogenic cell death and effective inhibition of solid tumor by CFAP demonstrates the clinical potency of such heterogeneous structure and may inspire more relevant designs for disease therapy.

RESUMEN

Given the growing scarcity of water and the continuous increase in emerging pollutants detected in water bodies, there is an imperative need to develop new, more effective, and sustainable treatments for wastewater. Advanced oxidation processes (AOPs) are considered a competitive technology for water treatment. Specifically, ozonation has received notable attention as a promising approach for degrading organic pollutants in wastewater. However, different groups of pollutants are hardly degradable via single ozonation. With continuous development, it has been shown that using engineered nanomaterials as nanocatalysts in catalytic ozonation can increase efficiency by turning this process into a low-selective AOP for pollutant degradation. Nanocatalysts promote ozone decomposition and form active free radicals responsible for increasing the degradation and mineralization of pollutants. This work reviews the performances of different nanomaterials as homogeneous and heterogeneous nanocatalysts in catalytic ozonation. This review focuses on applying metal- and carbon-based engineered nanomaterials as nanocatalysts in catalytic ozonation and on identifying the main future directions for using this type of AOP toward wastewater treatment.

RESUMEN

Formic acid (FA) dehydrogenation and CO2 hydrogenation to FA/formate represent promising methodologies for the efficient and clean storage and release of hydrogen, forming a CO2-neutral energy cycle. Here, we report the synthesis of highly dispersed and stable bimetallic Pd-based nanoparticles, immobilized on self-pillared silicalite-1 (SP-S-1) zeolite nanosheets using an incipient wetness co-impregnation technique. Owing to the highly accessible active sites, effective mass transfer, exceptional hydrophilicity, and the synergistic effect of the bimetallic species, the optimized PdCe0.2/SP-S-1 catalyst demonstrated unparalleled catalytic performance in both FA dehydrogenation and CO2 hydrogenation to formate. Remarkably, it achieved a hydrogen generation rate of 5974 molH2 molPd -1 h-1 and a formate production rate of 536 molformate molPd -1 h-1 at 50 °C, surpassing most previously reported heterogeneous catalysts under similar conditions. Density functional theory calculations reveal that the interfacial effect between Pd and cerium oxide clusters substantially reduces the activation barriers for both reactions, thereby increasing the catalytic performance. Our research not only showcases a compelling application of zeolite nanosheet-supported bimetallic nanocatalysts in CO2-mediated hydrogen storage and release but also contributes valuable insights towards the development of safe, efficient, and sustainable hydrogen technologies.

RESUMEN

Hydrogen energy, known for its high energy density, environmental friendliness, and renewability, stands out as a promising alternative to fossil fuels. However, its broader application is limited by the challenge of efficient and safe storage. In this context, solid-state hydrogen storage using nanomaterials has emerged as a viable solution to the drawbacks of traditional storage methods. This comprehensive review delves into the recent advancements in nanomaterials for solid-state hydrogen storage, elucidating the fundamental principles and mechanisms, highlighting significant material systems, and exploring the strategies of surface and interface engineering alongside catalytic enhancement. We also address the primary challenges and provide future perspectives on the development of nanomaterial-based hydrogen storage technologies. Key discussions include the role of nanomaterial size effects, surface modifications, nanocomposites, and nanocatalysts in optimizing storage performance.

RESUMEN

The application of Li-S batteries on large scale is held back by the sluggish sulfur kinetics and low synthesis efficiency of sulfur host. In addition, the preparation of catalysts that promote polysulfide redox kinetics is complex and time-consuming, reducing the cost of raw materials in Li-S. Here, a universal synthetic strategy for rapid fabrication of sulfur cathode and metal compounds nanocatalysts is reported based on microwave heating of graphene. Heat-sensitive materials can achieve rapid heating due to graphene reaching 500 ℃ within 4 s via microwave irradiation. The MoP-MoS2/rGO catalyst demonstrated in this work was synthesized within 60 s. When used for catalysts for Li-S batteries whose graphene/sulfur cathodes were also synthesized by microwave heating, enhanced catalytic effect for sulfur redox reaction was verified via experimental and DFT theoretical results. Benefiting from fast redox reaction (MoP), smooth Li+ diffusion pathways (MoS2), and large conductive network (rGO), the assembled Li-S battery with MoP-MoS2/rGO-Add@CS displays a remarkable initial specific capacity, stable lithium anode and good cycle stability (in pouch cells) using this two-pronged strategy. The work provides a practical strategy for advanced Li-S batteries toward a wide range of applications.

RESUMEN

The hydrogenation of CO2 to CH4 has gained considerable interest in terms of sustainable energy and environmental mitigation. In this regard, the present work aims to investigate the adsorptive concentration and CO2 methanation performance over CoFe and NiFe bimetallic catalysts supported on fumed alumina-silica SA96 support at 170-450 °C and under atmospheric pressure. The catalysts were prepared by wet impregnation method, subjected to calcination and further reduced with hydrogen, and their performance in CO2 methanation was investigated in a hydrogen-rich 2%CO2-55%H2-43%He gas mixture. In this study, we describe the crystal and mesoporous structures of the prepared catalysts by in-situ XRD and ex-situ nitrogen adsorption, evaluate the NiFe and CoFe metal surface states before and after catalysis by XPS, visualize the surface morphology by SEM, estimate the catalytic activity by gas chromatography, and investigate the adsorbed surface species, showing the presence of *HCOO/*HCO and *CO intermediates, determine two possible pathways of CH4 formation on the studied catalysts by temperature-programmed desorption mass spectrometry, and correlate the structural and surface properties with high CO2 conversions up to 100% and methanation selectivities up to 72%. The latter is related to changes in the elemental chemical states and surface composition of CoFe and NiFe nanocatalysts induced by treatment under reaction conditions, and the surface reconstruction during catalysis transfers the part of active 3d transition metals into the pores of the SA96 support. Our thorough characterization study with complementary techniques allowed us to conclude that this high activity is related to the formation of catalytically active Ni/Ni3Fe and Co/CoFeOx nanoscale crystallites under H2 reduction and their maintenance under CO2 methanation conditions. The successfully applied combination of CO2 chemisorption and thermodesorption techniques demonstrates the ability to adsorb the CO2 molecules by supported NiFe and CoFe nanocatalysts and the pure alumina-silica SA96 support.

Asunto(s)

RESUMEN

While oral probiotics show promise in treating inflammatory bowel disease, the primary challenge lies in sustaining their activity and retention within the inflamed gastrointestinal environment. In this work, we develop an engineered probiotic platform that is armed with biocatalytic and inflamed colon-targeting nanocoatings for multipronged management of IBD. Notably, we achieve the in situ growth of artificial nanocatalysts on probiotics through a bioinspired mineralization strategy. The resulting ferrihydrite nanostructures anchored on bacteria exhibit robust catalase-like activity across a broad pH range, effectively scavenging ROS to alleviate inflammation. The further envelopment with fucoidan-based shields confers probiotics with additional inflamed colon-targeting functions. Upon oral administration, the engineered probiotics display markedly improved viability and colonization within the inflamed intestine, and they further elicit boosted prophylactic and therapeutic efficacy against colitis through the synergistic interplay of nanocatalysis-based immunomodulation and probiotics-mediated microbiota reshaping. The robust and multifunctional probiotic platforms offer great potential for the comprehensive management of gastrointestinal disorders.

RESUMEN

The application of nano-catalysts in improving the ozonation removal efficiency for refractory organic compounds has been extensively investigated. However, cost-effective nano-catalysts separation remains a challenge. In this study, membrane separation processes were employed to separate nano-MgO catalysts from an ozonation system. A continuous nano-catalytic ozonation membrane separation (nCOMS) coupling system was successfully constructed for treating quinoline. The results showed that long hydraulic retention time (HRT) and high nano-MgO dosage could improve the quinolone removal efficiency but shorten operation cycles. At the optimal operation conditions of HRT = 4 h and nano-MgO dosage = 0.2 g/L, the nCOMS system achieved a stable quinoline removal efficiency of 85.2% for 240 min running with a transmembrane pressure lower than 10 kPa. The quinoline removal efficiency contribution for ozonation, catalysis and membrane separation was 57.1%, 24.9% and 18.0%, respectively. Compared to ozonation membrane separation system, the fouling rate index of the nCOMS system increased by 60% under optimal conditions, but the irreversible fouling was reduced to 28%. In addition, the nCOMS system exhibited reduced adverse effects of coexisting natural organic matter (NOM) on quinoline removal and membrane fouling. In conclusion, the nCOMS system demonstrated higher quinoline removal efficiency, lower irreversible fouling, and reduced adverse effect of coexisting NOM, thereby signifying its potential for practical applications in advanced treatment of industrial wastewater.

Asunto(s)

RESUMEN

Atomically thin two-dimensional (2D) semiconductors have high potential in optoelectronics and magneto-optics appliances due to their tunable band structures and physicochemical stability. The work demonstrates that Gd3+ incorporated 2D-g-C3N4 nanosheet (Gd3+/2D-g-C3N4 NS) is synthesized through chemisorption methodology for defect enrichment. The material characterizations reveal that the ion decoration enhances the surface area and defect concentration of the 2D sheet. The experimental observations have been further corroborated with the help of density functional theory (DFT) simulation. Spin asymmetry polarizations near the Fermi level, obtained through the partial density of states (PDOS) analyses, reveal the magnetic nature of the synthesized material, validating the room temperature ferromagnetism obtained through a vibrating-sample magnetometer (VSM). Gd3+/2D-g-C3N4 NS shows significant enhancement in saturation magnetization (Ms) experimentally and computationally compared to the pristine one. The magnetic catalyst shows 98% remediation efficiency for ultrasound-assisted visible-light-driven photodegradation of methyl orange (MO). The synergistic approach of liquid chromatography-mass spectrometry (LC-MS) analyses and DFT studies elucidates reaction intermediates and unveils the degradation mechanism. Post-characterization studies assure the stability of the magnetic catalyst through optical, chemical, magnetic, and microscopic analyses. So, the synthesized material can be proficiently used as a magnetic nanocatalyst in wastewater treatments and spin-electronics applications.

RESUMEN

Effective bimetallic nanoelectrocatalysis demands precise control of composition, structure, and understanding catalytic mechanisms. To address these challenges, we employ a two-in-one approach, integrating online synthesis with real-time imaging of bimetallic Au@Metal core-shell nanoparticles (Au@M NPs) via electrochemiluminescence microscopy (ECLM). Within 120 s, online electrodeposition and in situ catalytic activity screening alternate. ECLM captures transient faradaic processes during potential switches, visualizes electrochemical processes in real-time, and tracks catalytic activity dynamics at the single-particle level. Analysis using ECL photon flux density eliminates size effects and yields quantitative electrocatalytic activity results. Notably, a nonlinear activity trend corresponding to the shell metal to Au surface atomic ratio is discerned, quantifying the optimal surface component ratio of Au@M NPs. This approach offers a comprehensive understanding of catalytic behavior during the deposition process with high spatiotemporal resolution, which is crucial for tailoring efficient bimetallic nanocatalysts for diverse applications.

RESUMEN

The crystal phase, alongside the composition, morphology, architecture, facet, size, and dimensionality, has been recognized as a critical factor influencing the properties of noble metal nanomaterials in various applications. In particular, unconventional crystal phases can potentially enable fascinating properties in noble metal nanomaterials. Recent years have witnessed notable advances in the phase engineering of nanomaterials (PEN). Within the accessible strategies for phase engineering, the effect of strain cannot be ignored because strain can act not only as the driving force of phase transition but also as the origin of the diverse physicochemical properties of the unconventional crystal phase. In this review, we highlight the development of unconventional crystal-phase noble metal nanomaterials within strain engineering. We begin with a short introduction of the unconventional crystal phase and strain effect in noble metal nanomaterials. Next, the correlations of the structure and performance of strain-engineered unconventional crystal-phase noble metal nanomaterials in electrocatalysis are highlighted, as well as the phase transitions of noble metal nanomaterials induced by the strain effect. Lastly, the challenges and opportunities within this rapidly developing field (i.e., the strain engineering of unconventional crystal-phase noble metal nanocatalysts) are discussed.

RESUMEN

Balancing the accuracy and simplicity of aptasensors is a challenge in their construction. This study addresses this issue by leveraging the remarkable loading capacity and peroxidase-like catalytic activity of PtPdCu trimetallic nanoparticles, which reduces the reliance on precious metals. A dual-signal readout aptasensor for enrofloxacin (ENR) detection is designed, incorporating DNA dynamic network cascade reactions to further amplify the output signal. Exploiting the strong loading capacity of PtPdCu nanoparticles, they are self-assembled with thionine (Thi) to form a signal label capable of generating signals in two independent modes. The label exhibits excellent enzyme-like catalytic activity and enhances electron transfer capabilities. Differential pulse voltammetry (DPV) and square-wave voltammetry (SWV) are employed to independently read signals from the oxidation-reduction reaction of Thi and the catalytic oxidation of hydroquinone (HQ) to benzoquinone (BQ) by H2O2. The introduced DNA dynamic network cascade reaction modularizes sample processing and electrode surface signal generation, avoiding electrode contamination and efficiently increasing the output of the catalyzed hairpin assembly (CHA) cycle. Under optimized conditions, the developed aptasensor demonstrates detection limits of 0.112 (DPV mode) and 0.0203 pg/mL (SWV mode). Additionally, the sensor successfully detected enrofloxacin in real samples, expanding avenues for designing dual-mode signal amplification strategies.

Asunto(s)

RESUMEN

Active polymetallic atomic clusters can initiate heterogeneous catalytic reactions in the tumor microenvironment, and the products tend to cause manifold damage to cell metabolic functions. Herein, bimetallic PtPd atomic clusters (BAC) are constructed by the stripping of Pt and Pd nanoparticles on nitrogen-doped carbon and follow-up surface PEGylation, aiming at efficacious antineoplastic therapy through heterogeneous catalytic processes. After endocytosed by tumor cells, BAC with catalase-mimic activity can facilitate the decomposition of endogenous H2O2 into O2. The local oxygenation not only alleviates hypoxia to reduce the invasion ability of cancer cells but also enhances the yield of •O2- from O2 catalyzed by BAC. Meanwhile, BAC also exhibit peroxidase-mimic activity for •OH production from H2O2. The enrichment of reactive oxygen species (ROS), including the radicals of •OH and •O2-, causes significant oxidative cellular damage and triggers severe apoptosis. In another aspect, intrinsic glutathione (GSH) peroxidase-like activity of BAC can indirectly upregulate the level of lipid peroxides and promote ferroptosis. Such deleterious redox dyshomeostasis caused by ROS accumulation and GSH consumption also results in immunogenic cell death to stimulate antitumor immunity for metastasis suppression. Collectively, this paradigm is expected to inspire more facile designs of polymetallic atomic clusters in disease therapy.

Asunto(s)

RESUMEN

Electrochemical reduction of CO2 to highly valuable products is a promising way to reduce CO2 emissions. The shape and facets of metal nanocatalysts are the key parameters in determining the catalytic performance. However, the exposed crystal facets of ZnO with different morphologies and which facets achieve a high performance for CO2 reduction are still controversial. Here, we systematically investigate the effect of the facet-dependent reactivity of reduction of CO2 to CO on ZnO (nanowire, nanosheet, and flower-like). The ZnO nanosheet with exposed (110) facet exhibited prominent catalytic performance with a Faradaic efficiency of CO up to 84% and a current density of -10 mA cm-2 at -1.2 V versus RHE, far outperforming the ZnO nanowire (101) and ZnO nanoflower (103). Based on detailed characterizations and kinetic analysis, the ZnO nanosheet (110) with porous architecture increased the exposure of active sites. Further studies revealed that the high CO selectivity originated from the enhancement of CO2 adsorption and activation on the ZnO (110) facet, which promoted the conversion of CO2 toward CO. This study provides a new way to tailor the activity and selectivity of metal catalysts by engineering exposed specific facets.

RESUMEN

Employing tumor whole cells for tumor immunotherapy is a promising tumor therapy proposed in the early stage, but its therapeutic efficacy is weakened by the methods of eliminating pathogenicity and the mass ratio of the effective antigen carried by itself. Here, by adding gold ion to live cancer cells in the microfluidic droplets, this work obtains dead tumor whole cells with NIR-controlled catalytic ability whose pathogenicity is removed while plenary tumor antigens, major structure, and homing ability are reserved. The engineered tumor cell (Cell-Au) with the addition of prodrug provides 1O2 in an O2-free Russell mechanism, which serves better in a hypoxic tumor microenvironment. This tumor whole-cell catalytic vaccine (TWCV) promotes the activation of dendritic cells and the transformation of macrophages into tumor suppressor phenotype. In 4T1 tumor-bearing mice, the Cell-Au-based vaccine supports the polarization of cytotoxicity T cells, resulting in tumor eradication and long-term animal survival. Compared with antigen vaccines or adoptive cell therapy which takes months to obtain, this TWCV can be prepared in just a few days with satisfactory immune activation and tumor therapeutic efficacy, which provides an alternative way for the preparation of personalized tumor vaccines across tumor types and gives immunotherapy a new path.

Asunto(s)