Targeted Delivery of Active Sites by Oxygen Vacancy-Engineered Bimetal Silicate Nanozymes for Intratumoral Aggregation-Potentiated Catalytic Therapy

ACS Nano, Journal Year: 2024, Volume and Issue: 18(2), P. 1516 - 1530

Published: Jan. 3, 2024

Biodegradable silicate nanoconstructs have aroused tremendous interest in cancer therapeutics due to their variable framework composition and versatile functions. Nevertheless, low intratumoral retention still limits practical application. In this study, oxygen vacancy (OV)-enriched bimetallic nanozymes with Fe–Ca dual active sites via modification of oxidized sodium alginate gallic acid (GA) loading (OFeCaSA-V@GA) were developed for targeted aggregation-potentiated therapy. The band gap silica markedly decreased from 2.76 1.81 eV by codoping Fe3+ Ca2+, enabling its excitation a 650 nm laser generate reactive species. OV that occurred the hydrothermal synthetic stage OFeCaSA-V@GA can anchor metal ions form an atomic phase, offering massive fabrication method single-atom nanozymes. Density functional theory results reveal Ca promote adsorption H2O2, Fe accelerate dissociation thereby realizing synergetic catalytic effect. More importantly, delivery induce morphological transformation at tumor sites, leading high (the highest rate is 36.3%) theranostic components cells. Thus, finding may offer ingenious protocol designing engineering highly efficient long-retention nanodrugs.

Language: Английский

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Tuning d–p Orbital Hybridization of NiMoO₄@Mo₁₅Se₁₉/NiSe₂ Core‐Shell Nanomaterials via Asymmetric Coordination Interaction Enables the Water Oxidation Process

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(20)

Published: April 3, 2024

Abstract The electrocatalytic performance of MoNi‐based nanomaterials undergo selenization has garnered significant interest due to their modified electronic structure, while still posses certain challenges for obtained bimetallic selenides. Here, a novel electrocatalyst NiMoO 4 @Mo 15 Se 19 /NiSe 2 core‐shell is constructed promote the desorption OOH * which can facilitate water oxidation process. nanoarrays show that “cores” are mainly nanorods “shells” selenides nanoflakes, super architectures expand more active sites and accelerate electron transfer. Moreover, hybridization interaction between Ni 3d, Mo 4d, 4p orbitals leads an asymmetric distribution electric clouds, decreases adsorption energy transformation oxygen‐containing species. Electrochemical data displays overpotentials only 195 mV, 220 224 mV oxygen evolution reaction (OER) in alkaline freshwater, simulated seawater, natural seawater. current density decay negligible after 100 h stability at about 1.46 V with three‐electrode system low cost unique this work provide constructive solution designing efficient stable OER catalysts future.

Language: Английский

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(111) Facet‐oriented Cu₂Mg Intermetallic Compound with Cu₃‐Mg Sites for CO₂ Electroreduction to Ethanol with Industrial Current Density

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: March 4, 2024

Abstract The efficient ethanol electrosynthesis from CO 2 is challenging with low selectivity at high electrolysis rates, due to the competition H and other reduction products. Copper‐based bimetallic electrocatalysts are potential candidates for ‐to‐ethanol conversion, but secondary metal has mainly been focused on active components (such as Ag, Sn) electroreduction, which also promote of ethylene or products rather than ethanol. Limited attention given alkali‐earth metals their inherently chemical property. Herein, we rationally synthesized a (111) facet‐oriented nano Cu Mg (designated Mg(111)) intermetallic compound high‐density ordered 3 ‐Mg sites. in situ Raman spectroscopy density function theory calculations revealed that − + sites allowed increase *CO surface coverage, decrease reaction energy *CO−CO coupling, stabilize *CHCHOH intermediates, thus promoting formation pathway. Mg(111) catalyst exhibited FE C2H5OH 76.2±4.8 % 600 mA⋅cm −2 , peak value | j 720±34 almost 4 times using conventional (311) facets, comparable best reported values electroreduction.

Language: Английский

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Axial alignment of covalent organic framework membranes for giant osmotic energy harvesting

Nature Sustainability, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

Language: Английский

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Lanthanide single-atom catalysts for efficient CO2-to-CO electroreduction

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 27, 2025

Abstract Single-atom catalysts (SACs) have received increasing attention due to their 100% atomic utilization efficiency. The electrochemical CO 2 reduction reaction (CO RR) using SAC offers a promising approach for utilization, but achieving facile adsorption and desorption remains challenging traditional SACs. Instead of singling out specific atoms, we propose strategy utilizing atoms from the entire lanthanide (Ln) group facilitate RR. Density functional theory calculations, operando spectroscopy, X-ray absorption spectroscopy elucidate bridging mechanism representative erbium (Er) single-atom catalyst. As result, realize series Ln SACs spanning 14 elements that exhibit Faradaic efficiencies exceeding 90%. Er catalyst achieves high turnover frequency ~130,000 h − 1 at 500 mA cm . Moreover, 34.7% full-cell energy efficiency 70.4% single-pass conversion are obtained 200 with acidic electrolyte. This catalytic platform leverages collective potential group, introducing new possibilities efficient -to-CO beyond through exploration unique bonding motifs in catalysts.

Language: Английский

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A molecular view of single-atom catalysis toward carbon dioxide conversion

Chemical Science, Journal Year: 2024, Volume and Issue: 15(13), P. 4631 - 4708

Published: Jan. 1, 2024

We present critical advances in single-atom catalysis toward CO 2 transformation and address crucial issues about SACs from a molecular point of view.

Language: Английский

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Synergistic Effects of Amine Functional Groups and Enriched‐Atomic‐Iron Sites in Carbon Dots for Industrial‐Current–Density CO₂ Electroreduction

Small, Journal Year: 2024, Volume and Issue: 20(32)

Published: March 21, 2024

Abstract Metal phthalocyanine molecules with Me‐N 4 centers have shown promise in electrocatalytic CO 2 reduction (eCO R) for generation. However, iron (FePc) is an exception, exhibiting negligible eCO R activity due to a higher * COOH conversion barrier and stronger binding energy. Here, amine functional groups onto atomic‐Fe‐rich carbon dots (Af‐Fe‐CDs) are introduced via one‐step solvothermal molecule fusion approach. Af‐Fe‐CDs feature well‐defined Fe‐N active sites impressive Fe loading (up 8.5 wt%). The synergistic effect between electron‐donating yielded outstanding ‐to‐CO performance. At industrial‐relevant current densities exceeding 400 mA cm −2 flow cell, achieved >92% selectivity, surpassing state‐of‐the‐art electrocatalysts. situ electrochemical FTIR characterization combined theoretical calculations elucidated that integration significantly reduced energy barriers intermediate formation desorption, enhancing efficiency. proposed offers promising avenue high‐efficiency catalysts elevated atomic‐metal loadings.

Language: Английский

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Electrocatalysis Boosts the Methanol Thermocatalytic Dehydrogenation for High-Purity H₂ and CO Production

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9657 - 9664

Published: April 1, 2024

Hydrogen production from methanol represents an energy-sustainable way to produce ethanol, but it normally results in heavy CO2 emissions. The selective conversion of into H2 and valuable chemical feedstocks offers a promising strategy; however, is limited by the harsh operating conditions low efficiency. Herein, we realize efficient high-purity CO coupling thermocatalytic dehydrogenation with electrocatalytic hydrogen oxidation on bifunctional Ru/C catalyst. Electrocatalysis enables acceleration C–H cleavage reduces partial pressure at anode, which drives equilibrium significantly enhances dehydrogenation. Furthermore, bilayer + Pd/C electrode designed mitigate poisoning facilitate oxidation. As result, high yield (558.54 mmol h–1 g–1) purity (99.9%) was achieved integrating applied cell voltage 0.4 V 200 °C, superior conventional thermal processes, main product anode. This work presents new avenue for together synthesis methanol.

Language: Английский

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Unlocking the potential of alkaline-earth metal active centers for nitrogen activation and ammonia synthesis: the role of s–d orbital synergy

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(7), P. 4278 - 4289

Published: Jan. 1, 2024

N 2 can be activated via s–d orbital synergy of AE metal active centers, i.e. , metals's orbitals share electrons with their empty d orbitals, and then the partially occupied exchange σ π* .

Language: Английский

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Enhancing C₂₊ product selectivity in CO₂ electroreduction by enriching intermediates over carbon-based nanoreactors

Chemical Science, Journal Year: 2024, Volume and Issue: 15(22), P. 8451 - 8458

Published: Jan. 1, 2024

A carbon-based nanoreactor could enrich *CO intermediates through steric confinement, thus facilitating electrocatalytic C–C coupling.

Language: Английский

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