Metal-ligand dual-site single-atom nanozyme mimicking urate oxidase with high substrates specificity

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 8, 2024

Abstract In nature, coenzyme-independent oxidases have evolved in selective catalysis using isolated substrate-binding pockets. Single-atom nanozymes (SAzymes), an emerging type of non-protein artificial enzymes, are promising to simulate enzyme active centers, but owing the lack recognition sites, realizing substrate specificity is a formidable task. Here we report metal-ligand dual-site SAzyme (Ni-DAB) that exhibited selectivity uric acid (UA) oxidation. Ni-DAB mimics catalytic mechanism urate oxidase, which Ni metal center and C atom ligand serve as specific UA O 2 binding respectively, characterized by synchrotron soft X-ray absorption spectroscopy, situ near ambient pressure photoelectron isotope labeling. The theoretical calculations reveal high derived from not only delicate interaction between also complementary oxygen reduction at beta site ligand. As potential application, Ni-DAB-based biofuel cell human urine constructed. This work unlocks approach enzyme-like dual sites boosting enzymes.

Язык: Английский

---

Hydrophobic SiO₂ Armor: Stabilizing Cu^δ+ to Enhance CO₂ Electroreduction toward C₂₊ Products in Strong Acidic Environments

ACS Nano, Год журнала: 2024, Номер 18(23), С. 15303 - 15311

Опубликована: Май 28, 2024

Electroreduction of CO2 in highly acidic environments holds promise for enhancing utilization efficiency. Due to the HER interference and structural instability, however, challenges improving selectivity stability toward multicarbon (C2+) products remain. In this study, we proposed an "armor protection" strategy involving deposition ultrathin, hydrophobic SiO2 onto Cu surface (Cu/SiO2) through a simple one-step hydrolysis. Our results confirmed effective inhibition by layer, leading high Faradaic efficiency (FE) up 76.9% C2+ at current density 900 mA cm–2 under strongly condition with pH 1. The observed performance surpassed reported most previously studied Cu-based catalysts CO2RR systems. Furthermore, ultrathin shell was demonstrated effectively prevent reconstruction preserve oxidation state Cuδ+ active sites during CO2RR. Additionally, it hindered accumulation K+ ions on catalyst diffusion situ generated OH– away from electrode, thereby favoring product generation. Raman analyses coupled DFT simulations further elucidated that proficiently modulated *CO adsorption behavior Cu/SiO2 reducing energy, facilitating C–C coupling. This work offers compelling rationally designing exploiting stable environments.

Язык: Английский

---

Interstitial carbon induces enriched Cuδ+ sites in Cu2O nanoparticles to facilitate CO2 electroreduction to C2+ products

Nano Research, Год журнала: 2024, Номер 17(8), С. 7013 - 7019

Опубликована: Июнь 26, 2024

Язык: Английский

---

Atomically Dispersed Metal Catalysts for the Conversion of CO₂ into High‐Value C₂₊ Chemicals

Advanced Materials, Год журнала: 2024, Номер 36(37)

Опубликована: Май 19, 2024

Abstract The conversion of carbon dioxide (CO 2 ) into value‐added chemicals with two or more carbons (C 2+ is a promising strategy that cannot only mitigate anthropogenic CO emissions but also reduce the excessive dependence on fossil feedstocks. In recent years, atomically dispersed metal catalysts (ADCs), including single‐atom (SACs), dual‐atom (DACs), and single‐cluster (SCCs), emerged as attractive candidates for fixation reactions due to their unique properties, such maximum utilization active sites, tunable electronic structure, efficient elucidation catalytic mechanism, etc. This review provides an overview significant progress in synthesis characterization ADCs utilized photocatalytic, electrocatalytic, thermocatalytic toward high‐value C compounds. To provide insights designing chemical originating from , key factors influence activity selectivity are highlighted. Finally, relevant challenges opportunities discussed inspire new ideas generation ‐based products over ADCs.

Язык: Английский

---

Experimental and Theoretical Insights into Single Atoms, Dual Atoms, and Sub‐Nanocluster Catalysts for Electrochemical CO₂ Reduction (CO₂RR) to High‐Value Products

Advanced Materials, Год журнала: 2024, Номер 36(52)

Опубликована: Ноя. 26, 2024

Abstract Electrocatalytic carbon dioxide (CO 2 ) conversion into valuable chemicals paves the way for realization of recycling. Downsizing catalysts to single‐atom (SACs), dual‐atom (DACs), and sub‐nanocluster (SNCCs) has generated highly active selective CO transformation reduced products. This is due introduction numerous sites, unsaturated coordination environments, efficient atom utilization, confinement effect compared their nanoparticle counterparts. Herein, recent Cu‐based SACs are first reviewed newly emerged DACs SNCCs expanding catalysis electrocatalytic reduction RR) high‐value products discussed. Tandem SAC–nanocatalysts (NCs) (SAC–NCs) also discussed RR Then, non‐Cu‐based SACs, DACs, SAC–NCs, theoretical calculations various transition‐metal summarized. Compared previous achievements less‐reduced products, this review focuses on double objective achieving full increasing selectivity formation rate toward C–C coupled with additional emphasis stability catalysts. Finally, through combined experimental research, future outlooks offered further develop over isolated atoms sub‐nanometal clusters.

Язык: Английский

---

Confinement Synthesis of Atomic Copper‐Anchored Polymeric Carbon Nitride in Crystalline UiO‐66‐NH2 for High‐Performance CO2‐to‐CH3OH Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 29, 2024

Photocatalytic CO

Язык: Английский

---

Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis

Deleted Journal, Год журнала: 2024, Номер 1(2), С. 181 - 206

Опубликована: Авг. 4, 2024

Abstract Metal–organic frameworks (MOFs) have emerged as promising materials in the realm of electrocatalysis due to their high surface area, tunable porosity, and versatile chemical functionality. However, practical application has been hampered by inherent limitations such low electrical conductivity a limited number active metal sites. Researchers addressed these challenges through various strategies, including enhancing incorporating conductive nanoparticles, modifying structure composition MOFs replacing nodes functionalizing linkers, preparing catalysts thermal processes decarburization conversion into oxides, phosphides (MPs), sulfides (MSs). This review provided comprehensive summary strategies that were employed enhance electroactivity for improved electrocatalytic performance recent years. It also explored future directions potential innovations design synthesis MOF‐based electrocatalysts, offering valuable insights advancing sustainable energy technologies.

Язык: Английский

---

In Situ Reconstruction of Scalable Amorphous Indium-Based Metal–Organic Framework for CO₂ Electroreduction to Formate over an Ultrawide Potential Window

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(22), С. 28655 - 28663

Опубликована: Май 22, 2024

Amorphous metal–organic frameworks (aMOFs) are highly attractive for electrocatalytic applications due to their exceptional conductivity and abundant defect sites, but harsh preparation conditions of "top-down" strategy have hindered widespread use. Herein, the scalable production aMIL-68(In)-NH2 was successfully achieved through a facile "bottom-up" involving ligand competition with 2-methylimidazole. Multiple in situ ex characterizations reveal that evolutes into In/In2O3–x as genuine active sites during CO2 reduction (CO2RR) process. Moreover, retained amino groups could enhance adsorption. As expected, reconstructed catalyst demonstrates high formate Faradaic efficiency values (>90%) over wide potential range 800 mV flow cell, surpassing most top-ranking electrocatalysts. Density functional theory calculations oxygen vacancies induce more local charges around electroactive thereby promoting formation HCOO* intermediates. Furthermore, 16 g samples can be readily prepared one batch exhibit almost identical CO2RR performances. This work offers feasible batch-scale design amorphous MOFs efficient electrolytic CO2RR.

Язык: Английский

---

High Fe-Loading Single-Atom Catalyst Boosts ROS Production by Density Effect for Efficient Antibacterial Therapy

Nano-Micro Letters, Год журнала: 2024, Номер 17(1)

Опубликована: Окт. 4, 2024

Abstract The current single-atom catalysts (SACs) for medicine still suffer from the limited active site density. Here, we develop a synthetic method capable of increasing both metal loading and mass-specific activity SACs by exchanging zinc with iron. constructed iron (h 3 -FNC) high 6.27 wt% an optimized adjacent Fe distance ~ 4 Å exhibit excellent oxidase-like catalytic performance without significant decay after being stored six months promising antibacterial effects. Attractively, “density effect” has been found at high-enough doping amount, which individual sites become close enough to interact each other alter electronic structure, resulting in significantly boosted intrinsic single-atomic h -FNCs 2.3 times compared low- medium-loading SACs. Consequently, overall -FNC is highly improved, mass that are, respectively, 66 315 higher than those commercial Pt/C. In addition, demonstrate efficiently enhanced capability catalyzing oxygen reduction into superoxide anion (O 2 · − ) glutathione (GSH) depletion. Both vitro vivo assays superior efficacy promoting wound healing. This work presents intriguing activity-enhancement effect exhibits impressive therapeutic combating bacterial infections.

Язык: Английский

---

Electrocatalytic conversion of CO2 into selective carbonaceous fuels using metal-organic frameworks: An overview of recent progress and perspectives

Materials Today Chemistry, Год журнала: 2025, Номер 44, С. 102538 - 102538

Опубликована: Янв. 21, 2025

Язык: Английский

---