Interfacial Engineering of Bimetallic Ni/Co-MOFs with H-Substituted Graphdiyne for Ammonia Electrosynthesis from Nitrate

ACS Nano, Год журнала: 2023, Номер 17(7), С. 6687 - 6697

Опубликована: Март 17, 2023

The electrochemical synthesis of ammonia is highly dependent on the coupling reaction between nitrate and water, for which an electrocatalyst with a multifunctional interface anticipated to promote deoxygenation hydrogenation water. Herein, by engineering surface bimetallic Ni/Co-MOFs (NiCoBDC) hydrogen-substituted graphdiyne (HsGDY), hybrid nanoarray NiCoBDC@HsGDY has been achieved toward scale-up nitrate-to-ammonia conversion. On one hand, partial electron transfers from Ni2+ coordinatively unsaturated Co2+ NiCoBDC, not only promotes *NO3 but also activates water-dissociation *H Ni2+. other conformal coated HsGDY facilitates both electrons NO3- ions gathering NiCoBDC HsGDY, moves forward rate-determining step *N *H2O Co2+. As result, such delivers high NH3 yield rates Faradaic efficiency above 90% over wide potential pH windows. When assembled into galvanic Zn-NO3- battery, power density 3.66 mW cm-2 achieved, suggesting its in area aqueous Zn-based batteries.

Язык: Английский

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Precise Regulation of the Coordination Environment of Single Co(II) Sites in a Metal–Organic Framework for Boosting CO₂ Photoreduction

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8760 - 8769

Опубликована: Июнь 16, 2023

While the coordination environment around catalytic metal sites plays a crucial role in catalysis, its precise design and modulation still remain challenge. Herein, coordinated N atom number single Co installed on UiO-type metal–organic framework has been modulated to afford UiO-Co-Nx (x = 2, 3, 4) for photocatalytic CO2 reduction. Significantly, performance is affected by site, which UiO-Co-N3 exhibits superior activity other counterparts. Photo-/electrochemical results support fastest charge transfer kinetics between photosensitizer UiO-Co-N3. Theoretical calculations, together with acquired from situ diffuse reflectance infrared Fourier transform spectra, manifest lowest energy barriers of rate-determining step desorption CO* over among all samples.

Язык: Английский

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Size engineering of 2D MOF nanosheets for enhanced photodynamic antimicrobial therapy

Chinese Chemical Letters, Год журнала: 2023, Номер 34(9), С. 108140 - 108140

Опубликована: Янв. 14, 2023

Язык: Английский

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One-pot preparation of NiMn layered double hydroxide-MOF material for highly sensitive electrochemical sensing of glucose

Journal of Electroanalytical Chemistry, Год журнала: 2023, Номер 933, С. 117276 - 117276

Опубликована: Фев. 20, 2023

Язык: Английский

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Electrocatalytic Synthesis of Pyridine Oximes using in Situ Generated NH₂OH from NO species on Nanofiber Membranes Derived from NH₂‐MIL‐53(Al)

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 20, 2023

Pyridine oximes produced from aldehyde or ketone with hydroxylamine (NH2 OH) have been widely applied in pharmaceutics, enzymatic and sterilization. However, the important raw material NH2 OH exhibits corrosive unstable properties, leading to substantial energy consumption during storage transportation. Herein, this work presents a novel method for directly synthesizing highly valuable pyridine using situ generated electrocatalytic NO reduction well-design nanofiber membranes (Al-NFM) derived -MIL-53(Al). Particularly, 2-pyridinealdoxime, precursor of antidote pralidoxime (2-PAM) nerve agents suffering scarcity high cost, was achieved Faraday efficiency up 49.8 % yield 92.1 %, attributing selectivity production on Al-NFM, further easily reacted iodomethane produce 2-PAM. This study proposes creative approach, having wide universality other range functional groups, which not only facilitates conversion exhaust gas (NO) waste water (NO2- ) into chemicals especially utilization through electrochemistry, but also holds significant potential synthesis neuro detoxifying drugs humanity security.

Язык: Английский

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Noncentrosymmetric Lanthanide-Based MOF Materials Exhibiting Strong SHG Activity and NIR Luminescence of Er³⁺: Application in Nonlinear Optical Thermometry

ACS Applied Materials & Interfaces, Год журнала: 2023, Номер 15(2), С. 3244 - 3252

Опубликована: Янв. 5, 2023

Optically active luminescent materials based on lanthanide ions attract significant attention due to their unique spectroscopic properties, nonlinear optical activity, and the possibility of application as contactless sensors. Lanthanide metal-organic frameworks (Ln-MOFs) that exhibit strong second-harmonic generation (SHG) are optically in NIR region unexpectedly underrepresented. Moreover, such Ln-MOFs require ligands chiral and/or need multistep synthetic procedures. Here, we show pulsed laser irradiation noncentrosymmetric, isostructural Ln-MOF (MOF-Er3+ (1) codoped MOF-Yb3+/Er3+ (2)) constructed from simple, achiral organic substrates a one-step procedure results tunable SHG activity. The signals could be easily collected, exciting broad spectral range, ≈800 1500 nm, resulting intense color emission, observed entire visible region. upon excitation range ≈900 1025 also luminescence Er3+ ions, centered at ≈1550 nm. use 975 nm pulse allows simultaneous observations conventional emission signal, altogether tuned by composition materials. Taking benefits different thermal responses mentioned effects, have developed thermometer lanthanide-MOF In this system, signal decreases with temperature, whereas band slightly broadens, allowing ratiometric (Er3+ 1550 nm/SHG 488 nm) temperature monitoring. Our study provides groundwork for rational design readily available self-monitoring NLO-active desired electronic properties.

Язык: Английский

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Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal–Organic Frameworks for Boosting Photocatalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10798 - 10805

Опубликована: Апрель 5, 2024

Though the coordination environment of single metal sites has been recognized to be great importance in promoting catalysis, influence simultaneous precise modulation primary and secondary spheres on catalysis remains largely unknown. Herein, a series Ni(II) with altered have installed onto metal–organic frameworks (MOFs) UiO-67 skeleton, affording UiO–Ni–X–Y (X = S, O; Y H, Cl, CF3) X spheres, respectively. Upon deposition CdS nanoparticles, resulting composites present high photocatalytic H2 production rates, which optimized CdS/UiO–Ni–S–CF3 exhibits an excellent activity 13.44 mmol g–1, ∼500 folds pristine catalyst (29.6 μmol g–1 for CdS/UiO), 8 h, highlighting key role microenvironment around Ni sites. Charge kinetic analysis theoretical calculation results demonstrate that charge transfer dynamics reaction energy barrier are closely correlated their spheres. This work manifests advantages MOFs fabrication structurally catalysts elucidation particular influences catalytic performance.

Язык: Английский

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Solvent-free selective hydrogenation of nitroaromatics to azoxy compounds over Co single atoms decorated on Nb2O5 nanomeshes

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

Опубликована: Апрель 12, 2024

Abstract The solvent-free selective hydrogenation of nitroaromatics to azoxy compounds is highly important, yet challenging. Herein, we report an efficient strategy construct individually dispersed Co atoms decorated on niobium pentaoxide nanomeshes with unique geometric and electronic properties. use this supported single atom catalysts in the nitrobenzene azoxybenzene results high catalytic activity selectivity, 99% selectivity conversion within 0.5 h. Remarkably, it delivers exceptionally turnover frequency 40377 h –1 , which amongst similar state-of-the-art catalysts. In addition, demonstrates remarkable recyclability, reaction scalability, wide substrate scope. Density functional theory calculations reveal that are significantly promoted by properties strong metal-support interaction 1 /Nb 2 O 5 . absence precious metals, toxic solvents, reagents makes catalyst more appealing for synthesizing from nitroaromatics. Our findings suggest great potential access boosted thus offering blueprints design nanomaterials organocatalysis.

Язык: Английский

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A Robust Pyrazolate Metal–Organic Framework for Efficient Catalysis of Dehydrogenative C–O Cross Coupling Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 14174 - 14181

Опубликована: Май 9, 2024

Construction of robust heterogeneous catalysts with atomic precision is a long-sought pursuit in the catalysis field due to its fundamental significance taming chemical transformations. Herein, we present synthesis single-crystalline pyrazolate metal–organic framework (MOF) named PCN-300, bearing lamellar structure two distinct Cu centers and one-dimensional (1D) open channels when stacked. PCN-300 exhibits exceptional stability aqueous solutions across broad pH range from 1 14. In contrast, monomeric counterpart assembled through hydrogen bonding displays limited stability, emphasizing role Cu-pyrazolate coordination bonds robustness. Remarkably, synergy 1D channels, excellent active Cu-porphyrin sites endows outstanding catalytic activity cross dehydrogenative coupling reaction form C–O bond without "compulsory" ortho-position directing groups (yields up 96%), outperforming homogeneous catalysts. Moreover, superior recyclability compatibility various phenol substrates. Control experiments reveal between center computations unveil free radical pathway reaction. This study highlights power MOFs directly activating C–H catalyzing challenging transformations an environmentally friendly manner.

Язык: Английский

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Recent advance in metal-organic frameworks based catalysts for production of fine chemicals via thermal catalysis

Molecular Catalysis, Год журнала: 2025, Номер 573, С. 114811 - 114811

Опубликована: Янв. 7, 2025

Язык: Английский

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