Supported Metal Nanoparticles Research Articles

Exceptional Electrochemical HER Performance with Enhanced Electron Transfer between Ru Nanoparticles and Single Atoms Dispersed on a Carbon Substrate

AbstractPrecisely regulating the electronic structures of metal active species is highly desirable for electrocatalysis. However, carbon with inert surface provide weak metal–support interaction, which is insufficient to modulate the electronic structures of metal nanoparticles. Herein, we propose a new method to control the electrocatalytic behavior of supported metal nanoparticles by dispersing single metal atoms on an O‐doped graphene. Ideal atomic metal species are firstly computationally screened. We then verify this concept by deposition of Ru nanoparticles onto an O‐doped graphene decorated with single metal atoms (e.g., Fe, Co, and Ni) for hydrogen evolution reaction (HER). Consistent with theoretical predictions, such hybrid catalysts show outstanding HER performance, much superior to other reported electrocatalysts such as the state‐of‐the‐art Pt/C. This work offers a new strategy for modulating the activity and stability of metal nanoparticles for electrocatalysis processes.

On the Stability of Pt‐Based Catalysts in HBr/Br2 Solution

AbstractStability studies on supported metal nanoparticles are essential for gaining insight into the design and optimization of high‐performance materials. In this work, the dissolutions of Pt‐based catalysts in HBr/Br2 mixture of various concentration regimes were studied and correlated with material structural properties. The dissolution of metal nanoparticles was enhanced by adding Br2 to the HBr solution. Comparing with commercial Pt/C catalyst, the well‐alloyed PtIr/C catalyst was observed to exhibit high resistance towards dissolution. In addition, regulating the accessibility of the metal sites to dissolution‐inducing species contributed to the marked stability of the nanoparticles in HBr/Br2 solutions, as shown for the surface‐modified PtIr/C catalysts with organic diamine molecules.

Quantifying Competitive Degradation Processes in Supported Nanocatalyst Systems.

The stability of supported metal nanoparticles determines the activity and lifetime of heterogeneous catalysts. Catalysts can destabilize through several thermodynamic and kinetic pathways, and the competition between these mechanisms complicates efforts to quantify and predict the overall evolution of supported nanoparticles in reactive environments. Pairing in situ transmission electron microscopy with unsupervised machine learning, we quantify the destabilization of hundreds of supported Au nanoparticles in real-time to develop a model describing the observed particle evolution as a competition between evaporation and surface diffusion. Data mining of particle evolution statistics allows us to determine physically reasonable values for the model parameters, quantify the particle size at which the Gibbs-Thomson pressure accelerates the evaporation process, and explore how individual particle interactions deviate from the mean-field model. This approach can be applied to a wide range of supported nanoparticle systems, allowing quantitative insight into the mechanisms that control their evolution in reactive environments.

Nitrogen-doped graphdiyne for effective metal deposition and heterogeneous Suzuki-Miyaura coupling catalysis

For heterogeneous catalysts with nitrogen doped carbon materials as supporting substrates, accurate nitrogen (N) species and content is an important factor for promoting the catalytic activity. In this paper, N-doped graphdiyne (NGDY) was prepared from tetraethynylpyrazine (TEP) by bottom-up synthesis method as the support of metal nanoparticles. Specific pyridine nitrogen atoms are introduced in the N-doped carbon material. This unique structure makes it a promising material to support ultrafine metal particles or clusters. Microwave-assisted anchoring of Pd, Pt, Cu, Ni nanoparticles on NGDY generated novel hybrid composites, in which Pd-NGDY has high versatility for Suzuki-Miyaura reaction. DFT calculations revealed a charge transfer from NGDY to Pd NPs, and the free energy distribution showed a downward trend for Suzuki-Miyaura coupling reactions.

Titanosilicate zeolite supported Pt nanoparticles with electronic metal-support interactions for efficient methanol steam reforming

In situ release of hydrogen from liquid organic hydrogen carriers―such as methanol by steam reforming, offers a feasible way to potentially solve the problem of hydrogen storage and transport. Here we report that the titanosilicalite-1 (TS-1) zeolite support efficiently accelerates the Pt catalyzed methanol steam reforming (MSR), giving the hydrogen productivity at 639.7 molH2 molPt−1 h−1 at 250 °C, which steadily outperforms the Pt nanoparticles supported on other carriers, including ZSM-5 zeolite, amorphous SiO2, and TiO2 anatase. Further studies reveal that the electronic metal-support interactions (EMSIs) between Pt and TS-1 zeolite occurs, which modifies Pt nanoparticles surface charge state to accelerate the reaction. More importantly, the interactions could stabilize the Pt nanoparticles, achieving sinter-resistant Pt/TS-1 catalyst in the continuous MSR tests. This finding indicates the important role of heteroatoms in the zeolite framework for supported metal nanoparticles, which open a new way to guide the design of highly efficient heterogeneous catalysts in the future.

Cold Plasma Preparation of Pd/Graphene Catalyst for Reduction of p-Nitrophenol.

Supported metal nanoparticles with small size and high dispersion can improve the performance of heterogeneous catalysts. To prepare graphene-supported Pd catalysts, graphene and PdCl2 were used as support and Pd precursors, respectively. Pd/G-P and Pd/G-H catalysts were prepared by cold plasma and conventional thermal reduction, respectively, for the catalytic reduction of p-nitrophenol (4-NP). The reaction followed quasi-first-order kinetics, and the apparent rate constant of Pd/G-P and Pd/G-H was 0.0111 and 0.0042 s−1, respectively. The graphene support was exfoliated by thermal reduction and cold plasma, which benefits the 4-NP adsorption. Pd/G-P presented a higher performance because cold plasma promoted the migration of Pd species to the support outer surface. The Pd/C atomic ratio for Pd/G-P and Pd/G-H was 0.014 and 0.010, respectively. In addition, the Pd nanoparticles in Pd/G-P were smaller than those in Pd/G-H, which was beneficial for the catalytic reduction. The Pd/G-P sample presented abundant oxygen-containing functional groups, which anchored the metal nanoparticles and enhanced the metal-support interaction. This was further confirmed by the shift in the binding energy to a high value for Pd3d in Pd/G-P. The cold plasma method operated under atmospheric pressure is effective for the preparation of Pd/G catalysts with enhanced catalytic activity for 4-NP reduction.

Size-Controlled Synthesis of Pd Nanocatalysts on Defect-Engineered CeO2 for CO2 Hydrogenation.

The size effects of metal catalysts have been widely investigated to optimize their catalytic activity and selectivity. However, the size-controllable synthesis of uniform supported metal nanoparticles without surfactants and/or additives remains a great challenge. Herein, we developed a green, surfactant-free, and universal strategy to tailor the sizes of uniform Pd nanoparticles on metal oxides by an electroless chemical deposition method via defect engineering of supports. The nucleation and growth mechanism suggest a strong electrostatic interaction between the Pd precursor and low-defective CeO2 and a weak reducing capacity for low-defective CeO2, resulting in small Pd nanoparticles. Conversely, large Pd nanoparticles were formed on a highly defective CeO2 surface. Combined with various ex situ and in situ characterizations, a higher intrinsic activity of Pd for the CO2-to-CO hydrogenation was found on large Pd nanoparticles with higher electron density owing to their stronger H2 dissociation ability and H-spillover effects, as well as the larger number of oxygen vacancies generated in situ for CO2 activation under hydrogenation conditions.

Zeolite Fixed Metal Nanoparticles: New Perspective in Catalysis.

ConspectusLoading metal nanoparticles on the surface of solid supports has emerged as an efficient route for the preparation of heterogeneous catalysts. Notably, most of these supported metal nanoparticles still have shortcomings such as dissatisfactory activity and low product selectivity in catalysis. In addition, these metal nanoparticles also suffer from deactivation because of nanoparticle sintering, leaching, and coke formation under harsh conditions. The fixation of metal nanoparticles within zeolite crystals should have advantages of high activities for metal nanoparticles and excellent shape selectivity for zeolite micropores as well as extraordinary stability of metal nanoparticles immobilized with a stable zeolite framework, which is a good solution for the shortcomings of supported metal nanoparticles.Materials with metal nanostructures within the zeolite crystals are normally denoted as metal@zeolite, where the metal nanoparticles with diameters similar to those of industrial catalysts are usually larger than the micropore size. These metal nanoparticles are enveloped with the zeolite rigid framework to prevent migration under harsh reaction conditions, which is described as a fixed structure. The zeolite micropores allow the diffusion of reactants to the metal nanoparticles. As a result, metal@zeolite catalysts combine the features of both metal nanoparticles (high activity) and zeolites (shape selectivity and thermal stability), compared with the supported metal nanoparticles.In this Account, we describe how the zeolite micropore and metal nanoparticle synergistically work to improve the catalytic performance by the preparation of a variety of metal@zeolite catalysts. Multiple functions of zeolites with respect to the metal nanoparticles are highlighted, including control of the reactant/product diffusion in the micropores, the adjustment of reactant adsorption on the metal nanoparticles, and sieving the reactants and products with zeolite micropores. Furthermore, by optimizing the wettability of the zeolite external surface, the zeolite crystals could form a nanoreactor to efficiently enrich the crucial intermediates, thus boosting the performance in low-temperature methane oxidation. Also, the microporous confinement weakens the adsorption of C1 intermediates on the metal sites, accelerating the C-C coupling to improve C2 oxygenate productivity in syngas conversion. In particular, the zeolite framework efficiently stabilizes the metal nanoparticles against sintering and leaching to give durable catalysts. Clearly, this strategy not only guides the rational design of efficient heterogeneous catalysts for potential applications in a variety of industrial chemical reactions but also accelerates the fundamental understanding of the catalytic mechanisms by providing new model catalysts.

Mesocellular silica foams supported size-controlled Pd nanoparticles for racemic and asymmetric iodomethyl dihydrobenzofuran synthesis

Supported metal nanoparticles (NPs) catalysts in constructing benzene-fused cyclic framework with chirality is very challenging. Dihydrobenzofuran and its derivatives are significant heterocyclic units in biologically molecules. Herein, size-controlled Pd NPs fixed on mesoporous silica (Pd/MS-xT) SBA-15, FDU-12 and mesocellular silica foams (MCFs) were utilized to synthesize racemic and asymmetric iodomethyl dihydrobenzofuran for the first time. The size of Pd NPs was regulated by increasing NaBH4 reduction treatments times (-xT) and enlarging supports pore. Based on large mesopore of MCF-3, supported catalyst 3%Pd/MCF-3-4T possessed larger Pd size gave the excellent performance at 92% racemic yield. Under chiral phosphine modifier N–Me-Xu3, we implemented more deserving asymmetric reaction over 3%Pd/MCF-3-1T with smaller Pd NPs. TGA for organic surface coverage demonstrated that the substrate preferred larger Pd NPs, N–Me-Xu3 capped more easily on smaller ones. Besides, effects of reaction medium and N–Me-Xu3 additive quantity further revealed the coordination of chiral modifier on Pd/MCF-3 was the determinant. For broader visions, the performance dependence based on surface properties of heterogeneous catalyst would play crucial contributions towards construction of complexed organic molecules.

Quantitative Determination of the Surface Distribution of Supported Metal Nanoparticles: A Laser Ablation–ICP–MS Based Approach

A laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) based method is proposed for the quantitative determination of the spatial distribution of metal nanoparticles (NPs) supported on planar substrates. The surface is sampled using tailored ablation patterns and the data are used to define three-dimensional functions describing the spatial distribution of NPs. The volume integrals of such interpolated surfaces are calibrated to obtain the mass distribution of Ag NPs by correlation with the total mass of metal as determined by metal extraction and ICP–MS analysis. Once this mass calibration is carried out on a sacrificial sample, quantifications can be performed over multiple samples by a simple micro-destructive LA–ICP–MS analysis without requiring the extraction/dissolution of metal NPs. The proposed approach is here tested using a model sample consisting of a low-density polyethylene (LDPE) disk decorated with silver NPs, achieving high spatial resolution over cm2-sized samples and very high sensitivity. The developed method is accordingly a useful analytical tool for applications requiring both the total mass and the spatial distribution of metal NPs to be determined without damaging the sample surface (e.g., composite functional materials and NPs, decorated catalysts or electrodic materials).

Metal Nanoparticles Immobilized on Molecularly Modified Surfaces: Versatile Catalytic Systems for Controlled Hydrogenation and Hydrogenolysis.

ConspectusThe synthesis and use of supported metal nanoparticle catalysts have a long-standing tradition in catalysis, typically associated with the field of heterogeneous catalysis. More recently, the development and understanding of catalytic systems composed of metal nanoparticles (NPs) that are synthesized from organometallic precursors on molecularly modified surfaces (MMSs) have opened a conceptually new approach to the design of multifunctional catalysts (NPs@MMS). These complex yet fascinating materials bridge molecular (“homogeneous”) and material (“heterogeneous”) approaches to catalysis and provide access to catalytic systems with tailor-made reactivity through judicious combinations of supports, molecular modifiers, and nanoparticle precursors. A particularly promising field of application is the controlled activation and transfer of dihydrogen, enabling highly selective hydrogenation and hydrogenolysis reactions as relevant for the conversion of biogenic feedstocks and platform chemicals as well as for novel synthetic pathways to fine chemicals and even pharmaceuticals. Consequently, the topic offers an emerging field for interdisciplinary research activities involving organometallic chemists, material scientists, synthetic organic chemists, and catalysis experts.This Account will provide a brief overview of the historical background and cover examples from the most recent developments in the field. A coherent account on the methodological and experimental basis will be given from the long-standing experience in our laboratories. MMSs are widely accessible via chemisorption and physisorption methods for the generation of stable molecular environments on solid surfaces, whereby a special emphasis is given here to ionic liquid-type molecules as modifiers (supported ionic liquid phases, SILPs) and silica as support material. Metal nanoparticles are synthesized following an organometallic approach, allowing the controlled formation of small and uniformly dispersed monometallic or multimetallic NPs in defined composition. A combination of techniques from molecular and material characterization provides a detailed insight into the structure of the resulting materials across various scales (electron microscopy, solid-state NMR, XPS, XAS, etc.).The molecular functionalities grafted on the silica surface have a pronounced influence on the formation, stabilization, and reactivity of the NPs. The complementary and synergistic fine-tuning of the metal and its molecular environment in NPs@MMSs allow in particular the control of the activation of hydrogen and its transfer to substrates. Monometallic (Ru, Rh, Pd) monofunctional NPs@MMSs possess excellent activities for the hydrogenation of alkenes, alkynes, and arenes for which a nonpolarized (homolytic) activation of H2 is predominant. The incorporation of 3d metals in noble metal NPs to give bimetallic (FeRu, CoRh, etc.) monofunctional NPs@MMSs favors a more polarized H2 activation and thus its transfer to the C=O bond, while at the same time preventing the arrangement of noble metal atoms necessary for ring hydrogenation. The incorporation of reactive functionalities, such as, for example, a −SO3H moiety on NPs@MMSs, results in bifunctional catalysts enabling the heterolytic cleavage corresponding to a formal H–/H+ transfer. Consequently, such catalysts possess excellent deoxygenation activity with strong synergistic effects arising from an intimate contact between the nanoparticles and the molecular functionality.While many more efforts are still required to explore, control, and understand the chemistry of NPs@MMS catalysts fully, the currently available examples already highlight the large potential of this approach for the rational design of multifunctional catalytic systems.

Catalytic wet hydrogen peroxide oxidation of isoeugenol to vanillin using microwave-assisted synthesized metal loaded catalysts

• Supported metal nanoparticles (Cu, W, Mo) on a silica matrix using a one-pot microwave-assisted protocol. • Catalytic activity evaluated in the oxidation of isoeugenol into vanillin. • Moderate conversions, up to 50–60 % (for Cu-MINT). • Acceptable selectivities towards vanillin production (22–45 %). • High catalyst stability (imperceptible decrease of activity after the fourth use). Supported metal nanoparticles (Cu, W, Mo among others) have been stabilized on a silica matrix following an efficient and sustainable one-pot microwave-assisted protocol. The materials synthesized were characterized, mainly, by nitrogen adsorption desorption measurements, X-ray diffraction (XRD), scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDS). The materials exhibited large surface area and pore size in the mesopore range. The incorporation of metal particles in the silica matrix was also confirmed with particle size in a wide range between 2 and 52 nm. The catalytic activity of the resulting materials was evaluated in the catalytic wet oxidation of isoeugenol into vanillin using hydrogen peroxide as oxidant. The catalysts shown moderate conversions, up to 50–60 % for Cu-MINT with acceptable selectivity towards vanillin production (22–45 %), obtaining dimers as main side products. The stability of the catalysts was investigated as well, obtaining an imperceptible decrease after the fourth use.

Effect of electron tunneling through the oxide film grown on metal substrate upon the efficiency of molecular reaction over the oxide supported metal nanoparticles: A case of CO oxidation on Au/Al2O3/Mo(110)

Formation of gold nanosized particles supported by aluminum oxide film grown on Mo(110) substrate and oxidation of carbon monoxide molecules on their surface have been in-situ studied in ultra-high vacuum by means of Auger electron spectroscopy (AES), reflection-absorption infrared spectroscopy (RAIRS), low energy electron diffraction (LEED), atomic force microscopy (AFM), temperature programmed desorption (TPD) and work function measurements. The main focus was to follow how the thickness of the alumina film influences the efficiency of CO oxidation in an attempt to find out an evidence of possible effect of electron tunneling between the metal substrate and the Au particle through the oxide interlayer. Providing the largest degree of surface identity of the studied metal/oxide system at different thicknesses of the alumina film (2, 4, 6 and 8 monolayers), it was found that the CO oxidation efficiency, defined as CO2 to CO TPD peaks intensity ratio, as well as the activation energy of CO oxidation, exponentially depend upon the oxide film thickness. Taking into account the known fact that the CO oxidation efficiency depends on the amount of excess charge acquired by Au particle, the latter suggests that electron tunneling adds efficiency to the oxidation process, although not significantly.

Recent advances in cellulose supported metal nanoparticles as green and sustainable catalysis for organic synthesis

Organic reactions generally involve a variety of catalysts and solvents, which may be inflammable, toxic, and/or corrosive. Consequently, most of these reactions highly influence the environment. However, recent science and technology applications shift towards eco-friendly and sustainable resources and processes. Nanocatalysis has recently become an emerging field of science owing to its high reactivity, productivity, and selectivity. Cellulose supported metal nanoparticles (NPs) have been broadly applied in catalysis toward the development of green and sustainable chemical transformation processes. Those catalysts can be easily recycled several times without losing their reactivity. Metal nanoparticles have recently attracted more attention as a result of their distinctive characteristics in comparison to their equivalent bulk metals. Those characteristics include a large surface-to-volume ratio, high porosity, and tunable structural morphology. Controlling the characteristics of nanoparticles particularly with respect to their structural morphology, particle size and dispersibility are essential because those will identify their catalytic activity. Recent developments in controlling dispersibility, particle size, and morphological shape of metal nanoparticles paved the way to optimize the nanoparticle geometry for improved catalytic activity. This review focuses on the fabrication and application of cellulose supported metal nanoparticles as promising catalysts for green modern organic synthesis and aims to present cellulose supported metal nanoparticles as a green, sustainable and renewable alternative to conventional catalysts for future industrial applications. The major groups of noble and transition metal nanoparticles are highlighted.

Markedly improved performance of oxide-supported catalysts in hot basic water by three facile ways in synergy

Use oxide-supported catalyst in green solvent, hot water : Au is anchored on oxide via Au┄O-M interaction (M = Fe, Ti, etc). Basic aqueous catalytic system may destruct a part of O M bonds into oxygen vacancies and weaken Au/support interaction, causing leaching and aggregation of Au. Three simple methods synergistically improve reusability of catalyst. • Three facile ways synergistically improve catalyst reusability in green solvent, water. • They raise support stability and Au/support interaction to reduce leaching and aggregation of Au. • Nano supports interact with Au more strongly, and are more stable in hot basic water. • Nano TiO 2 is more stable due to the stronger surface Ti O bond, in line with BOLS theory. Obtaining reusable catalysts and using water as a green solvent still remain huge challenges. Various oxides are frequently used as the support, however, the aqueous catalytic systems, particularly in hot basic water, may decrease their stability and thus cause leaching or aggregation of the supported metal nanoparticles (NPs). In this work, three very simple methods in catalyst preparation are demonstrated to greatly improve the reusability of oxide-supported catalysts in 100 °C basic water, by systematically studying a series of oxides as well as carbons as support of gold (Au) NPs and employing Suzuki-Miyaura cross-coupling (SMCC) reaction as a probe. These methods are prerequisites for obtaining both excellent activity and recyclability. Absence of any of them will badly improve leaching or aggregation of Au NPs. The reasons for the synergistically improved reusability are also elucidated in details. Though it’s extremely hard to thoroughly overcome leaching in hot water, this work achieves the application of Au/oxide to SMCC reaction in water with higher utilization efficiency of Au than some reported work in organic solvent or with other supports. The present work can serve as supplementary strategies to assist in designing high-performance oxide-supported catalysts for varieties of similar aqueous systems.

Study of the Direct CO2 Carboxylation Reaction on Supported Metal Nanoparticles

2,5-furandicarboxylic acid (2,5-FDCA) is a biomass derivate of high importance that is used as a building block in the synthesis of green polymers such as poly(ethylene furandicarboxylate) (PEF). PEF is presumed to be an ideal substitute for the predominant polymer in industry, the poly(ethylene terephthalate) (PET). Current routes for 2,5-FDCA synthesis require 5-hydroxymethylfurfural (HMF) as a reactant, which generates undesirable co-products due to the complicated oxidation step. Therefore, direct CO2 carboxylation of furoic acid salts (FA, produced from furfural, derivate of inedible lignocellulosic biomass) to 2,5-FDCA is potentially a good alternative. Herein, we present the primary results obtained on the carboxylation reaction of potassium 2-furoate (K2F) to synthesize 2,5-FDCA, using heterogeneous catalysts. An experimental setup was firstly validated, and then several operation conditions were optimized, using heterogeneous catalysts instead of the semi-heterogeneous counterparts (molten salts). Ag/SiO2 catalyst showed interesting results regarding the K2F conversion and space–time yield of 2,5-FDCA.

Supported Metal Nanoparticles in Metal‐Organic Monoliths for Assembly of a Catalytic Microfluidic Reactor

AbstractA novel strategy has been developed to fabricate an Au@CrADC (ADC=5‐aminobenzene‐1,3‐dicarboxylate) metal‐organic monolithic capillary in microfluidic reactors. Monolithic Cr3+‐based metal‐organic gel (MOG) as catalyst support is synthesized inside fused‐silica capillary employing a two‐step procedure including surface modification of carboxyl group to provide anchoring sites and subsequent MOG formation. Subsequently, Au nanoparticles are in situ immobilized in the monolithic MOG support as active catalysts. The resulting Au@CrADC monolithic capillary is used to assemble a catalytic microfluidic reactor. The catalytic activity of the Au@CrADC reactor is probed by using the oxidative alkyne coupling reaction to synthesize 1,3‐diynes. The catalytic microfluidic reactor demonstrates significantly enhanced catalytic activity in comparison with the corresponding reactions under batch conditions. Additionally, the microfluidic reactor shows high stability with no significant catalytic deactivation during repeated uses.

Palladium Nanoparticles Immobilized on a Resorcin[4]arene-Based Metal–Organic Framework for Hydrogenation of Nitroarenes

Metal–organic framework (MOF)-supported metal nanoparticles (NPs) have been proven to be highly efficient in catalytic fields. In this work, palladium NPs were rationally confined in a MOF [CuI4(Si...

Design and Characterization of ALD-Based Overcoats for Supported Metal Nanoparticle Catalysts

Supported metal nanoparticle (SMN) catalysts are enormously crucial for many catalytic applications. However, catalyst deactivation, caused by sintering and coke formation, is a ubiquitous problem ...

An intriguing electrochemical impedance aptasensor based on a porous organic framework supported silver nanoparticles for ultrasensitively detecting theophylline

Porous organic frameworks (POFs) are excellently stable porous materials, which can be employed as host platforms to support metal nanoparticles as functional composites for various applications. Herein, a novel POF is successfully prepared via Friedel-Crafts reaction. Silver nanoparticles (Ag NPs) are embedded in the prepared POF to generate an Ag@POF composite, which not only possesses high surface area, outstanding physicochemical stability and outstretched π-conjugation skeleton, but also exhibits preferable electrochemical stability and conductivity. This composite is able to immobilize a mass of aptamer strands to fabricate an intriguing electrochemical aptasensor. Electrochemical impedance spectroscopy (EIS) is a commonly used technology to analyze the electrochemical signal variation. The Ag@POF-based biosensor shows the excellent electrochemical detection behavior through analyzing EIS. For instance theophylline as a research mode, the Ag@POF based electrochemical aptasensor reveals ultra-sensitiveness, high selectivity, remarkable stability, good repeatability and simple operability even in various real samples. Notably, this aptasensor has the sensitive detection performance with the limit of detection of 0.191 pg/mL (1.06 pmol/L) in a wide concentration range of 5.0 × 10-4 – 5.0 ng/mL (2.78 × 10-3 – 27.8 nmol/L).