In the realm of nanopore sensor technology, an enduring challenge lies in achieving the discerning detection of small biomolecules with a sufficiently high signal-to-noise ratio. This study introduces a method for reliably quantifying the concentration of target small molecules, utilizing tetrahedral DNA nanostructures as surrogates for the captured molecules through a magnetic-bead-based competition substitution mechanism. Magnetic Fe3O4-DNA tetrahedron nanoparticles (MNPs) are incorporated into a nanopore electrochemical system for small-molecule sensing. In the presence of the target, the DNA tetrahedron, featuring an aptamer tail acting as a molecular carrier, detaches from the MNPs due to aptamer deformation. Following removal of the MNPs, the DNA tetrahedron bound to the target traversed the nanopore by applying a positive potential. This approach exhibits various advantages, including heightened sensitivity, selectivity, an improved signal-to-noise ratio (SNR), and robust anti-interference capabilities. Our findings demonstrate that this innovative methodology has the potential to significantly enhance the sensing of various small-molecule targets by nanopores, thereby advancing the sensitivity and dynamic range. This progress holds promise for the development of precise clinical diagnostic tools.
Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in-situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1% at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.
The development of cost-effective and highly efficient electrocatalysts is critical to help electrochemical non-enzymatic sensors achieve high performance. Here, a new class of catalyst, Ru single atoms confined on Cu nanotubes as a single-atom alloy (Ru1Cu NTs), with a unique electronic structure and property, was developed to construct a novel electrochemical non-enzymatic glucose sensor for the first time. The Ru1Cu NTs with a diameter of about 24.0 nm showed a much lower oxidation potential (0.38 V) and 9.0-fold higher response (66.5 µA) current than Cu nanowires (Cu NWs, oxidation potential 0.47 V and current 7.4 µA) for glucose electrocatalysis. Moreover, as an electrochemical non-enzymatic glucose sensor, Ru1Cu NTs not only exhibited twofold higher sensitivity (54.9 µA mM-1 cm-2) and wider linear range (0.5-8 mM) than Cu NWs, but also showed a low detection limit (5.0 µM), excellent selectivity, and great stability. According to theoretical calculation results, the outstanding catalytic and sensing performance of Ru1Cu NTs could be ascribed to the upshift of the d-band center that helped promote glucose adsorption. This work presents a new avenue for developing highly active catalysts for electrochemical non-enzymatic sensors.
Urinary tract infections (UTIs), which can lead to pyelonephritis, urosepsis, and even death, are among the most prevalent infectious diseases worldwide, with a notable increase in treatment costs due to the emergence of drug-resistant pathogens. Current diagnostic strategies for UTIs, such as urine culture and flow cytometry, require time-consuming protocols and expensive equipment. We present here a machine learning-assisted colorimetric sensor array based on recognition of ligand-functionalized Fe single-atom nanozymes (SANs) for the identification of microorganisms at the order, genus, and species levels. Colorimetric sensor arrays are built from the SAN Fe1-NC functionalized with four types of recognition ligands, generating unique microbial identification fingerprints. By integrating the colorimetric sensor arrays with a trained computational classification model, the platform can identify more than 10 microorganisms in UTI urine samples within 1 h. Diagnostic accuracy of up to 97% was achieved in 60 UTI clinical samples, holding great potential for translation into clinical practice applications.
Colorimetry , Machine Learning , Urinary Tract Infections , Urinary Tract Infections/diagnosis , Urinary Tract Infections/microbiology , Urinary Tract Infections/urine , Colorimetry/methods , Humans , Iron/chemistry , Biosensing Techniques/methods
Developing in situ/operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Herein, we report the fabrication of highly ordered rhombic gold nanocube superlattices (GNSs) as substrates for surface-enhanced infrared absorption spectroscopy (SEIRAS) with significantly enhanced SEIRA effect, which can be controlled by manipulating the randomness of GNSs. Finite difference time domain simulations reveal that the electromagnetic effect accounts for the significantly improved spectroscopic vibrations on the GNSs. In situ SEIRAS results show that the vibrations of CO on the Cu2O surfaces have been enhanced by 2.4 ± 0.5 and 18.0 ± 1.3 times using GNSs as substrates compared to those on traditional chemically deposited gold films in acidic and neutral electrolytes, respectively. Combined with isotopic labeling experiments, the reaction mechanisms for C-C coupling of CO electroreduction on Cu-based catalysts are revealed using the GNSs substrates.
Understanding the structure-stability relationship of catalysts is imperative for the development of high-performance electrocatalytic devices. Herein, we utilize operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) to quantitatively monitor the evolution of Cu single-atom catalysts (SACs) during the electrochemical reduction of CO2 (CO2RR). Cu SACs are converted into 2-nm Cu nanoparticles through a reconstruction process during CO2RR. The evolution rate of Cu SACs is highly dependent on the substrates of the catalysts due to the coordination difference. Density functional theory calculations demonstrate that the stability of Cu SACs is highly dependent on their formation energy, which can be manipulated by controlling the affinity between Cu sites and substrates. This work highlights the use of operando ATR-SEIRAS to achieve mechanistic understanding of structure-stability relationship for long-term applications.
In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co2+ can enhance the electron backdonation via the dxz/dyz-2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.
Single-atom catalysts exhibit superior CO2 -to-CO catalytic activity, but poor kinetics of proton-coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe-P atom paired catalyst onto nitrogen doped graphitic layer (Fe1 /PNG) to accelerate PCET step. Fe1 /PNG delivers an industrial CO current of 1â A with FECO over 90 % at 2.5â V in a membrane-electrode assembly, overperforming the CO current of Fe1 /NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe-P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2 , and enhancing the activity of CO2 reduction. This atom-pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single-atom catalysts.
Constructing atomic catalytic pair emerges as an attractive strategy to achieve better catalytic performance. Herein, an atomic Ir1 âP1 /NPG catalyst with asymmetric IrâN2 P1 sites that delivers superb activity and selectivity for hydrogenation of various functionalized nitrostyrene is reported. In the hydrogenation reaction of 3-nitrostyrene, Ir1 âP1 /NPG (NPG refers to N, P-codoped graphene) shows a turnover frequency of 1197 h-1 , while the reaction cannot occur over Ir1 /NG (NG refers to N-doped graphene). Compared to Ir1 /NG, the charge density of the Ir site in Ir1 âP1 /NPG is greatly elevated, which is conducive to H2 dissociation. Moreover, as revealed by density functional theory calculations and poisoning experiments, the P site in Ir1 âP1 /NPG is found able to bind nitrostyrene, while the neighboring Ir site provides H to reduce the nitro group in chemoselective hydrogenation of nitrostyrene. This work offers a successful example of establishing atomic catalytic pair for driving important chemical reactions, paving the way for the development of more advanced catalysts to further improve the catalytic performance.
Single-atom catalysts supported on semiconductors can serve as active sites for efficient oxygen reduction to hydrogen peroxide (H2O2). However, researchers have long been puzzled by the lack of guidance on optimizing the performance of single-atom photocatalysts. In this study, we propose a versatile strategy that utilizes carbon vacancies to regulate the electronic configuration of antimony (Sb) atoms on carbon nitrides (C3N4). This strategy has been found to significantly enhance the photocatalytic production of H2O2. The H2O2 evolution rate of Sb single-atom on carbon vacancy-rich C3N4 (designated as Sb1/Cv-C3N4) is 5.369 mmol g-1h-1, which is 10.9 times higher than C3N4 alone. By combining experimental characterizations and density functional theory simulations, we reveal the strong electronic interaction between Sb atoms and carbon vacancy-rich C3N4. This interaction is capable for maintaining the electron-rich state of Sb atoms, facilitating efficient electron transfer to pauling-type absorbed oxygen, and ultimately enhancing the formation of *OOH intermediates. This innovative defect-engineering approach can manipulate the electronic configuration of single-atom catalysts, providing a new avenue to boost the photocatalytic oxygen reduction reaction towards H2O2 production.
The structure of nanomaterials and nanodevices determines their functionality and applications. A single uniform nanochannel with a high aspect ratio is an attractive structure due to its unique rigid structures, easy preparation, and diverse pore structures and it holds significant promising importance in fields such as nanopore sensing and nanomanufacturing. Although the metal-nanoparticle-assistant silicon etching technique can produce uniform nanochannels, however, the fabrication of single through nanochannels remains a challenge thus far. A simple and versatile strategy is developed that allows for the retention of individual gold nanoparticle on a substrate, enabling single-nanoparticle nanomachining. This method involves three steps: the formation of a carbon protective layer on individual nanoparticles via electron-beam irradiation, selective removal of unprotected nanoparticles using a corrosive agent, and subsequent elimination of the carbon layer. This enables the fabrication of a single submillimeter-long uniform through nanochannel in the silicon wafer, which can be employed for nanopore sensing and shape-based nanoparticle distinguishing. The developed method can also facilitate single-nanoparticle studies and nanomachining for a broad application in materials science, electronics, micro/nano-optics, and catalysis.
In the electrochemical CO2 reduction reaction (CO2RR), CO2 activation is always the first step, followed by the subsequent hydrogenation. The catalytic performance of CO2RR is intrinsically restricted by the competition between molecular CO2 activation and CO2 reduction product release. Here, we design a heteronuclear Fe1-Mo1 dual-metal catalytic pair on ordered porous carbon that features a high catalytic performance for driving electrochemical CO2 reduction to CO. Combining real-time near-ambient pressure X-ray photoelectron spectroscopy, operando 57Fe Mössbauer spectroscopy, and in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements with density functional theory calculations, chemical adsorption of CO2 is observed on the Fe1-Mo1 catalytic pair through a bridge configuration, which prompts the bending of the CO2 molecule for CO2 activation and then facilitates the subsequent hydrogeneration reaction. More importantly, the dynamic adsorption configuration transition from the bridge configuration of CO2 on Fe1-Mo1 to the linear configuration of CO on the Fe1 center results in breaking the scaling relationship in CO2RR, simultaneously promoting the CO2 activation and the CO release.
The single-molecule technique for investigation of an unlabeled protein in solution is very attractive but with great challenges. Nanopore sensing as a label-free tool can be used for collecting the structural information of individual proteins, but currently offers only limited capabilities due to the fast translocation of the target. Here, a reliable and facile method is developed to convert the silicon nitride nanopore to a stable nanonet platform for single-entity sensing by electrophoretic or electroosmotic trapping. A nanonet is fabricated based on a material reorganization process caused by electron-beam and light-irradiation treatment. Using protein molecules as a model, it is revealed that the solid-state nanonet can produce collision and trapping flipping signals of the protein, which provides more structural information than traditional nanopore sensing. More importantly, thanks to the excellent stability of the solid-state silicon nitride nanonet, it is demonstrated that the ultraviolet-light-irradiation-induced structural-change process of an individual protein can be captured. The developed nanonet supplies a robust platform for single-entity studies but is not limited to proteins.
Nanopores , Silicon Compounds/chemistry , Nanotechnology
It is critical to develop high-performance electrocatalyst for electrochemical nonenzymatic glucose sensing. In this work, a single-atom Pt supported on Cu@CuO core-shell nanowires (Pt1 /Cu@CuO NWs) for electrochemical nonenzymatic glucose sensor is designed. Pt1 /Cu@CuO NWs exhibit excellent electrocatalytic oxidation toward glucose with 70 mV lower onset potential (0.131 V) and 2.4 times higher response current than Cu NWs. Sensors fabricated using Pt1 /Cu@CuO NWs also show high sensitivity (852.163 µA mM-1 cm-2 ), low detection limit (3.6 µM), wide linear range (0.01-5.18 µM), excellent selectivity, and great long-term stability. The outstanding sensing performance of Pt1 /Cu@CuO NWs, investigated by experiments and density functional theory (DFT) calculations, is attributed to the synergistic effect between Pt single atoms and Cu@CuO core-shell nanowires that generates strong binding energy of glucose on the nanowires. The work provides a new pathway for exploring highly active SACs for electrochemical nonenzymatic glucose sensor.
Direct Z-scheme Cu7 S4 /CdS Janus photocatalysts are successfully prepared by cation exchange method. Extensive studies containing single-nanoparticle impact electrochemistry are performed and reveal that optimizing the Cu7 S4 /CdS ratio can decrease the accumulation of holes on valence band of CdS for inhibiting photo-corrosion and promote the accumulation of electrons on the conduction band of Cu7 S4 for boosting the electron reducibility. With the optimized heterostructures, hydrogen evolution is remarkable promoted up to 21.62â mmol/g/h and quantum efficiency is up to 14.37% using polylactic acid plastic waste as feedstock.
Photochemical Processes , Sulfides , Sulfides/chemistry , Catalysis , Hydrogen/chemistry , Plastics
The fascinating phenomenon that plasmon excitation can convert isotropic silver nanospheres to anisotropic nanoprisms has already been developed into a general synthetic technique since the discovery in 2001. However, the mechanism governing the morphology conversion is described with different reaction processes. So far, the mechanism based on redox reactions dominated anisotropic growth by plasmon-produced hot carriers is widely accepted and developed. Here, we successfully achieved plasmon-driven high yield conversion of gold nanospheres into nanoplates with iodine as the inducer. To investigate the mechanism, nanopore sensing technology is established to statistically study the intermediate species at the single-nanoparticle level. Surprisingly, the morphology conversion is proved as a hot hole-controlled coalescence-dominated growth process. This work conclusively elucidates that a controllable plasmon-driven nanoparticle-coalescence mechanism could enable the production of well-defined anisotropic metal nanostructures and suggests that the nanopore sensing could be of general use for studying the growth process of nanomaterials.
Metal Nanoparticles , Nanopores , Gold/chemistry , Metal Nanoparticles/chemistry , Silver/chemistry , Surface Plasmon Resonance/methods
Heteroatom doped atomically dispersed Fe1 -NC catalysts have been found to show excellent activity toward oxygen reduction reaction (ORR). However, the origin of the enhanced activity is still controversial because the structure-function relationship governing the enhancement remains elusive. Herein, sulfur(S)-doped Fe1 -NC catalyst was obtained as a model, which displays a superior activity for ORR towards the traditional Fe-NC materials. 57 Fe Mössbauer spectroscopy and electron paramagnetic resonance spectroscopy revealed that incorporation of S in the second coordination sphere of Fe1 -NC can induce the transition of spin polarization configuration. Operando 57 Fe Mössbauer spectra definitively identified the low spin single-Fe3+ -atom of C-FeN4 -S moiety as the active site for ORR. Moreover, DFT calculations unveiled that lower spin state of the Fe center after the S doping promotes OH* desorption process. This work elucidates the underlying mechanisms towards S doping for enhancing ORR activity, and paves a way to investigate the function of broader heteroatom doped Fe1 -NC catalysts to offer a general guideline for spin-state-determined ORR.
A photochemical method is used to grow Au nanoplates in high yield from in situ generated Au cluster seeds through the galvanic replacement reaction. The morphology of nanoplates can be further controllably tuned by adjusting the pH, and enhanced morphology determined non-linear optics performances are obtained.
Compared with the large variety of solid gold nanostructures, synthetic approaches for their hollow counterparts are limited, largely confined to chemical and irradiation-based etching of preformed nanostructures. In particular, the preparation of through nanopore structures is extremely challenging. Here, a unique strategy for direct synthesis of gold nanopores in solution without the need for sacrificial templates or postsynthesis processing is reported. By controlling the degree of crystal screw dislocation, a single through pore with diameter ranging from sub-nanometer to tens of nanometers, in the center of large gold nanoplates, can be engineered with precision. Ionic current rectification behaviors are observed using the gold nanopore, potentially enabling new capabilities in biosensing, sequencing, and imaging.
After more than a decade, it is still unknown whether the plasmon-mediated growth of silver nanostructures can be extended to the synthesis of other noble metals, as the molecular mechanisms governing the growth process remain elusive. Herein, we demonstrate the plasmon-driven synthesis of gold nanoprisms and elucidate the details of the photochemical growth mechanism at the single-nanoparticle level. Our investigation reveals that the surfactant polyvinylpyrrolidone preferentially adsorbs along the nanoprism perimeter and serves as a photochemical relay to direct the anisotropic growth of gold nanoprisms. This discovery confers a unique function to polyvinylpyrrolidone that is fundamentally different from its widely accepted role as a crystal-face-blocking ligand. Additionally, we find that nanocrystal twinning exerts a profound influence on the kinetics of this photochemical process by controlling the transport of plasmon-generated hot electrons to polyvinylpyrrolidone. These insights establish a molecular-level description of the underlying mechanisms regulating the plasmon-driven synthesis of gold nanoprisms.
