Promising Mass-Productive 4-Inch Commercial SERS Sensor with Particle in Micro-Nano Porous Ag/Si/Ag Structure Using in Auxiliary Diagnosis of Early Lung Cancer.

The construction of commercial surface enhanced Raman scattering (SERS) sensors suitable for clinical applications is a pending problem, which is heavily limited by the low production of high-performance SERS bases, because they usually require fine or complicated micro/nano structures. To solve this issue, herein, a promising mass-productive 4-inch ultrasensitive SERS substrate available for early lung cancer diagnosis is proposed, which is designed with a special architecture of particle in micro-nano porous structure. Benefitting from the effective cascaded electric field coupling inside the particle-in-cavity structure and efficient Knudsen diffusion of molecules within the nanohole, the substrate exhibits remarkable SERS performance for gaseous malignancy biomarker, with the limit of detection is 0.1 ppb and the average relative standard deviation value at different scales (from cm2 to µm2 ) is ≈16.5%. In practical application, this large-sized sensor can be further divided into small ones (1 × 1 cm2 ), and more than 65 chips will be obtained from just one 4-inch wafer, greatly increasing the output of commercial SERS sensor. Further, a medical breath bag composed of this small chip is designed and studied in detail here, which suggested high-specificity recognition for lung cancer biomarker in mixed mimetic exhalation tests.

Precise real-time quantification for photocatalytic reaction: integration of the sensitivein-situSERS sensor and high-efficiency photocatalyst.

Recently,in-situsurface-enhanced Raman spectroscopy (SERS) is gradually becoming an important method for monitoring photocatalytic reaction processes, in which the quantification potential is a vital factor in determining whether this technology can be truly applied in the future. In order to improve the quantification performance ofin-situSERS and explore a precise operando Raman detection for photocatalytic reactions, an architecture of heterostructural Cu2O/ZnO/Ag nano round brush has been designed and discussed in this work. This structure is an integration of sensitivein-situSERS sensor and high-efficiency photocatalyst, realizing real-time monitoring of photocatalytic reaction in a wide concentration range from 20 to 3 mg l-1. The coefficient of determination between different detection methods is beyond 0.86 in this range, implying the high-precise quantification of this platform. Comprehensive analysis on structure effect, SERS performance, photocatalytic property, electric filed characteristic, etc were all systematically made and discussed in detail for this platform. This work presents a precise preliminar real-time photocatalytic monitoring usingin-situSERS detection, which is a new attempt and also meaningful reference for otherin-situanalytical technology.

Preparation of a superhydrophobic AgNP/GF substrate and its SERS application in a complex detection environment.

Surface-enhanced Raman scattering (SERS) is widely considered to be a fingerprint spectrum that can realize molecular identification, and it continues to receive a lot of attention due to its high sensitivity and powerful qualitative analysis capabilities. In recent years, there has been a lot of work and reports on super-sensitive SERS substrates, but often the enhanced ability of the substrate is also effective for impurities and irrelevant molecules. Therefore, a problem that still remains to be solved is how to perform effective trace detection of specific substances in a complex detection environment. Herein, a superhydrophobic Ag nanoparticle/glass microfibre filter (AgNP/GF) substrate was designed to realize the Raman detection of complex multiphase solutions. The hydrophobic three-dimensional net-like structure provides efficient Raman enhancement, making the substrate have extremely high detection limits for dye molecules and even achieving specific detection of the hexane phase component (thiram molecule) in a multiphase solution.

SERS substrate with wettability difference for molecular self-concentrating detection.

The surface-enhanced Raman spectroscopy (SERS) has attracted much attention due to the powerful capability of quantificational analysis. Nowadays, most of the enhancement effect by SERS substrate is provided by the 'hot spots' occupying relatively small space. When the amount of analyte is too low, it is difficult to ensure that all the probe molecules can be placed into the 'hot spots', which is a headache in SERS quatification. In order to solve this problem, we have developed a structure of CuO nanowires/Ag nanoparticles with wettability capacity difference, which can aggregate molecules in water and oil simultaneously under two different mechanisms. The limit of detection and enhancement factor of this structure are estimated as 10-15M and 1.55 × 1011respectively (for rhodamine 6G, R6G). In a proof-in-principle experiment of sewage detection, it successfully achieved the aggregation and additional enhancement of both the R6G molecules in aqueous solution and thiuram molecules in toluene, realizing efficient and accurate Raman detection.

Heterostructured Cu2O-Au nanowire as a dual-functional nanocomposite for environmental pollutant degradation and hydrogen peroxide sensing.

Materials engineering is generally regarded as one of the most effective methods in the construction of photocatalysts, but it still faces many challenges. In this context, we designed and prepared a three-dimensional (3D) heterostructure of nanowires (NWs) formed by Cu2O core and an Au shell. The Cu2O-Au NWs not only show fine photocatalytic ability but also proved to have Fenton-like chemical properties and can be used as a hydrogen peroxide sensor. Moreover, this heterostructure realizes an integration of catalytic efficiency, retrievability, and versatility. In further consideration of the facile preparation process and low-cost material source of the structure, the Cu2O-Au NWs show a promising application prospect in the field of multifunctional photocatalysts.

Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters.

The limitations of the Haber-Bosch reaction, particularly high-temperature operation, have ignited new interests in low-temperature ammonia-synthesis scenarios. Ambient N2 electroreduction is a compelling alternative but is impeded by a low ammonia production rate (mostly <10 mmol gcat-1 h-1), a small partial current density (<1 mA cm-2), and a high-selectivity hydrogen-evolving side reaction. Herein, we report that room-temperature nitrate electroreduction catalyzed by strained ruthenium nanoclusters generates ammonia at a higher rate (5.56 mol gcat-1 h-1) than the Haber-Bosch process. The primary contributor to such performance is hydrogen radicals, which are generated by suppressing hydrogen-hydrogen dimerization during water splitting enabled by the tensile lattice strains. The radicals expedite nitrate-to-ammonia conversion by hydrogenating intermediates of the rate-limiting steps at lower kinetic barriers. The strained nanostructures can maintain nearly 100% ammonia-evolving selectivity at >120 mA cm-2 current densities for 100 h due to the robust subsurface Ru-O coordination. These findings highlight the potential of nitrate electroreduction in real-world, low-temperature ammonia synthesis.

Hierarchical Particle-In-Quasicavity Architecture for Ultratrace In Situ Raman Sensing and Its Application in Real-Time Monitoring of Toxic Pollutants.

Unstable detection environment is one of the biggest interferences for in situ surface-enhanced Raman spectroscopy (SERS) using in real-time monitoring of toxic pollutants, leading to unreliable results. To address this problem, we have designed and prepared a cavity-based particle-in-quasicavity (PIQC) architecture composed of hierarchical ZnO/Ag nanosheets and nanoprotrusions for improving the in situ SERS performance under a liquid environment. Benefitting from the special cascaded optical field mode, the PIQC ZnO/Ag exhibits excellent in situ SERS detectability, with 10-18 M of limit of detection for rhodamine 6G and 12.8% of signal relative standard deviation value. Furthermore, by means of a microfluidic chip, this PIQC structure is proved to have the quantitative analysis feasibility and realizes real-time monitoring of the 3,3',4,4'-tetrachlorobiphenyl, a representative global environmental hazard, under the flowing environment. The strategy in this paper provides a brand new idea to promote the application of in situ SERS in contaminant monitoring and is also instructive for light control in other optical fields.

Synthesis of Semiconducting 2H-Phase WTe2 Nanosheets with Large Positive Magnetoresistance.

Tungsten ditelluride (WTe2) is provoking immense interest because of its unique electronic properties, but studies about its semiconducting hexagonal (2H) phase are quite rare. Herein, we report the synthesis of semiconducting 2H WTe2 nanosheets with large positive magnetoresistance, for the first time, by a simple lithium-intercalation-assisted exfoliation strategy. Systematic characterizations including high-resolution transmission electron microscopy, X-ray diffraction, and Raman and X-ray photoelectron spectroscopies provide clear evidence to distinguish the structure of 2H WTe2 nanosheets from the orthorhombic (Td) phase bulk counterpart. The corresponding electronic phase transition from metal to semiconductor is also confirmed by density of states calculation, optical absorption, and electrical transport property measurements. Besides, the 2H WTe2 nanosheets exhibit large positive magnetoresistance with values of up to 29.5% (10 K) and 16.2% (300 K) at 9 T. Overall, these findings open up a promising avenue into the exploration of WTe2-based materials in the semiconductor field.

In situ detection of trace pollutants: a cost-effective SERS substrate of blackberry-like silver/graphene oxide nanoparticle cluster based on quick self-assembly technology.

To realize fast detection of trace hazardous chemicals, a SERS substrate with the structure of a blackberry-like silver/graphene oxide nanoparticle cluster (Ag/GO NPC) has been designed and prepared through a quick capillarity-assistant self-assembly technology in this paper. Benefitting from the abundant "hot spots" and active oxygen sites brought by this Ag/GO NPC, the substrate shows good Raman performance for malachite green (MG), a common abusive germicide in aquaculture, with lowest limit of detection below 0.1 µg/L (3.48 × 10-10 mol/L). Detailed analyses are taken on both the formation process and enhancement mechanism of this SERS substrate, and the finite-difference time-domain simulations are utilized as well to prove our hypotheses. Further constructing this structure on polyethylene terephthalate (PET) film, a translucent flexible SERS substrate can be obtained, realizing a fast in situ detection of trace MG in the fishpond subsequently. In consideration of the facile preparation process, good SERS enhancement and affordable materials (PET, Cu, Ag and GO, etc.), this substrate presents high cost performance and a promising application prospect.

Promoted water splitting by efficient electron transfer between Au nanoparticles and hematite nanoplates: a theoretical and experimental study.

An ideal interface model combining a hematite nanoplate-based photoanode with Au nanoparticles (NPs) is proposed for elucidating the specific role of Au NPs in photoelectrochemical performances. The theoretical and experimental results reveal that Au/Fe2O3 nanoplates can lead to an enhanced localized electric field at the metal-semiconductor interface upon the formation of surface plasmon resonance and hot electrons, which can be injected into the conduction band of the semiconductor, thus improving the efficiency of the generation and separation of electron-hole pairs. As expected, the Au/Fe2O3 nanoplate-based photoelectrode possessed a higher carrier density and a photocurrent of 1.7 mA cm-2 and 3.8 mA cm-2 at 1.23 V and 1.5 V vs. RHE, which are nearly 5 times and 30 times larger than that of the Au/Fe2O3 nanocrystals and pristine Fe2O3 nanoplate-based photoelectrodes, respectively.

High stability luminophores: fluorescent CsPbX3 (X = Cl, Br and I) nanofiber prepared by one-step electrospinning method.

The novel fluorescent nanofiber membranes of CsPbX3 (FNMs/CPX, X = Cl, Br, I) with a wide photoluminescence range from 405 nm to 675 nm are fabricated by a one-step electrospinning method in this paper. Owing to the polymer cladding, these FNMs/CPX show much better thermal and humid stability compared to the common CsPbX3 particles, and the corresponding white light-emitting diode prepared by them also exhibits excellent optical properties. Without adopting any complicated processes, this method opens up a brand new way for the perovskite materials using in lighting and display fields.

Iron-Incorporated α-Ni(OH)2 Hierarchical Nanosheet Arrays for Electrocatalytic Urea Oxidation.

An iron-incorporated α-Ni(OH)2 nanosheet array catalyst characterized by hierarchical surface nanobelts and robust urea oxidation performance are reported. The unique single-crystalline belt-on-sheet hierarchical nanostructure was identified and it endows more reactive edges for the Ni2+ -to-Ni3+ pre-oxidation process to boost the generation of active high-valence species for the urea oxidation reaction (UOR). Benefitting from the optimal Fe concentration, the UOR activity was further optimized owing to the favorable reaction kinetics. With the synergistic benefits of the increased surface areas, improved charge transfer behavior, favorable reaction kinetics and excellent structural stability, the iron-incorporated α-Ni(OH)2 hierarchical nanosheet array catalyst displays significantly improved UOR performance with both high activity and outstanding operational stability. This work could guide the design of advanced UOR catalysts for wastewater treatment and clean energy production in the future.

Visualization and Inhibition of Mitochondria-Nuclear Translocation of Apoptosis Inducing Factor by a Graphene Oxide-DNA Nanosensor.

High concentrations of oxidized low density lipoprotein (oxLDL) induce aberrant apoptosis of vascular smooth muscle cells (VSMCs) in atherosclerotic plaques. This apoptosis cannot be blocked completely by the inhibition of caspase, and it eventually potentiates plaque disruption and risk for cardiovascular disease. Given the important role of apoptosis inducing factor (AIF) in caspase-independent apoptosis, here we develop an AIF-targeting nanosensor by the assembly of graphene oxide (GO) nanosheets and dye-labeled DNA hybrid structures. This nanosensor selectively localizes in the cytosol of VSMCs, where it exhibits a "turn-off" fluorescence signal. Under oxLDL stimuli, the release of AIF from mitochondria into cytosol liberates the DNA hybrid structures from the surface of GO and results in a "turn-on" fluorescence signal. This nanosensor is shown to possess rapid response, high sensitivity, and selectivity for AIF that enables real-time imaging of AIF translocation in VSMCs. Using this novel nanosensor, a better assessment of the apoptotic level of VSMCs and a more accurate evaluation of the extent of atherosclerotic lesions can be obtained. More importantly, the abundant binding between DNA hybrid structures and AIF inhibits the translocation of AIF into the nucleus and subsequent apoptosis in VSMCs. This inhibition may help stabilize plaque and reduce the risk of heart attack and stroke.

Ultrathin two-dimensional inorganic materials: new opportunities for solid state nanochemistry.

CONSPECTUS: The ultimate goal of solid state chemistry is to gain a clear correlation between atomic, defect, and electronic structure and intrinsic properties of solid state materials. Solid materials can generally be classified as amorphous, quasicrystalline, and crystalline based on their atomic arrangement, in which crystalline materials can be further divided into single crystals, microcrystals, and nanocrystals. Conventional solid state chemistry mainly focuses on studying single crystals and microcrystals, while recently nanocrystals have become a hot research topic in the field of solid state chemistry. As more and more nanocrystalline materials have been artificially fabricated, the solid state chemistry for studying those nanosolids has become a new subdiscipline: solid state nanochemistry. However, solid state nanochemistry, usually called "nanochemistry" for short, primarily studies the microstructures and macroscopic properties of a nanomaterial's aggregation states. Due to abundant microstructures in the aggregation states, it is only possible to build a simple but imprecise correlation between the microscopic morphology and the macroscopic properties of the nanostructures. Notably, atomically thin two-dimensional inorganic materials provide an ideal platform to establish clear structure-property relationships in the field of solid state nanochemistry, thanks to their homogeneous dispersion without the assistance of a capping ligand. In addition, their atomic structures including coordination number, bond length, and disorder degree of the examined atoms can be clearly disclosed by X-ray absorption fine structure spectroscopy. Also, their more exposed interior atoms would inevitably induce the formation of various defects, which would have a non-negligible effect on their physicochemical properties. Based on the obtained atomic and defect structural characteristics, density-functional calculations are performed to study their electronic structures. Then, after the properties of the individual ultrathin two-dimensional materials or their assembled highly oriented thin film-based nanodevices are measured, the explicit relationship between atomic, defect, and electronic structure and intrinsic properties could be established. In this Account, we focus on our recent advances in the field of solid state nanochemistry, including atomic structure characterization of ultrathin two-dimensional inorganic materials by X-ray absorption fine structure spectroscopy, characterization of their different types of structural defects by positron annihilation spectra and electron spin resonance, and investigation of their electronic structure by density-functional calculations. In addition, we summarize the close correlation between atomic, defect, and electronic structure variations and the optoelectronic, electrical, magnetic, and thermal properties of ultrathin two-dimensional materials. Finally, we also propose the major challenges and opportunities that face solid state nanochemistry. We believe that all the past achievements in ultrathin two-dimensional materials could bring new opportunities for solid state nanochemistry.

Atomically-thin two-dimensional sheets for understanding active sites in catalysis.

Catalysis can speed up chemical reactions and it usually occurs on the low coordinated steps, edges, terraces, kinks and corner atoms that are often called "active sites". However, the atomic level interplay between active sites and catalytic activity is still an open question, owing to the large difference between idealized models and real catalysts. This stimulates us to pursue a suitable material model for studying the active sites-catalytic activity relationship, in which the atomically-thin two-dimensional sheets could serve as an ideal model, owing to their relatively simple type of active site and the ultrahigh fraction of active sites that are comparable to the overall atoms. In this tutorial review, we focus on the recent progress in disclosing the factors that affect the activity of reactive sites, including characterization of atomic coordination number, structural defects and disorder in ultrathin two-dimensional sheets by X-ray absorption fine structure spectroscopy, positron annihilation spectroscopy, electron spin resonance and high resolution transmission electron microscopy. Also, we overview their applications in CO catalytic oxidation, photocatalytic water splitting, electrocatalytic oxygen and hydrogen evolution reactions, and hence highlight the atomic level interplay among coordination number, structural defects/disorder, active sites and catalytic activity in the two-dimensional sheets with atomic thickness. Finally, we also present the major challenges and opportunities regarding the role of active sites in catalysis. We believe that this review provides critical insights for understanding the catalysis and hence helps to develop new catalysts with high catalytic activity.

Single Unit Cell Bismuth Tungstate Layers Realizing Robust Solar CO2 Reduction to Methanol.

Solar CO2 reduction into hydrocarbons helps to solve the global warming and energy crisis. However, conventional semiconductors usually suffer from low photoactivity and poor photostability. Here, atomically-thin oxide-based semiconductors are proposed as excellent platforms to overcome this drawback. As a prototype, single-unit-cell Bi2WO6 layers are first synthesized by virtue of a lamellar Bi-oleate intermediate. The single-unit-cell thickness allows 3-times larger CO2 adsorption capacity and higher photoabsorption than bulk Bi2WO6. Also, the increased conductivity, verified by density functional theory calculations and temperature-dependent resistivities, favors fast carrier transport. The carrier lifetime increased from 14.7 to 83.2 ns, revealed by time-resolved fluorescence spectroscopy, which accounts for the improved electron-hole separation efficacy. As a result, the single-unit-cell Bi2WO6 layers achieve a methanol formation rate of 75 µmol g(-1) h(-1), 125-times higher than that of bulk Bi2WO6. The catalytic activity of the single-unit-cell layers proceeds without deactivation even after 2 days. This work will shed light on designing efficient and robust photoreduction CO2 catalysts.

Metallic single-unit-cell orthorhombic cobalt diselenide atomic layers: robust water-electrolysis catalysts.

The bottleneck in water electrolysis lies in the kinetically sluggish oxygen evolution reaction (OER). Herein, conceptually new metallic non-metal atomic layers are proposed to overcome this drawback. Metallic single-unit-cell CoSe2 sheets with an orthorhombic phase are synthesized by thermally exfoliating a lamellar CoSe2 -DETA hybrid. The metallic character of orthorhombic CoSe2 atomic layers, verified by DFT calculations and temperature-dependent resistivities, allows fast oxygen evolution kinetics with a lowered overpotential of 0.27 V. The single-unit-cell thickness means 66.7 % of the Co(2+) ions are exposed on the surface and serve as the catalytically active sites. The lowered Co(2+) coordination number down to 1.3 and 2.6, gives a lower Tafel slope of 64 mV dec(-1) and higher turnover frequency of 745 h(-1) . Thus, the single-unit-cell CoSe2 sheets have around 2 and 4.5 times higher catalytic activity compared with the lamellar CoSe2 -DETA hybrid and bulk CoSe2 .

Atomic-Layer-Confined Doping for Atomic-Level Insights into Visible-Light Water Splitting.

A model of doping confined in atomic layers is proposed for atomic-level insights into the effect of doping on photocatalysis. Co doping confined in three atomic layers of In2S3 was implemented with a lamellar hybrid intermediate strategy. Density functional calculations reveal that the introduction of Co ions brings about several new energy levels and increased density of states at the conduction band minimum, leading to sharply increased visible-light absorption and three times higher carrier concentration. Ultrafast transient absorption spectroscopy reveals that the electron transfer time of about 1.6 ps from the valence band to newly formed localized states is due to Co doping. The 25-fold increase in average recovery lifetime is believed to be responsible for the increased of electron-hole separation. The synthesized Co-doped In2S3 (three atomic layers) yield a photocurrent of 1.17 mA cm(-2) at 1.5 V vs. RHE, nearly 10 and 17 times higher than that of the perfect In2S3 (three atomic layers) and the bulk counterpart, respectively.

Oxygen vacancies confined in ultrathin indium oxide porous sheets for promoted visible-light water splitting.

Finding an ideal model for disclosing the role of oxygen vacancies in photocatalysis remains a huge challenge. Herein, O-vacancies confined in atomically thin sheets is proposed as an excellent platform to study the O-vacancy-photocatalysis relationship. As an example, O-vacancy-rich/-poor 5-atom-thick In2O3 porous sheets are first synthesized via a mesoscopic-assembly fast-heating strategy, taking advantage of an artificial hexagonal mesostructured In-oleate complex. Theoretical/experimental results reveal that the O-vacancies endow 5-atom-thick In2O3 sheets with a new donor level and increased states of density, hence narrowing the band gap from the UV to visible regime and improving the carrier separation efficiency. As expected, the O-vacancy-rich ultrathin In2O3 porous sheets-based photoelectrode exhibits a visible-light photocurrent of 1.73 mA/cm(2), over 2.5 and 15 times larger than that of the O-vacancy-poor ultrathin In2O3 porous sheets- and bulk In2O3-based photoelectrodes.

Ultrahigh energy density realized by a single-layer ß-Co(OH)2 all-solid-state asymmetric supercapacitor.

A conceptually new all-solid-state asymmetric supercapacitor based on atomically thin sheets is presented which offers the opportunity to optimize supercapacitor properties on an atomic level. As a prototype, ß-Co(OH)2 single layers with five-atoms layer thickness were synthesized through an oriented-attachment strategy. The increased density-of-states and 100 % exposed hydrogen atoms endow the ß-Co(OH)2 single-layers-based electrode with a large capacitance of 2028 F g(-1) . The corresponding all-solid-state asymmetric supercapacitor achieves a high cell voltage of 1.8 V and an exceptional energy density of 98.9 Wh kg(-1) at an ultrahigh power density of 17 981 W kg(-1) . Also, this integrated nanodevice exhibits excellent cyclability with 93.2 % capacitance retention after 10 000 cycles, holding great promise for constructing high-energy storage nanodevices.