Synthesis of Graphdiyne Hollow Spheres and Multiwalled Nanotubes and Applications in Water Purification and Raman Sensing.

Controlling the structure of graphdiyne (GDY) is crucial for the discovery of new properties and the development of new applications. Herein, the microemulsion synthesis of GDY hollow spheres (HSs) and multiwalled nanotubes composed of ultrathin nanosheets is reported for the first time. The formation of an oil-in-water (O/W) microemulsion is found to be a key factor controlling the growth of GDY. These GDY HSs have fully exposed surfaces because of the avoidance of overlapping between nanosheets, thereby showing an ultrahigh specific surface area of 1246 m2 g-1 and potential applications in the fields of water purification and Raman sensing.

Exploring the Fate of Copper Ions in the Synthesis of Graphdiyne.

Copper is a crucial catalyst in the synthesis of graphdiyne (GDY). However, as catalysts, the final fate of the copper ions has hardly been concerned, which are usually treated as impurities. Here, it is observed that after simple washing with water and ethanol, GDY still contains a certain amount of copper ions, and demonstrated that the copper ions are adsorbed at the atomic layers of GDY. Furthermore, we transformed in situ the copper ions into ultrathin Cu nanocrystals, and the obtained Cu/GDY hybrids can be generally converted into a series of metal/GDY hybrid materials, such as Ag/GDY, Au/GDY, Pt/GDY, Pd/GDY, and Rh/GDY. The Cu/GDY hybrids exhibit extraordinary surface enhanced Raman scattering effect and can be applied in pollutant efficient enrichment and detection.

Heteropolyacids: An Ultrasensitive Ionic Volume-Enhanced Raman Scattering Platform.

Surface-enhanced Raman scattering (SERS) is regarded as the most direct and powerful tool to identify chemical fingerprints. However, current SERS substrate materials still face some critical challenges, including low molecular utilization efficiency and low selectivity. Herein, a novel oxygen vacancy heteropolyacid─H10Fe3Mo21O51 (HFMO)─is developed as a high-performance volume-enhanced Raman scattering (VERS)-active platform. Due to its merit of water solubility, HFMO forms a special coordination bond with the probe molecule at the molecular level, which allows its enhancing ability to be comparable to that of noble metals. An enhancement factor of 1.26 × 109 and a very low detection limit of 10-13 M for rhodamine 6G were obtained. A robust O-N coordination bond was formed between the anion of HFMO and the probe molecule, resulting in a special electron transfer path (Mo-O-N) with high selectivity, which is verified using X-ray photoelectron spectroscopy analysis and density functional theory calculations. That is to say, the proposed HFMO platform has excellent VERS enhancing effect, specifically for the molecules containing the imino group (e.g., methyl blue, detection limit: 10-11 M), offering the merits of high reproducibility and uniformity, high-temperature resistance, long-time laser irradiation, and strong acid resistance. Such an initial effort on the ionic type VERS platform may enable the further development of highly sensitive, highly selective, and water-soluble VERS technology.

Ultrathin Graphdiyne Nanowires with Diameters below 3 nm: Synthesis, Photoelectric Effect, and Enhanced Raman Sensing.

Due to the intrinsic layered structure, graphdiyne (GDY) strongly tends to form 2D materials, therefore, most of the current research are based on GDY 2D structures. Up to now, the synthesis of its ultrathin nanowires with a high aspect ratio has not been reported. Here, the ultrathin GDY nanowires with diameters below 3 nm are reported for the first time by a two-phase interface synthesis method, which has excellent crystallinity and an aspect ratio of more than 2500. Evidence shows that the GDY ultrathin nanowires are formed by the oriented-attachment mechanism of nanoparticles. The GDY ultrathin nanowires exhibit a significant quantum confinement effect, enhanced photoelectric effect, and promising applications in surface-enhanced Raman sensing.

A Metallic Niobium Nitride with Open Nanocavities for Surface-Enhanced Raman Spectroscopy.

The construction of open hot-spot structures that facilitate the entry of analytes is crucial for surface-enhanced Raman spectroscopy. Here, metallic niobium nitride (NbN) three-dimensional (3D) hierarchical networks with open nanocavity structure are first found to exhibit a strong visible-light localized surface plasmon resonance (LSPR) effect and extraordinary surface-enhanced Raman scattering (SERS) performance. The unique nanocavity structure allows easy entry of molecules, promoting the utilization of electromagnetic hot spots. The NbN substrate has a lowest detection limit of 1.0 × 10-12 M and a Raman enhancement factor (EF) of 1.4 × 108 for contaminants. Furthermore, the NbN hierarchical networks possess outstanding environmental durability, high signal reproducibility, and detection universality. The remarkable SERS sensitivity of the NbN substrate can be attributed to the joint effect of LSPR and interfacial charge transport (CT).

Directly Convert Carbonaceous Microspheres to Three-Dimensional Porous Carbon Microspheres with a Robust Self-Supporting Structure as a Metal-Free SERS Substrate for Online High-Throughput Analysis.

It is of great significance for practical applications to directly convert readily available biomass carbon into three-dimensional (3D) porous carbon microspheres with a self-supporting structure. Herein, we report the convenient conversion of biomass carbon microspheres to hierarchical porous carbon microspheres (HP-CMSs) with a robust self-supporting framework structure. A general SiO2-induced etching mechanism is proposed for the formation of the HP-CMSs. Benefiting from this robust 3D self-supporting frame structure, these HP-CMSs have outstanding mechanical, chemical, and thermal stability. As a metal-free surface-enhanced Raman scattering (SERS) substrate with an ultrahigh specific surface area (4216 m2 g-1) and a high density of active sites, the HP-CMSs exhibit high sensitivity with a detection limit of 10-10 M and a Raman enhancement factor of 3.5 × 106. By integrating the enrichment and sensing functions of the HP-CMSs in a microfluidic channel, online high-throughput SERS detection of 20 samples within 5 min is achieved in a single channel, and the relative standard deviation of the signals between samples is only 5.1%. The current work develops a convenient preparation method that converts sustainable biomass carbon to 3D hierarchical porous carbon and provides a potential material for sensing, energy, catalysis, and other fields.

Moving MoO2/C Nanospheres with the Functions of Enrichment and Sensing for Online-High-Throughput SERS Detection.

The development of online surface-enhanced Raman spectroscopy (SERS) detection methods is crucial to achieving high-throughput efficiency. Herein, a non-noble-metal moving substrate that integrates the functions of enrichment and sensing is developed for the microfluidic online-high-throughput detection of pollutants. The lowest limit of detection of 1 × 10-12 M and a Raman enhancement factor of 6.3 × 108 are obtained on the nanospheres. In a single detection channel, the analysis of 20 samples is achieved within 5 min, and the relative standard deviation of the signals is less than 6.8%. Compared with static SERS detection of fixed substrates, this dynamic SERS detection method greatly reduces the contamination memory effect of the analyte residue, enabling it to perform the sequential quantitative detection of samples with large concentration differences. Moreover, the current online SERS platform realizes the rapid quantitative detection of multicomponent samples.

Selective Preparation of Mo2N and MoN with High Surface Area for Flexible SERS Sensing.

γ-Mo2N and δ-MoN are the two most important molybdenum nitrides, but controllable preparation of them with high surface area has not been achieved. Herein, we achieved selective preparation of γ-Mo2N and δ-MoN. The key factor for the selective preparation of γ-Mo2N and δ-MoN is to control the crystal phase of the precursor MoO3. In H2O and NH3 mixed gas, the α-MoO3 nanoribbons are nitridated to obtain γ-Mo2N single-crystal porous nanobelts, while the h-MoO3 prisms are nitrided to obtain δ-MoN hierarchical porous columns. The corrosion effect of H2O plays a key role in the formation of single-crystal porous structure. The γ-Mo2N flexible membrane composed of the single-crystal porous nanobelts exhibits strong localized surface plasmon resonance and surface enhanced Raman scattering effect, which show highly sensitive response to polychlorinated phenol.

General Microwave Route to Single-Crystal Porous Transition Metal Nitrides for Highly Sensitive and Stable Raman Scattering Substrates.

The synthesis of metallic transition metal nitrides (TMNs) has traditionally been performed under harsh conditions, which makes it difficult to prepare TMNs with high surface area and porosity due to the grain sintering. Herein, we report a general and rapid (30 s) microwave synthesis method for preparing TMNs with high specific surface area (122.6-141.7 m2 g-1) and porosity (0.29-0.34 cm3 g-1). Novel single-crystal porous WN, Mo2N, and V2N are first prepared by this method, which exhibits strong surface plasmon resonance, photothermal conversion, and surface-enhanced Raman scattering effects. Different from the conventional low-temperature microwave absorbing media such as water and polymers, as new concept absorbing media, hydrated metal oxides and metallic metal oxides are found to have a remarkable high-temperature microwave heating effect and play key roles in the formation of TMNs. The current research results provide a new-concept microwave method for preparing high lattice energy compounds with high specific surface.

δ-MoN Yolk Microspheres with Ultrathin Nanosheets for a Wide-Spectrum, Sensitive, and Durable Surface-Enhanced Raman Scattering Substrate.

Facing the complex environment of on-site detection, the development of active substrates with wide-spectrum surface-enhanced Raman scattering (SERS) activity is essential. Herein, we report on the low temperature and reproducible synthesis of plasmonic δ-MoN yolk microspheres by in situ-nitriding amorphous MoO2 microspheres at 500 °C and 1 atm. The yolk-structured δ-MoN exhibits strong and wide-spectrum surface plasmon resonance and SERS effects and can perform highly selective detection for probes with different absorption wavelengths under excitation of 532, 633, and 785 nm lasers, with a limitation of 10-11 M and an enhanced factor of 3.6 × 107. Moreover, the plasmonic δ-MoN yolk microspheres have high environmental durability, which can maintain high sensitivity in strong acid and alkaline solutions.

Highly Sensitive W18O49 Mesocrystal Raman Scattering Substrate with Large-Area Signal Uniformity.

Although mesocrystals with ordered building units have great potential in many fields because of the large amount of organic molecules used as structure-directing agents during their synthesis process, severe matrix interference makes their surface-enhanced Raman scattering (SERS) properties rarely understood. Herein, a rapid (20 s) and green microwave synthetic route is developed for the 100 g scale preparation of plasmonic W18O49 mesocrystals with no additives. The ultrathin (1.5 nm) and oxygen vacancy-rich W18O49 nanowires as a building unit greatly improve the interface charge transfer, while the periodic mesocrystal structure significantly enhances the localized surface plasmon resonance effect and creates high-density electromagnetic hot spots among the nanowires. An outstanding enhancement factor of 1.2 × 107 and an ultralow detectable limit of 10-11 M are achieved, and the single-molecule imaging is also realized on this mesocrystal-based SERS substrate. Moreover, the relative standard deviation of the fabricated large-area (2.2 cm2) SERS substrate is only 6.8%.

Nitrogen-Doped Titanium Monoxide Flexible Membrane for a Low-Cost, Biocompatible, and Durable Raman Scattering Substrate.

The development of low-cost, biocompatible, and durable high-performance substrates is an urgent issue in the field of surface-enhanced Raman scattering (SERS). Herein, by reducing and exfoliating the TiO2-layered nanoplates in the gas phase, nitrogen-doped titanium monoxide (N-TiO) ultrathin nanosheets composed of 2-3 single layers with a thickness of only ∼1.2 nm are synthesized. Compared with pure TiO, the oxidation resistance of N-TiO is greatly improved, in which the oxidation threshold is significantly increased from 187.5 to 415.6 °C. The N-TiO ultrathin nanosheets are found to have strong surface plasmon resonance in the visible region. These ultrathin N-TiO nanosheets can be easily assembled into a large-scale flexible membrane and exhibit remarkable SERS effects. Moreover, this low-cost flexible SERS substrate combines the high durability of noble-metal substrates and the high biocompatibility of semiconductor substrates.

Alternative to Noble Metal Substrates: Metallic and Plasmonic Ti3O5 Hierarchical Microspheres for Surface Enhanced Raman Spectroscopy.

Compared with noble metals, improving the sensitivity of semiconducting surface-enhanced Raman scattering (SERS) substrates is of great significance to their fundamental research and practical application of Raman spectroscopy. In this paper, it is found that the SERS sensitivity is increased by 10 000 times by reducing the semiconducting TiO2 microspheres to quasi-metallic Ti3O5 microspheres. Its lowest detectable limit is up to 10-10 M, which may be the best among the non-noble metal substrates and even reaches or exceeds certain Au/Ag nanostructures to the best of our knowledge. This new type of non-noble metal SERS substrate breaks through the bottleneck of poor stability of conventional semiconductor substrate and can withstand high temperature oxidation at 200 °C and strong acid-base corrosion without performance degradation. Benefiting from its excellent ability of visible-light photocatalytic degradation of organic molecules, the substrate can be reused. Moreover, the new material also exhibits excellent photothermal conversion properties.

Plasmonic MoO2 Nanospheres as a Highly Sensitive and Stable Non-Noble Metal Substrate for Multicomponent Surface-Enhanced Raman Analysis.

Semiconductor-based surface-enhanced Raman spectroscopy is getting more and more attention because of its great price advantage. One of the biggest obstacles to the large-scale application of it is the poor stability. Here, we report that plasmonic MoO2 nanospheres can be used as a highly sensitive and stable semiconducting-substrate material for surface-enhanced Raman scattering (SERS). By using the MoO2 nanospheres as Raman substrates, a series of typical compounds with high attention can be accurately detected. This new non-noble metal substrate material shows a very high detection limit of 10-8 M, and exhibits great near-field enhancement with one of the highest enhancement factor of 4.8 × 106 reported to date. More importantly, the oxide with intermediate valence displays unexpected ultrahigh stability, which can withstand the corrosion of strong acid and strong alkali as well as 150 °C high temperature oxidation in air. Moreover, the accurate detection of multicomponent samples was also successful on this substrate. These results show that some simple metal oxides with intermediate valence may become sensitive and stable SERS substrate materials due to their abundant free electrons and structure that easily causes hot spots.

Au photosensitized TiO2 ultrathin nanosheets with {001} exposed facets.

We report a general route for the direct growth of metal particles on TiO2 nanosheets with (001) exposed facets by an oxygen-vacancy-driven self-redox reaction. As there is no need for thermal treatment to remove stabilizing agents, the structure of the nanoparticles can be retained, preserving the active sites associated with high activity.

[Identification of pearl powder using microscopic infrared reflectance spectroscopy].

Pearl is a precious ornament and traditional Chinese medicine, which application history in China is more than 2000 years. It is well known that the chemical ingredients of shell and pearl are very similar, which all of them including calcium carbonate and various amino acids. Generally, shell powders also can be used as medicine; however, its medicinal value is much lower than that of pearl powders. Due to the feature similarity between pearl powders and shell powders, the distinguishment of them by detecting chemical composition and morphology is very difficult. It should be noted that shell powders have been often posing as pearl powders in markets, which seriously infringes the interests of consumers. Identification of pearl powder was investigated by microscopic infrared reflectance spectroscopy, and pearl powder as well as shell powder was calcined at different temperatures for different time before infrared reflectance spectroscopy analysis. The experimental results indicated that when calcined at 400 °C for 30 minutes under atmospheric pressure, aragonite in pearl powder partly transformed into calcite, while aragonite in shell powder completely transformed into calcite. At the same time, the difference in phase transition between the pearl powders 'and shell powders can be easily detected by using the microscopic infrared reflectance spectroscopy. Therefore, based on the difference in their phase transition process, infrared reflectance spectroscopy can be used to identify phase transformation differences between pearl powder and shell powder. It's more meaningfully that the proposed infrared reflectance spec- troscopy method was also investigated for the applicability to other common counterfeits, such as oyster shell powders and abalone shell powders, and the results show that the method can be a simple, efficiently and accurately method for identification of pearl powder.

Surfactant-free interfacial growth of graphdiyne hollow microspheres and the mechanistic origin of their SERS activity.

As a two-dimensional carbon allotrope, graphdiyne possesses a direct band gap, excellent charge carrier mobility, and uniformly distributed pores. Here, a surfactant-free growth method is developed to efficiently synthesize graphdiyne hollow microspheres at liquid‒liquid interfaces with a self-supporting structure, which avoids the influence of surfactants on product properties. We demonstrate that pristine graphdiyne hollow microspheres, without any additional functionalization, show a strong surface-enhanced Raman scattering effect with an enhancement factor of 3.7 × 107 and a detection limit of 1 × 10-12 M for rhodamine 6 G, which is approximately 1000 times that of graphene. Experimental measurements and first-principles density functional theory simulations confirm the hypothesis that the surface-enhanced Raman scattering activity can be attributed to an efficiency interfacial charge transfer within the graphdiyne-molecule system.

Tungsten Nitride with a Two-Dimensional Multilayer Structure for Boosting the Surface-Enhanced Raman Effect.

The development of high-performance surface-enhanced Raman scattering (SERS) substrates is an urgent and important task. Here, tungsten nitride (WN) with a two-dimensional (2D) multilayer structure has been successfully prepared through a nitriding WO2.90 precursor. In addition to the highly active "hot spots" formed on the surface of the WN sheets, a large number of gaps between the nanosheets also exhibit a strong local surface plasmon resonance effect, which greatly improves the SERS activity. Evaluated as the SERS substrate, the WN with a 2D multilayer structure exhibits good SERS characteristics and good homogeneity and stability, even after strong acid, strong alkali, or long-term light treatment. Significantly, typical environmental contaminants such as dichlorophenol and butylated hydroxyanisole also exhibit strong Raman enhancement signals. This research provides a new method for designing inexpensive, high-activity, and universal SERS substrates.

Molecular assembly of carbon nitride-based composite membranes for photocatalytic sterilization and wound healing.

Polymeric carbon nitride (pCN) has attracted increasing interest as a metal-free photocatalyst because of its high efficiency in reactive oxygen species (ROS) generation. However, due to poor solubility, compounding pCN at the molecular level into more advanced nanocomposites remains a challenge. Herein, we report the dissolution of pCN in polyphosphoric acid (PPA) for the first time and fluid-phase assembly with carbon nanotubes (CNTs) into a flexible free-standing membrane. Mechanism and generality studies disclosed that the coordination of the acidity, viscosity, and adsorption energy of the solvents led to the successful dissolution of pCN. Interestingly, the pCN/CNTs molecular composite membrane exhibited not only superior mechanical properties and cycling performance as a result of strengthened π-π interfacial interaction, but also outstanding inactivation of E. coli and S. aureus in sterilization and wound healing for laboratory mice via photogenerated oxygen radicals. It would open a new era of pCN for biomedical applications in molecular composite membranes, beyond the traditional solar fuel applications in powders.

In situ growth of metal particles on 3D urchin-like WO3 nanostructures.

Metal/semiconductor hybrid materials of various sizes and morphologies have many applications in areas such as catalysis and sensing. Various organic agents are necessary to stabilize metal nanoparticles during synthesis, which leads to a layer of organic compounds present at the interfaces between the metal particles and the semiconductor supports. Generally, high-temperature oxidative treatment is used to remove the organics, which can extensively change the size and morphology of the particles, in turn altering their activity. Here we report a facile method for direct growth of noble-metal particles on WO(3) through an in situ redox reaction between weakly reductive WO(2.72) and oxidative metal salts in aqueous solution. This synthetic strategy has the advantages that it takes place in one step and requires no foreign reducing agents, stabilizing agents, or pretreatment of the precursors, making it a practical method for the controlled synthesis of metal/semiconductor hybrid nanomaterials. This synthetic method may open up a new way to develop metal-nanoparticle-loaded semiconductor composites.