Effective utilization of abundant solar energy for desalination of seawater and purification of wastewater is one of sustainable techniques for production of clean water, helping relieve global water resource shortage. Herein, we fabricate a vertically aligned reduced graphene oxide/Ti3C2Tx MXene (A-RGO/MX) hybrid hydrogel with aligned channels as an independent solar steam generation device for highly efficient solar steam generation. The vertically aligned channels, generated by a liquid nitrogen-assisted directional-freezing process, not only rapidly transport water upward to the evaporation surface for efficient solar steam generation, but also facilitate multiple reflections of solar light inside the channels for efficient solar light absorption. The deliberate slight reduction endows the RGO with plenty of polar groups, decreasing the water vaporization enthalpy effectively and hence accelerating water evaporation efficiently. The MXene sheets, infiltrated inside the A-RGO hydrogel on the basis of Marangoni effect, enhance light absorption capacity and photothermal conversion performance. As a result, the A-RGO/MX hybrid hydrogel achieves a water evaporation rate of 2.09 kg·m−2·h−1 with a high conversion efficiency of 93.5% under 1-sun irradiation. Additionally, this photothermal conversion hydrogel rapidly desalinates seawater and purifies wastewater to generate clean water with outstanding ion rejection rates of above 99% for most ions.
Aqueous rechargeable batteries are a possible strategy for large-scale energy storage systems. However, limited choices of anode materials restrict their further application. Here we report phenazine (PNZ) as stable anode materials in different alkali-ion (Li+, Na+, K+) electrolyte. A novel full cell is assembled by phenazine anode, Na0.44MnO2 cathode and 10 M NaOH electrolyte to further explore the electrochemical performance of phenazine anode. This battery is able to achieve high capacity (176.7 mAh·g?1 at 4 C (1.2·Ag?1)), ultralong cycling life (capacity retention of 80% after 13,000 cycles at 4 C), and excellent rate capacity (92 mAh·g?1 at 100 C (30 A·g?1)). The reaction mechanism of PNZ during charge—discharge process is demonstrated by in situ Raman spectroscopy, in situ Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Furthermore, the system is able to successfully operate at wide temperature range from ?20 to 70 °C and achieves remarkable electrochemical performance.
Carbon coating has been a routine strategy for improving the performance of Si-based anode materials for lithium-ion batteries. The ability to tailor the thickness, homogeneity and graphitization degree of carbon-coating layers is essential for addressing issues that hamper the real applications of Si anodes. Herein, we report the construction of two-dimensional (2D) assemblies of interconnected Si@graphitic carbon yolk-shell nanoparticles (2D-Si@gC) from commercial Si powders by exploiting oleic acid (OA). The OA molecules act as both the surface-coating ligands for facilitating 2D nanoparticle assembly and the precursor for forming uniform and conformal graphitic shells as thin as 4 nm. The as-prepared 2D-Si@gC with rationally designed void space exhibits excellent rate capability and cycling stability when used as anode materials for lithium-ion batteries, delivering a capacity of 1,150 mAh·g−1 at an ultrahigh current density of 10 A·g−1 and maintaining a stabilized capacity of 1,275 mAh·g−1 after 200 cycles at 4 A·g−1. The formation of yolk-shell nanoparticles confines the deposition of solid electrolyte interphase (SEI) onto the outer carbon shell, while simultaneously providing sufficient space for volumetric expansion of Si nanoparticles. These attributes effectively mitigate the thickness variations of the entire electrode during repeated lithiation and delithiation, which combined with the unique 2D architecture and interconnected graphitic carbon shells of 2D-Si@gC contributes to its superior rate capability and cycling performance.
The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules. However, both thiolate-metal complex and electrostatic interaction are liable to detachment upon strong mechanical forces such as sonication, leading to limited stability and applications. To address this, we utilized ultrasmall water soluble melanin nanoparticles (MNPs) as the capping agent, which exhibited strong metal binding capability with the oxide layer of gallium based LMs and resulted in enhanced stability. Interestingly, shape-controlled synthesis of LM nanodroplets can be achieved by the incorporation of MNPs. Various EGaIn nanostructures including nanorice, nanosphere and nanorod were obtained by simply tuning the feed ratio, sonication time, and suspension temperature. Among these shapes, EGaIn nanorice has the best photothermal conversion efficiency, which could be leveraged for photothermal therapy.
A novel tri-layer approach for immobilizing metal nanoparticles in SiO2 supports is presented. In this work, we show that under rapid heating to temperatures of approximately 1,000 °C, metal nanoparticles less than 15 nm in size will entrench in the SiO2 layer on a silicon wafer to create pores as deep as 250 nm. We studied and characterized this entrenching behavior and subsequent nanopore formation for a wide variety of metal nanoparticles, including Au, Ag, Pt, Pd, and Cu. We also demonstrate that an Al2O3 layer acts as a barrier to such pore formation. Thus, by creating a tri-layer architecture consisting of SiO2 on Al2O3 on silicon wafers, we can control the depth to which nanoparticles entrench between 3–5 nm. This small range allows one to entrench particles for the purpose of immobilization but still present them above the surface. The two advances of moving into the sub-15 nm size regime and of controlled particle immobilization through entrenchment have important implications in studying site-isolated and stabilized metal nanoparticles for applications in sensing, separations, and catalysis.
Electronic sensors based on biomaterials can lead to novel green technologies that are low cost, renewable, and eco-friendly. Here we demonstrate bioelectronic ammonia sensors made from protein nanowires harvested from the microorganism Geobacter sulfurreducens. The nanowire sensor responds to a broad range of ammonia concentrations (10 to 106 ppb), which covers the range relevant for industrial, environmental, and biomedical applications. The sensor also demonstrates high selectivity to ammonia compared to moisture and other common gases found in human breath. These results provide a proof-of-concept demonstration for developing protein nanowire based gas sensors for applications in industry, agriculture, environmental monitoring, and healthcare.
A diverse range of remarkable boron nitride (BN) nanostructures subsuming nano-horns, nano-rods, nano-platelets, and clusters of hollow nanospheres (nano-onions, arguably of greatest applied and fundamental interest) have been produced exclusively from crystalline BN precursor powder via lamp ablation. The procedure is safe, devoid of toxic reagents, simple, rapid and scalable—generating some genres of nanoparticles that had previously proved elusive. Product structure and composition were unambiguously assessed by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy.
Two-dimensional (2D) nanomaterials have attracted a great deal of attention since the discovery of graphene in 2004, due to their intriguing physicochemical properties and wide-ranging applications in catalysis, energy-related devices, electronics and optoelectronics. To maximize the potential of 2D nanomaterials for their technological applications, controlled assembly of 2D nanobulding blocks into integrated systems is critically needed. This mini review summarizes the reported strategies of 2D materials-based assembly into integrated functional nanostructures, from in-situ assembly method to post-synthesis assembly. The applications of 2D assembled integrated structures are also covered, especially in the areas of energy, electronics and sensing, and we conclude with discussion on the remaining challenges and potential directions in this emerging field.
Anisotropic two-dimensional (2D) materials exhibit lattice-orientation dependent optical and electrical properties. Carriers doping of such materials has been used to modulate their energy band structures for opto-electronic applications. Herein, we show that by stacking monolayer rhenium disulfide (ReS2) on a flat gold film, the electrons doping in ReS2 can affect the in-plane anisotropic Raman enhancement of molecules adsorbed on ReS2. The change of enhancement factor and the degree of anisotropy in enhancement with layer number are sensitively dependent on the doping level of ReS2 by gold, which is further confirmed by Kelvin probe force microscopy (KPFM) measurements. These findings could open an avenue for probing anisotropic electronic interactions between molecules and 2D materials with low symmetry using Raman enhancement effect.
The electrochemical nitrogen reduction reaction (NRR) as an energy-efficient approach for ammonia synthesis is hampered by the low ammonia yield and ambiguous reaction mechanism. Herein, phosphorus-doped carbon nanotube (P-CNTs) is developed as an efficient metal-free electrocatalyst for NRR with a remarkable NH3 yield of 24.4 μg·h−1·mg−1cat. and partial current density of 0.61 mA·cm−2. Such superior activity is found to be from P doping and highly conjugated CNTs substrate. Experimental and theoretical investigations discover that the electron-deficient phosphorus sites with Lewis acidity should be genuine active sites and NRR on P-CNTs follows the distal pathway. These findings provide insightful understanding on NRR processes on P-CNTs, opening up opportunities for the rational design of highly-active cost-effective metal-free catalysts for electrochemical ammonia synthesis.
Sub-stoichiometric MoO3−x nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications. However, the synthesis of one-dimensional (1D) plasmonic MoO3−x nanostructures with widely tunable plasmonic absorption has remained a significant challenge because of their serious morphological destruction and phase change with increasing the concentration of oxygen vacancies. Here we demonstrate a surface-ligand protected reduction strategy for the synthesis of 1D MoO3−x nanobelts with tunable plasmonic absorption in a wide wavelength range from 200 to 2,500 nm. Polyethylene glycol (PEG-400) is used as both the reductant to produce oxygen vacancies and the surface protected ligands to maintain 1D morphology during the formation process of MoO3−x nanobelts, enabling the widely tunable plasmonic absorption. Owing to their broad plasmonic absorption and unique 1D nanostructure, we further demonstrate the application of 1D MoO3−x nanobelts as photothermal film for interfacial solar evaporator. The surface-ligand protected reduction strategy provides a new avenue for the developing plasmonic semiconductor oxides with maintained particle morphology and thus enriching their wide applications.
Oligo(p-phenyleneethynylene)s (OPEs) end-capped with (alkynyl)bis(diphosphine)ruthenium and thiol/thiolate groups stabilize ca. 2 nm diameter gold nanoparticles (AuNPs). The morphology, elemental composition and stability of the resultant organometallic OPE/AuNP hybrid materials have been defined using a combination of molecular- and nano-material chacterization techniques. The hybrids display long-term stability in solution (more than a month), good solubility in organic solvents, reversible ruthenium-centered oxidation, and transparency beyond 800 nm, and possess very strong nonlinear absorption activity at the first biological window, and unprecedented two-photon absorption activity in the second biological window (σ2 up to 38,000 GM at 1,050 nm).
The capability of preparing three-dimensional (3D) printable living inks provides a unique way to harness the activity of microbes and use them in functional devices. Here we demonstrate the incorporation of the living bacteria Shewanella Oneidensis MR-1 (S. Oneidensis MR-1) directly into an ink used for creating 3D printed structures. Significantly, S. Oneidensis MR-1 survives the 3D printing process by showing prominent activity in degrading the methyl orange azo dye. Through the addition of carbon black to this ink, we further demonstrate the direct printing of a living microbial fuel cell (MFC) anode. To our knowledge, this is the first report on implementing 3D printed bacteria structure as a living electrode for an MFC system. The capability of printing living and functional 3D bacterial structure could open up new possibilities in design and fabrication of microbial devices as well as fundamental research on the interaction between different bacterial strains, electrode materials, and surrounding environments.
Highly active, durable and inexpensive oxygen evolution reaction (OER) catalysts are crucial for achieving practical and high-efficiency water splitting. Herein, hierarchical interconnected NixCo1−xOOH nanosheet arrays supported on TiO2/Ti substrate have been fabricated through a facile photodeposition method. Compared with pristine NiOOH, the obtained NixCo1−xOOH nanosheet arrays possess larger exposed electrochemical active surface area, faster transfer and collection of electrons and stronger electronic interaction, showing a low overpotential of 350 mV at a current density of 10 mA·cm−2 and a small Tafel slope of 41 mV·dec−1 in basic solutions, with the OER performance superior to pristine NiOOH and most Ni-based catalysts. Furthermore, the NixCo1−xOOH electrode demonstrates excellent stability at the current density of 10 mA·cm−2 for 24 hours, which is attributed to the structural maintenance caused by the good adhesion of the catalyst and the substrate. Our study provides an alternative approach for the rational design of highly active and promising OER electrocatalysts.
Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm2 in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr2O3. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.
Energy and environmental issues presently attract a great deal of scientific attention. Recently, two-dimensional MXenes and MXene-based nanomaterials have attracted increasing interest because of their unique properties (e.g., remarkable safety, a very large interlayer spacing, environmental flexibility, a large surface area, and thermal conductivity). In 2011, multilayered MXenes (Ti3C2Tx, a new family of two-dimensional (2D) materials) produced by etching an A layer from a MAX phase of Ti3AlC2, were first described by researchers at Drexel University. The term “MXene” was coined to distinguish this new family of 2D materials from graphene, and applies to both the original MAX phases and MXenes fabricated from them. We present a comprehensive review of recent studies on energy and environmental applications of MXene and MXene-based nanomaterials, including energy conversion and storage, adsorption, membrane, photocatalysis, and antimicrobial. Future research needs are discussed briefly with current challenges that must be overcome before we completely understand the extraordinary properties of MXene and MXene-based nanomaterials.
In the present work, we report the growth of all-inorganic perovskite nanorings with dual compositional phases of CsPbBr3 and CsPb2Br5 via a facile hot injection process. The self-coiling of CsPbBr3-CsPb2Br5 nanorings is driven by the axial stress generated on the outside surface of the as-synthesized nanobelts, which results from the lattice mismatch during the transformation of CsPbBr3 to CsPb2Br5. The tailored growth of nanorings could be achieved by adjusting the key experimental parameters such as reaction temperature, reaction time and stirring speed during the cooling process. The photoluminescence intensity and quantum yield of nanorings are higher than those of CsPbBr3 nanobelts, accompanied by a narrower full width at half maximum (FWHM), suggesting their high potential for constructing self-assembled optoelectronic nanodevices.
Subtle structural changes during electrochemical processes often relate to the degradation of electrode materials. Characterizing the minute-variations in complementary aspects such as crystal structure, chemical bonds, and electron/ion conductivity will give an in-depth understanding on the reaction mechanism of electrode materials, as well as revealing pathways for optimization. Here, vanadium pentoxide (V2O5), a typical cathode material suffering from severe capacity decay during cycling, is characterized by in-situ X-ray diffraction (XRD) and in-situ Raman spectroscopy combined with electrochemical tests. The phase transitions of V2O5 within the 0–1 Li/V ratio are characterized in detail. The V–O and V–V distances became more extended and shrank compared to the original ones after charge/discharge process, respectively. Combined with electrochemical tests, these variations are vital to the crystal structure cracking, which is linked with capacity fading. This work demonstrates that chemical bond changes between the transition metal and oxygen upon cycling serve as the origin of the capacity fading.