Electrochemical reduction of carbon dioxide is one of the methods which have the capability to recycle CO2 into valuable products for energy and industrial applications. This research article describes about a new electrocatalyst “reduced graphene oxide supported gold nanoparticles” for selective electrochemical conversion of carbon dioxide to carbon monoxide. The main aim for conversion of CO2 to CO lies in the fact that the latter is an important component of syn gas (a mixture of hydrogen and carbon monoxide), which is then converted into liquid fuel via well-known industrial process called Fischer-Tropsch process. In this work, we have synthesized different composites of the gold nanoparticles supported on defective reduced graphene oxide to evaluate the catalytic activity of reduced graphene oxide (RGO)-supported gold nanoparticles and the role of defective RGO support towards the electrochemical reduction of CO2. Electrochemical and impedance measurements demonstrate that higher concentration of gold nanoparticles on the graphene support led to remarkable decrease in the onset potential of 240 mV and increase in the current density for CO2 reduction. Lower impedance and Tafel slope values also clearly support our findings for the better performance of RGOAu than bare Au for CO2 reduction.
In recent years, two-dimensional confined catalysis, i.e., the enhanced catalytic reactions in confined space between metal surface and two-dimensional overlayer, makes a hit and opens up a new way to enhance the performance of catalysts. In this work, graphdiyne overlayer was proposed as a more excellent material than graphene or hexagonal boron nitride for two-dimensional confined catalysis on Pt(111) surface. Density functional theory calculations revealed the superiority of graphdiyne overlayer originates from the steric hindrance effect which increases the catalytic ability and lowers the reaction barriers. Moreover, with the big triangle holes as natural gas tunnels, graphdiyne possesses higher efficiency for the transit of gaseous reactants and products than graphene or hexagonal boron nitride. The results in this work would benefit future development of two-dimensional confined catalysis.
Dendritic Pt–Cu nanoparticles were synthesized by a facile one-step method with the help of surfactant Brij58 at room temperature, and we also studied the effects of different Pt–Cu ratios on the morphology and size of nanoparticles. In addition, we further tuned the morphology of the Pt–Cu nanostructures by introducing bromide ions, eventually leading to the appearance of some tripod-like structures. Compared with dendritic Pt–Cu and commercial Pt black, these tripod-like Pt–Cu nanostructures exhibited higher electrocatalytic activity and CO tolerance for catalyzing methanol oxidation.
Novel feather duster-like nickel sulfide (NiS) @ molybdenum sulfide (MoS2) with hierarchical array structure is synthesized via a simple one-step hydrothermal method, in which a major structure of rod-like NiS in the center and a secondary structure of MoS2 nanosheets with a thickness of about 15–55 nm on the surface. The feather duster-like NiS@MoS2 is employed as the counter electrode (CE) material for the dye-sensitized solar cell (DSSC), which exhibits superior electrocatalytic activity due to its feather duster-like hierarchical array structure can not only support the fast electron transfer and electrolyte diffusion channels, but also can provide high specific surface area (238.19 m2 g?1) with abundant active catalytic sites and large electron injection efficiency from CE to electrolyte. The DSSC based on the NiS@MoS2 CE achieves a competitive photoelectric conversion efficiency of 8.58%, which is higher than that of the NiS (7.13%), MoS2 (7.33%), and Pt (8.16%) CEs under the same conditions.
Graphical abstract Novel feather duster-like NiS@MoS2 hierarchical structure array with superior electrocatalytic activity was fabricated by a simple one-step hydrothermal method.
Porous carbon monoliths have attracted great interest in many fields due to their easy availability, large specific surface area, desirable electronic conductivity, and tunable pore structure. In this work, hierarchical porous nitrogen-doped partial graphitized carbon monoliths (N–MC–Fe) with ordered mesoporous have been successfully synthesized by using resorcinol-formaldehyde as precursors, iron salts as catalyst, and mixed triblock copolymers as templates via a one-step hydrothermal method. In the reactant system, hexamethylenetetramine (HMT) is used as nitrogen source and one of the carbon precursors under hydrothermal conditions instead of using toxic formaldehyde. The N–MC–Fe show hierarchically porous structures, with interconnected macroporous and ordered hexagonally arranged mesoporous. Nitrogen element is in situ doped into carbon through decomposition of HMT. Iron catalyst is helpful to improve the graphitization degree and pore volume of N–MC–Fe. The synthesis strategy is user-friendly, cost-effective, and can be easily scaled up for production. As supercapacitors, the N–MC–Fe show good capacity with high specific capacitance and good electrochemical stability.
Graphical abstract Hierarchical porous nitrogen-doped partial graphitized carbon monoliths with ordered mesoporous have been successfully synthesized by using resorcinol-formaldehyde as precursors, iron as catalyst, and mixed triblock copolymers as templates via a one-step hydrothermal method.
Carbon-coated ZnFe2O4 spheres with sizes of ~110–180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g?1 and maintains a reversible capacity of 775 mAh g?1 after 150 cycles at a current density of 500 mA g?1. After being tested at 2 A g?1 for 700 cycles, the capacity still retains 617 mAh g?1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating (~3–6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe2O4 spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries.
In this study, a simple one-pot method was adopted to synthetize Pd/Pt core/shell nanostructures with truncated-octahedral morphology. The morphology of the obtained Pd/Pt nanoparticles was characterized by transmission electron microscopy (TEM) and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). In addition, the composition was determined by energy-dispersive X-ray spectroscopy (EDS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the electric structures were studied by powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Based on the above results, it could be noticed that Pd/Pt core/shell nanostructures with truncated-octahedral morphology were produced, where the core consisted of Pd atoms and the shell consisted of Pt atoms. In order to test the catalytic properties of the prepared Pd/Pt nanoparticles, cyclic voltammetry (CV) was carried out in 0.5 M H2SO4 and 0.5 M H2SO4 + 1 M HCOOH. Compared with commercial Pt black, the Pd/Pt core/shell nanostructures with truncated-octahedral morphology exhibited higher activity and stability toward formic acid oxidation.
Plasmonic metal nanoparticles have shown great promise in enhancing the light absorption of organic dyes and thus improving the performance of dye-sensitized solar cells (DSSCs). However, as the plasmon resonance of spherical nanoparticles is limited to a single wavelength maximum (e.g., ~ 520 nm for Au nanoparticles), we have here utilized silica-coated gold nanorods (Au@SiO2 NRs) to improve the performance at higher wavelengths as well. By adjusting the aspect ratio of the Au@SiO2 NRs, we can shift their absorption maxima to better match the absorption spectrum of the utilized dye (here we targeted the 600–800 nm range). The main challenge in utilizing anisotropic nanoparticles in DSSCs is their deformation during the heating step required to sinter the mesoporous TiO2 photoanode and we show that the Au@SiO2 NRs start to deform already at temperatures as low as 200 °C. In order to circumvent this problem, we incorporated the Au@SiO2 NRs in a TiO2 nanoparticle suspension that does not need high sintering temperatures to produce a functional photoanode. With various characterization methods, we observed that adding the plasmonic particles also affected the structure of the produced films. Nonetheless, utilizing this low-temperature processing protocol, we were able to minimize the structural deformation of the gold nanorods and preserve their characteristic plasmon peaks. This allowed us to see a clear redshift of the maximum in the incident photon-to-current efficiency spectra of the plasmonic devices (Δλ ~ 14 nm), which further proves the great potential of utilizing Au@SiO2 NRs in DSSCs.
In this study Pt, Re, and SnO2 nanoparticles (NPs) were combined in a controlled manner into binary and ternary combinations for a possible application for ethanol oxidation. For this purpose, zeta potentials as a function of the pH of the individual NPs solutions were measured. In order to successfully combine the NPs into Pt/SnO2 and Re/SnO2 NPs, the solutions were mixed together at a pH guaranteeing opposite zeta potentials of the metal and oxide NPs. The individually synthesized NPs and their binary/ternary combinations were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) analysis. FTIR and XPS spectroscopy showed that the individually synthesized Pt and Re NPs are metallic and the Sn component was oxidized to SnO2. STEM showed that all NPs are well crystallized and the sizes of the Pt, Re, and SnO2 NPs were 2.2, 1.0, and 3.4 nm, respectively. Moreover, EDS analysis confirmed the successful formation of binary Pt/SnO2 and Re/SnO2 NP, as well as ternary Pt/Re/SnO2 NP combinations. This study shows that by controlling the zeta potential of individual metal and oxide NPs, it is possible to assemble them into binary and ternary combinations.
Preparation, characterization, and electrocatalytic study of the electrodeposited Pt and Pd (e.g., Pt and PtPd) catalysts on titanium dioxide (TiO2) modified reduced graphene oxide (rGO) support for formic acid oxidation were performed. The catalyst composites are labeled as xPt/rGO-TiO2, xPtyPd/rGO-TiO2, and yPd/rGO-TiO2 where x and y are cycle numbers of metal electrodeposition (x and y?=?2–6). The characterizations of the catalysts were performed by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Small and dispersed metal nanoparticles are obtained on rGO-TiO2. The catalytic performances for formic acid oxidation were measured by cyclic voltammetry (CV) and chronoamperometry (CA). The electrocatalytic results reveal that the bimetallic 4Pt2Pd/rGO-TiO2 catalyst facilitates formic acid oxidations at the lowest potentials and generates the highest oxidation currents and also improves the highest CO oxidation compared to the monometallic 6Pt/rGO-TiO2 catalyst. According to the experimental data, the Pd and TiO2 enhance the electrocatalytic activity of the catalysts towards the formic acid oxidation; the improved catalytic performance of the prepared catalysts strongly relates to the high electrochemically active surface area (ECSA) investigated.
Ruthenium/reduced graphene oxide nanocomposites (Ru/rGO NCs) were synthesized via an electrostatic self-assembly approach. Polyvinylpyrrolidone (PVP) stabilized and positively charged metallic ruthenium nanoclusters about 1.2 nm were synthesized and uniformly loaded onto negatively charged graphene oxide (GO) sheets via strong electrostatic interactions. The as-prepared Ru/rGO NCs exhibited superior performance in catalytic hydrolysis of sodium borohydride (NaBH4) to generate H2. The hydrogen generation rate was up to 14.87 L H2 min?1 gcat?1 at 318 K with relatively low activation energy of 38.12 kJ mol?1. Kinetics study confirmed that the hydrolysis of NaBH4 was first order with respect to concentration of catalysts. Besides, the conversion of NaBH4 remained at 97% and catalytic activity retained more than 70% after 5 reaction cycles at room temperature. These results suggested that the Ru/rGO NCs have a promising prospect in the field of clean energy.
Tin-based composites are promising high-capacity anode materials for Li-ion batteries, but they usually exhibit poor cycling stability because of their large volume expansion during the Li uptake and release process. We reported a facile solvothermal method to produce nanosheet-assembled SnS microspheres and a rational strategy to improve the electrochemical performance of SnS microspheres by anchoring on reduced graphene oxide (RGO) networks. The as-prepared SnS/RGO nanocomposites were characterized by XRD, SEM, TEM, TGA, and Raman spectra. The electrochemical results show that the SnS/RGO electrode exhibited high reversible capacity and good cycling stability (delivered a capacity of 760 mAh g?1 after 100 cycles at a current density of 100 mA g?1). The superior electrochemical performance can be attributed to the large available surface area, high conductivity, and fast transportation of electrons and Li-ions; these are benefited from the unique hybrid structure and the synergistic effect between SnS and RGO.
Graphical AbstractTOC Anode materials of nanosheet-assembled SnS microspheres anchored with RGO sheets have been simply synthesized via a facile solvothermal route and subsequently RGO anchoring. When used as the anode for Li-ion batteries, they show a high specific capacity of 760 mA h g?1 after 100 cycles at the current density of 100 mA g?1.
A simple solid-state method has been applied to synthesize Ni/reduced graphene oxide (Ni/rGO) nanocomposite under ambient condition. Ni nanoparticles with size of 10–30 nm supported on reduced graphene oxide (rGO) nanosheets are obtained through one-pot solid-state co-reduction among nickel chloride, graphene oxide, and sodium borohydride. The Ni/rGO nanohybrid shows enhanced catalytic activity toward the reduction of p-nitrophenol (PNP) into p-aminophenol compared with Ni nanoparticles. The results of kinetic research display that the pseudo-first-order rate constant for hydrogenation reaction of PNP with Ni/rGO nanocomposite is 7.66 × 10?3 s?1, which is higher than that of Ni nanoparticles (4.48 × 10?3 s?1). It also presents superior turnover frequency (TOF, 5.36 h?1) and lower activation energy (Ea, 29.65 kJ mol?1) in the hydrogenation of PNP with Ni/rGO nanocomposite. Furthermore, composite catalyst can be magnetically separated and reused for five cycles. The large surface area and high electron transfer property of rGO support are beneficial for good catalytic performance of Ni/rGO nanocomposite. Our study demonstrates a simple approach to fabricate metal-rGO heterogeneous nanostructures with advanced functions.
The distributed Bragg reflectors (DBRs) consisting of alternating layers of ZnO and heavy doped amorphous silicon (a-Si) have been fabricated by magnetron sputtering. It is novel to find that the optical absorptions exist in the stopband of the DBRs, and that many discrete strong optical absorption peaks exist in the wavelength range of visible to near-infrared. The calculated results by FDTD show that the absorptions in the stopband mainly exist in the first a-Si layer, and that the light absorbed by other a-Si layers inside contributes to the two absorption peaks in near-infrared range. The strong absorptions ranged from visible to infrared open new possibilities to the enhancement of the performance of amorphous silicon solar cells.
The effect of interaction of low-index atomic planes, (100), (110), and (111) terminating CdSe platelet nanocrystals is examined using molecular dynamics (MD) simulations. Asymmetry of the environment of atoms at the end surface layers leads to anisotropic deformation of the cubic lattice and to a relative shift of Cd and Se sub-lattices. Interference of distortions of the crystal lattice originating at the terminal surfaces leads to changes of symmetry of the CdSe lattice in the whole sample volume. In the models, 2–3 nm thick, for all types of surfaces under examination, the initial cubic lattice symmetry gets lost in the whole sample volume.
Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles (diameter?=?11.9?±?1.0 nm). The reactions were fully regioselective with monosubstituted ethylenes and ethyl cyanoformiate, while mixtures of cycloadducts were obtained in the presence of methyl propiolate. The intervention of iron oxide nanoparticles allowed carrying out the cycloadditions at milder conditions compared to the metal-free thermal processes. A labile intermediate has been proposed to explain this behavior.
Graphical abstract Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles.
Using density functional theory calculations, we systematically investigated the effects of numbers and types of transition metals (TM) on the magnetic property of SnSe2 bilayer nanosheet. Our results revealed that, when one TM is introduced into the interlayer, the magnetic moment induced by the Co and Ni is tiny while it is largely strengthened with the doping of V, Cr, Mn, and Fe. When two TMs are inserted into the interlayer, V and Cr make the system change into a weak antiferromagnetism (AFM) state while Mn-, Fe-, Co-doped systems display a weak ferromagnetism (FM) ground state. These FM states have the magnetic moments which double those of the one TM–doping systems. With the TM numbers further increasing to four, the robust AFM and FM features appear with the doping of Fe and Mn, respectively. Ni cannot induce any magnetism whatever the numbers of Ni are filling in. Interestingly, with the increase of the numbers of dopants, transitions from FM to AFM and AFM to FM are predicted to be realized on Fe-SnSe2 and Cr-SnSe2 systems, respectively. This kind of transition may be important for the applications in spintronic devices.
The results of molecular dynamics (MD) simulations of CdSe crystals terminated by low-index atomic planes, (100), (110) and (111), are presented. The effect of the crystal termination on the atomic arrangement (interatomic distances) at the surface and underneath the surface is examined. It is shown that the crystal lattice is distorted in lateral and normal directions to the depth of up to about 2 nm from the surface. The exact characteristic of the changes of interatomic distances is specific to the type of the atomic plane terminating the crystal lattice. At some surfaces, the very last monoatomic layer loses the long-range ordering and becomes quasi amorphous. The atoms group into randomly distributed pairs or short linear groups.
Sm3+-doped SrSnO3 (SrSnO3:Sm3+) nanopowders were synthesized by a simple hydrothermal method and followed by a heat treatment process. The as-synthesized nanopowders were assembled in dye-sensitized solar cells (DSSCs) to investigate their photoelectric properties. X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive spectrometer (EDS) confirmed the formation of SrSnO3:Sm3+ nanopowders with perovskite structure. The ultraviolet-visible absorption spectra and photoluminescence spectra indicate a down-conversion from ultraviolet light to visible light which matches the strong absorption region of the N719 dye. The DSSC based on SrSnO3:Sm3+ photo-anode improved its photoelectric conversion efficiency (η) via the down-conversion of doped Sm3+. Under the irradiation of the simulated sunlight with 100 mW/cm2, the DSSC based on SrSnO3 doping with Sm3+ of 0.6 wt% showed the highest η of 1.54%, which improved 71.11% compared with the DSSC based on pure SrSnO3.
The most important limitation for boron neutron capture therapy of cancer is the selective accumulation of boron compounds in tumor tissues in significant quantities. In this paper, we describe the possibility to use magnetic Ni/Fe nanotubes as carriers for boron delivery. Carborane derivatives containing 10 and 21 boron atoms per molecule were immobilized on Ni/Fe nanotubes by covalent and ionic interactions. Magnetic properties of NTs were investigated by Mössbauer spectroscopy. Structure, element, chemical composition, and morphology of obtained magnetic nanotubes were studied by XRD, SEM-EDA, and FTIR spectroscopy. Results indicate success immobilization of carborane derivatives on Ni/Fe nanotubes and great potential to use them as carriers for boron neutron cancer therapy of cancer.
