Manipulating d-d orbital hybridization induced by Mo-doped Co_(9)S_(8) nanorod arrays for high-efficiency water electrolysis

Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.

Composites of In/C hexagonal nanorods and graphene nanosheets for high-performance electromagnetic wave absorption

In recent years,electromagnetic wave(EMW)absorption has been extensively investigated for solving EMW radiation and pollution.The metal-organic frameworks(MOFs)have attracted attention due to their low density and unique structure,which can meet the requirements of strong reflection loss(RL)and wide absorption bandwidth of EMW absorption materials.In this manuscript,indium nanoparticles/porous carbon(In/C)nanorods composites were prepared via the pyrolysis of nanorods-like In-MOFs at a low temperature of450°C.Indium nanoparticles are evenly attached and embedded on porous carbon.Low electrical conductivity of In/C nanorods is unfavorable to EMW absorption performance,which is due to the low temperature carbonization.Thus,graphene(Gr)nanosheets with high electrical conductivity are introduced to adjust electromagnetic parameters of In/C nanorods for enhancing EMW absorption.The minimum RL of the In/C-Gr-4 composite is up to-43.7 dB with a thin thickness of 1.30 mm.In addition,when the thickness is further reduced to 1.14 mm,the minimum RL of-39.3 dB at 16.1 GHz and effective absorption bandwidth of 3.7 GHz(from 14.3 to 18.0 GHz)can be achieved.This work indicates that In/C-Gr composites show excellent EMW absorption performance.

Investigation of photoelectrocatalytic degradation mechanism of methylene blue by a-Fe_(2)O_(3) nanorods array

Efficiently and thoroughly degrading organic dyes in wastewater is of great importance and challenge.Herein,vertically oriented mesoporous a-Fe_(2)O_(3)nanorods array(a-Fe_(2)O_(3)-NA)is directly grown on fluorine-doped tin oxide(FTO)glass and employed as the photoanode for photoelectrocatalytic degradation of methylene blue simulated dye wastewater.The Ovsites on the a-Fe_(2)O_(3)-NA surface are the active sites for methylene blue(MB)adsorption.Electrons transfer from the adsorbed MB to Fe-O is detected.Compared with electrocatalytic and photocatalytic degradation processes,the photoelectrocatalytic(PEC)process exhibited the best degrading performance and the largest kinetic constant.Hydroxyl,superoxide free radicals,and photo-generated holes play a jointly leading role in the PEC degradation.A possible degrading pathway is suggested by liquid chromatography-mass spectroscopy analysis.This work demonstrates that photoelectrocatalysis by a-Fe_(2)O_(3)-NA has a remarkable superiority over photocatalysis and electrocatalysis in MB degradation.The in-depth investigation of photoelectrocatalytic degradation mechanism in this study is meaningful for organic wastewater treatment.

Molecular dynamics simulation of interaction between nanorod and phospholipid molecules bilayer

Natural and artificially prepared nanorods'surfaces have proved to have good bactericidal effect and self-cleaning property.In order to investigate whether nanorods can kill the enveloped virus,like destroying bacterial cell,we study the interaction between nanorods and virus envelope by establishing the models of nanorods with different sizes as well as the planar membrane and vesicle under the Dry Martini force field of molecular dynamics simulation.The results show that owing to the van der Waals attraction between nanorods and the tail hydrocarbon chain groups of phospholipid molecules,the phospholipid molecules on virus envelope are adsorbed to nanorods on a large scale.This process will increase the surface tension of lipid membrane and reduce the order of lipid molecules,resulting in irreparable damage to planar lipid membrane.Nanorods with different diameters have different effects on vesicle envelope,the larger the diameter of nanorod,the weaker the van der Waals effect on the unit cross-sectional area is and the smaller the degree of vesicle deformation.There is synergy between the nanorods in the nanorod array,which can enhance the speed and scale of lipid adsorption.The vesicle adsorbed in the array are difficult to desorb,and even if desorbed,vesicle will be seriously damaged.The deformation rate of the vesicle adsorbed in the nanorod array exceeds 100%,implying that the nanorod array has a strong destructive effect on the vesicle.This preliminarily proves the feasibility of nanorod array on a surface against enveloped virus,and provides a reference for the design of corresponding nanorods surface.

From kesterite 2D nanosheets to wurtzite 1D nanorods:controllable synthesis of Cu-Zn-Sn-S and their application in electrocatalytic hydrogen evolution

As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solvent,plays a significant role in the assisting synthesis of CZTS NCs due to the ligand effect.Herein,we adopted a facile one-pot colloidal method for achieving the structure evolution of CZTS NCs from 2D nanosheets to 1D nanorods assisted through the continuous addition of OM.During the process,the mechanism of OM-induced morphology evolution was further discussed.When merely adding pure 1-dodecanethiol(DDT)as the solvent,the CZTS nanosheets were obtained.As OM was gradually added to the reaction,the CZTS NCs began to grow along the sides of the nanosheets and gradually shrink at the top,followed by the formation of stable nanorods.In acidic electrolytic conditions,the CZTS NCs with 1.0 OM addition display the optimal HER activity with a low overpotential of 561 m V at 10 m A/cm^(2) and a small Tafel slope of 157.6 m V/dec compared with other CZTS samples.The enhancement of HER activity could be attributed to the contribution of the synergistic effect of the diverse crystal facets to the reaction.

Au@Ag Core-shell Nanorods Self-assembled on Polyelectrolyte Multilayers for Ultra-High Sensitivity SERS Fiber Probes

We demonstrated a chemical process in the fabrication of a SERS fiber probe with an ultrahigh sensitivity.The synthesis was carried out by preparing Au@Ag core-shell nanorods (Au@Ag-NRs) selfassembled on polyelectrolyte (PE) multilayers,for which Au@Ag-NRs were controlled by adjusting the silver layer thickness.The effect of silver layer thickness of Au@Ag-NRs on the SERS performance of the fiber probe was investigated.The SERS fiber probe shows the best performance when the silver layer thickness is controlled at 8.57 nm.Under the condition of optimizing silver layer thickness,the fiber probe exhibits ultra-high sensitivity (i e,10^(-10) M crystalline violet,CV),good reproducibility (i e,RSD of 3.5%) and stability.Besides,electromagnetic field distribution of the SERS fiber probe was also investigated.The strongest enhancement is found within the core of fiber,whereas a weakened electromagnetic field exists in the fiber cladding layer.The SERS fiber probe can be a good candidate in ultra-trace detection for biomedical and environmental areas.

Manifolding active sites and in situ/operando electrochemical-Raman spectroscopic studies of single-metal nanoparticle-decorated CuO nanorods in furfural biomass valorization to H_(2) and 2-furoic acid

Here,CuO nanorods fabricated via pulsed laser ablation in liquids were decorated with Ir,Pd,and Ru NPs(loading~7 wt%) through pulsed laser irradiation in the liquids process.The resulting NPs-decorated CuO nanorods were characterized spectroscopically and employed as multifunctional electrocatalysts in OER,HER,and the furfural oxidation reactions(FOR).Ir-CuO nanorods afford the lowest overpotential of~345 mV(HER) and 414 mV(OER) at 10 mA cm^(-2),provide the highest 2-furoic acid yield(~10.85 mM) with 64.9% selectivity,and the best Faradaic efficiency~72.7% in 2 h of FOR at 1.58 V(vs.RHE).In situ electrochemical-Raman analysis of the Ir-CuO detects the formation of the crucial intermediates,such as Cu(Ⅲ)-oxide,Cu(OH)_(2),and Ir_x(OH)_y,on the electrode-electrolyte surface,which act as a promoter for HER and OER.The Ir-CuO ‖ Ir-CuO in a coupled HER and FOR-electrolyzer operates at~200 mV lower voltage,compared with the conventional electrolyzer and embodies the dual advantage of energy-saving H_(2) and 2-furoic acid production.

Atomic Dispersion of Rh on Interconnected Mo_(2)C Nanosheet Network Intimately Embedded in 3D Ni_(x)MoO_(y) Nanorod Arrays for pH-Universal Hydrogen Evolution

Herein,a simple synthetic approach is employed for the atomic dispersion of Rh atoms(Rh SAs)over the surface of interconnected Mo_(2)C nanosheets intimately embedded in a three-dimensional Ni_(x)MoO_(y)nanorod arrays(Ni_(x)MoO_(y)NRs)framework;we found that the introduction of both isolated Rh SAs and Ni_(x)MoO_(y)NRs adjusts the electrocatalytic function of the host Mo_(2)C toward the direction of being an advanced and highly stable electrocatalyst for efficient hydrogen evolution at pH-universal conditions.As a result,the proposed catalyst outperforms most recently reported transition metal-based catalysts,and its performance even rivals that of commercial Pt/C,as demonstrated by its ultralow overpotentials of 31.7,109.7,and 95.4 mV at a current density of 10 mA cm^(-2),along with its small Tafel slopes of 42.4,51.2,and 46.8 mV dec^(-1)in acidic,neutral,and alkaline conditions,respectively.In addition,the catalyst shows remarkable long-term stability over all pH values with good maintenance of its catalytic activity and structural characteristics after continuous operation.

Structural, Optical and Photocatalytic Properties of Cu2+ Doped ZnO Nanorods with Using HMTA Solvent Prepared by Hydrothermal Method

In this experiment, Cu2+ doped ZnO (Cu-ZnO) nanorods materials have been fabricated by hydrothermal method. Cu2+ ions were doped into ZnO with ratios of 2, 5 and 7 mol.% (compared to the mole’s number of Zn2+). The hexamethylenetetramine (HMTA) solvent used for the fabrication of Cu-ZnO nanorods with the mole ratio of Zn2+:HMTA = 1:4. The characteristics of the materials were analyzed by techniques, such as XRD, Raman shift, SEM and UV-vis diffuse reflectance spectra (DRS). The photocatalytic properties of the materials were investigated by the decomposition of the methylene blue (MB) dye solution under ultraviolet light. The results show that the size of Cu-ZnO nanorods was reduced when the Cu2+ doping ratio increased from 2 mol.% to 7 mol.%. The decomposition efficiency of the MB dye solution reached 92% - 97%, corresponding to the Cu2+ doping ratio changed from 2 - 7 mol.% (after 40 minutes of ultraviolet irradiation). The highest efficiency for the decomposition of the MB solution was obtained at a Cu2+ doping ratio of 2 mol.%.

Synthesis and Characterization of Nickel Nanorods Transferred from Hydrotherally Decomposed Rod-like NiS

Powders of hexagonal-structured single-crystalline nickel sulfide nanorods have been synthesized in cetyltrimethy ammonium bromide （CTAB）/water/hexane/n-pentanol quaternary microemulsion under hydrothermal conditions by using the reaction of carbamide and carbon disulfide as a sulfide source. Single-crystalline nickel nanorods have been synthesized via thermal decomposition by using single-crystalline nickel sulfide nanorods as precursor. The influence of different reaction parameters on the morphology of the products has been investigated. The structure, morphology and magnetic properties of the products were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, calorimeter （TGA-DSC） and vibrating sample magnetometer showed that the specific saturation magnetization （σs） and 37.5 emu/g and 68.50e, respectively. thermogravimetric analysis-differential scanning （VSM）. The results of coercivity values （Hc） magnetic measurements of nickel nanorods were

Fluorescent Silicon Nanorods-Based Nanotheranostic Agents for Multimodal Imaging-Guided Photothermal Therapy

The utilization of diagnosis to guide/aid therapy procedures has shown great prospects in the era of personalized medicine along with the recognition of tumor heterogeneity and complexity.Herein,a kind of multifunctional silicon-based nanostructure,i.e.,gold nanoparticles-decorated fluorescent silicon nanorods(Au@SiNRs),is fabricated and exploited for tumor-targeted multimodal imaging-guided photothermal therapy.In particular,the prepared Au@SiNRs feature high photothermal conversion efficiency(~43.9%)and strong photothermal stability(photothermal performance stays constant after five-cycle NIR laser irradiation),making them high-performance agents for simultaneously photoacoustic and infrared thermal imaging.The Au@SiNRs are readily modified with targeting peptide ligands,enabling an enhanced tumor accumulation with a high value of^8.74%ID g?1.Taking advantages of these unique merits,the Au@SiNRs are superbly suitable for specifically ablating tumors in vivo without appreciable toxicity under the guidance of multimodal imaging.Typically,all the mice treated with the Au@SiNRs remain alive,and no distinct tumor recurrence is observed during 60-day investigation.

Mg(OH)_2 Nanorods Synthesized by A Facile Hydrothermal Method in the Presence of CTAB

Magnesium hydroxide(Mg(OH)_2) nanorods were synthesized by a simple and facile hydrothermal method in the presence of cetyltetramethylammonium bromide(CTAB) as a surfactant. Nanorods of magnesium oxide Mg O were also induced by thermal decomposition of Mg(OH)_2 nanorods at 700. By using disk diffusion technique, the Mg(OH)_2 nanorods were found to exhibit higher antibacterial efficiency against several tested bacterial strains.

Synthesis of ZnO nanorods and their optical absorption in visible-light region

Single crystalline ZnO nanorods were prepared by the hydrothermal method with synthesized ZnCl2·4Zn（OH）2 as the precursor. Morphologies of the nanorods were controlled by various reaction conditions with cetyltrimethylammonium bromide （CTAB） as the modifying agent. The nanorods were characterized by XRD, TEM, UV-Vis spectra, and IR spectra. The microstructure of holes in nanosize was observed on the surface of the nanorods. The UV-Vis spectra indicate that the as-prepared ZnO nanorods have absorption of visible-hght as well as ultraviolet-light. Therefore, these nanorods may be good candidates for visible-light photocatalysis materials from the viewpoint of practical applications. The reason for visible-light absorption was discussed in this article.

MoS2 nanorods with inner caves through synchronous encapsulation of sulfur for high performance Li–S cathodes

Lithium–sulfur(Li–S)batteries have become one of the most promising candidates for next-generation batteries owing to their high specific capacity,low cost,and environment-friendliness.Many efforts have been made to mitigate the"shuttle effect"through physical adsorption and chemical bonding.MoS2 has been proposed as a cathode material to provide effective anchoring sites for lithium polysulfides(Li PSs),but is still limited by its layer structure.Herein,we designed novel MoS2 nanorods with inner caves based on our previous work,and performed synchronous encapsulation of sulfur during the synthesis process.The outer MoS2 tubular shells physically inhibit the outward diffusion of polysulfide species while the inner particles chemically anchor the polysulfides to prevent shuttling.As the cathode matrix in Li–S batteries,the electrochemical results deliver a high initial discharge capacity of 1213 mAhg^-1 for sulfur at 0.1 C.After cycling at 1 C for 300 cycles,the cells exhibit a capacity decay of only 0.076%per cycle and high average coulombic efficiency over 95%.The tubular MoS2 structure is an innovative and appealing design,which could be regarded as a prospective substrate for the improved performance of Li–S batteries.

Hybrid Field-Effect Transistors and Photodetectors Based on Organic Semiconductor and CsPbI_3 Perovskite Nanorods Bilayer Structure

The outstanding performances of nanostructured allinorganic CsPbX_3(X = I, Br, Cl) perovskites in optoelectronic applications can be attributed to their unique combination of a suitable bandgap, high absorption coefficient, and long carrier lifetime, which are desirable for photodetectors. However, the photosensing performances of the CsPbI_3 nanomaterials are limited by their low charge-transport efficiency. In this study, a phototransistor with a bilayer structure of an organic semiconductor layer of 2,7-dioctyl [1] benzothieno[3,2-b] [1] benzothiophene and CsPbI_3 nanorod layer was fabricated. The high-quality CsPbI_3 nanorod layer obtained using a simple dip-coating method provided decent transistor performance of the hybrid transistor device.The perovskite layer efficiently absorbs light, while the organicsemiconductor layer acts as a transport channel for injected photogenerated carriers and provides gate modulation. The hybrid phototransistor exhibits high performance owing to the synergistic function of the photogating effect and field effect in the transistor,with a photoresponsivity as high as 4300 A W^(-1), ultra-high photosensitivity of 2.2 9 106, and excellent stability over 1 month.This study provides a strategy to combine the advantages of perovskite nanorods and organic semiconductors in fabrication of high-performance photodetectors.

Syntheses, Morphologies and Properties of BiOI Nanolamellas and BiSI Nanorods

Well defined BiOI nanolamellas and BiSI nanorods have been synthesized by a solventless method. The phase identity, morphology, growth orientation, and conversion from lamella to rod have been investigated. Several experimental facts suggest that the growth orientations of BiOI nanolamellas and BiSI nanorods are guided by their corresponding crystal structure motifs. The optical band gaps of BiOI and BiSI are measured to be 1.97 and 1.61 eV, and the visible light photocatalytic activity of BiOI lamellas is primarily measured.

Fabrication and magnetic properties of NiFe_2O_4 nanorods

NiFe2O4 nanorods have been successfully synthesized via thermal treatment of the rod-like precursor fabricated by Ni-doped （x-FeOOH, which was enwrapped by the complex of citric acid and Niz~. The morphology evolution during the calcination of the precursor nanorods was investigated with transmission electron microscopy （TEM）, and the phase and the magnetic properties of samples were analyzed through X-ray diffraction （XRD） and vibrating sample magnetometer （VSM）. The results indicated that the diameter of the NiFe204 nanorods obtained ranged between 30 and 50 nm, and the length ranged between 2 and 3 um. As the calcination temperature was up to 600℃, the coercivity, saturation magnetization, and remanent magnetization of the samples were 36.1 kA.m^-1, 27.2 A.m2.kg^-1, and 5.3 A.m2.kg^-1, respectively. The NiFe2O4 nanorods prepared have higher shape anisotropy and superior magnetic properties than those with irregular shapes.

Hydrothermal growth of well-aligned TiO_2 nanorod arrays: Dependence of morphology upon hydrothermal reaction conditions

Well-aligned TiO2 nanorod arrays （TNAs） were prepared on pretreated quartz substrates via hydrothermal method.The effect of the different preparation conditions on the growth morphologies of TNAs was systematically investigated by X-ray diffraction （XRD） and field-emission scanning electron microscopy （FE-SEM）.The photocatalytic properties were tested by photodegradation of a methyl blue solution.It is demonstrated that the hydrothermal reaction conditions,such as precursor concentration,hydrothermal reaction temperature,and hydrothermal reaction times,can greatly affect the growth of TNAs.Controlling the preparation process,TNAs with 2 μm in length and 140-170 nm in diameter and well-aligned orientation have been successfully prepared.The photocatalytic experiment results indicate that TNAs have much better photocatalytic activity than TiO2 nanoparticles.

High-precision regulation synthesis of Fe-doped Co_(2)P nanorod bundles as efficient electrocatalysts for hydrogen evolution in all-pH range and seawater

The hydrogen evolution reaction(HER)via water electrolysis has gained immense research attention.Seawater electrolysis provides great opportunities for sustainable energy production,but is extremely challenging.Transition metal phosphides are promising candidate electrocatalysts.Herein,we prepared a novel Fe-Co_(2)P bundle of nanorods(BNRs)for catalyzing the HER in seawater electrolysis and over the entire p H range.Cobalt phosphides with different crystal phases and morphologies were obtained by varying the Fe doping amount.The Co:Fe molar ratio of 1:0.5 was found to be optimum.The Fe doping improved the HER performance of Co_(2)P over the entire p H range by providing favorable electronic properties and morphology,lattice distortion,and special coordination environment.The Fe-Co_(2)P BNRs showed higher catalytic activity than 20%Pt/C in seawater at high potentials.The density functional theory calculations revealed that the Fe doping reduced the hydrogen binding strength of Co_(2)P to efficiently accelerate the HER kinetics and produce a favorable charge density.This study provides valuable insights into the design and development of high-efficiency HER catalysts for large-scale seawater electrolysis.

Effects of surface adsorbed oxygen, applied voltage, and temperature on UV photoresponse of ZnO nanorods

The ultraviolet（UV） photoresponses of ZnO nanorods directly grown on and between two micro Au-electrodes by using electric-field-assisted wet chemical method are measured comprehensively under different conditions, including ambient environment, applied bias voltage, gate voltage and temperature. Experimental results indicate that the photoresponses of the ZnO nanorods can be modulated by surface oxygen adsorptions, applied voltages, as well as temperatures. A model taking into account both surface adsorbed oxygen and electron-hole activities inside ZnO nanorods is proposed. The enhancement effect of the bias voltage on photoresponse is also analyzed. Experimental results shows that the UV response time（to 63%） of ZnO nanorods in air and at 59°C could be shortened from 34.8 s to 0.24 s with a bias of 4 V applied between anode and cathode.