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.

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.%.

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.

功能纳米材料光热抗肿瘤实验设计

将科研课题和功能纳米材料实验教学有机融合,依托校仪器共享平台,设计了光热抗肿瘤综合实验。实验课前以视频、文献和课件等形式介绍背景知识,课堂上进行纳米材料光热抗肿瘤机制讲解,并结合实验目的启发学生自行设计实验方案。实验通过多元评价考核体系,促进学生综合能力提升;将大型仪器使用纳入实验教学,激发学生科研热情;在以科研带教学、以教学促科研方面取得了良好效果。

Au@α-Fe_(2)O_(3)纳米棒的制备及光催化性能

本工作通过水热法与磁控溅射法结合成功构建了表面均匀沉积纳米Au粒子的α-Fe_(2)O_(3)(Au@α-Fe_(2)O_(3))纳米棒,纳米Au粒子的负载量和形态分别由磁控溅射时间和热处理温度调控。在沉积5.1%的纳米Au粒子后,因纳米Au的表面等离子体共振(SPR)效应,Au@α-Fe_(2)O_(3)纳米棒在550 nm处出现了一个新的吸收峰,其带隙由2.20 eV变窄至1.95 eV。Au@α-Fe_(2)O_(3)纳米棒的荧光强度和电化学阻抗显著降低,光电流从0.27μA·cm^(-2)增大至0.45μA·cm^(-2)。纳米Au粒子既拓宽了Au@α-Fe_(2)O_(3)纳米棒的可见光吸收性能,又抑制了电子-空穴对的复合。与α-Fe_(2)O_(3)纳米棒相比,Au@α-Fe_(2)O_(3)纳米棒的光催化性能变得更加稳定,Au@α-Fe_(2)O_(3)纳米棒的光催化效率提高约一倍。

Pt NPs增强ZnO@ZnS核-壳异质纳米棒光催化产氢性能研究

采用原位光沉积方法将铂纳米颗粒(Pt NPs)负载在核-壳异质纳米棒ZnO@ZnS表面,制备出ZnO@ZnS/Pt复合光催化剂。调控Pt NPs在ZnO@ZnS表面的负载量,探究了不同质量的Pt NPs对光催化产氢气性能的影响。结果表明,当贵金属Pt的负载量为2%(ZnO@ZnS/Pt-2)时,复合光催化产H_(2)性能最好,产氢速率为4.52 mmol/(g·h),是ZnO@ZnS的1.8倍,催化剂表现出优异的催化稳定性。在此复合材料中,贵金属Pt纳米颗粒作为助催化剂,Pt对H~+具有较低的吸附能,优先吸附H~+,光生电子转移到Pt纳米粒子表面,H^(+)在其表面得到光生电子,被还原为氢气,成功地抑制了光生电子和空穴的复合,有效地提升了催化剂的催化性能。

基于金纳米棒刻蚀比色法检测铁、铜离子

采用种子生长法制备金纳米棒(AuNRs)以构建光学传感器,用于Fe^(3+)和Cu^(2+)的高选择性快速可视化检测。在酸性环境中,Fe^(3+)和Cu^(2+)通过与KI溶液反应,将I-氧化成I2。I2刻蚀AuNRs,导致其纵向表面等离子体共振(LSPR)吸收峰蓝移,从而实现对Fe^(3+)和Cu^(2+)的检测。结果表明,反应温度为50℃时,添加0.8 mL 0.1 mol·L^(-1)HCl、2 mL AuNRs生长液和20 mmol·L^(-1)KI溶液,与2 mL 500μmol·L^(-1)Fe^(3+)或30μmol·L^(-1)Cu^(2+)反应25或90 min,可将AuNRs刻蚀至LSPR吸收峰消失。该方法对Fe^(3+)和Cu^(2+)检测具有高选择性和准确性,对于Fe^(3+)、Cu^(2+)共存体系的检测,可通过加入适量F-与Fe^(3+)生成配合物[FeF_(6)]^(3-)完成对Fe^(3+)的化学掩蔽,消除Fe^(3+)的干扰,实现共存体系中Cu^(2+)的准确检测。

5%Ag掺杂对MNO_(2)纳米棒和海胆微球形貌及其甲苯氧化性能的影响

采用水热法制备了MNO_(2)纳米棒和海胆微球,并原位掺杂5%Ag制备了Mn-Ag复合氧化物,利用SEM、XRD、BET、Raman等表征技术对其结构进行表征,并考察不同催化剂对甲苯的去除性能。结果表明:(NH_(4))_(2)S_(2)O_(8)的掺入量会对MNO_(2)的形貌产生影响,当其掺入量为2.28 g时,形成MNO_(2)纳米棒,当其掺入量为6.84 g时,形成MNO_(2)海胆微球;MNO_(2)纳米棒掺杂5%的Ag后,形貌未发生变化,但当MNO_(2)海胆微球掺杂5%Ag时,表面的纳米线较MNO_(2)海胆微球有所增长,且出现了缠绕现象,形成了空心鸟巢状结构;5%Ag掺杂后,对MNO_(2)纳米棒和MNO_(2)海胆微球的晶型未产生影响,均为α-MNO_(2),但5%Ag-MNO_(2)纳米棒出现了Mn2O_(3)的衍射峰;MNO_(2)海胆微球较MNO_(2)纳米棒的比表面积、孔径和孔容均增大,且Ag的掺杂进一步提高了MNO_(2)海胆微球的比表面积、孔径和孔容;MNO_(2)海胆微球比MNO_(2)纳米棒具有更好的甲苯去除性能,且5%Ag掺杂后,MNO_(2)海胆微球对甲苯的去除性能达到最好。

Heterostructured BiOI@La(OH)_3 nanorods with enhanced visible light photocatalytic NO removal

Heterostructured BiOI@La（OH）3 nanorod photocatalysts were prepared by a facile chemical impregnation method.The enhanced visible light absorption and charge carrier separation can be simultaneously realized after the introduction of BiOI particles into La（OH）3 nanorods.The BiOI@La（OH）3 composites were applied for visible light photocatalytic oxidization of NO in air and exhibited an enhanced activity compared with BiOI and pure La（OH）3 nanorods.The results show that the energy levels between the La（OH）3 and BiOI phases matched well with each other,thus forming a heterojunctioned BiOI@La（OH）3 structure.This band structure matching could promote the separation and transfer of photoinduced electron-hole pairs at the interface,resulting in enhanced photocatalytic performance under visible light irradiation.The photocatalytic performance of BiOI@La（OH）3 is shown to be dependent on the mass ratio of BiOI to La（OH）3.The highest photocatalytic performance can be achieved when the mass ratio of BiOI to La（OH）3 is controlled at 1.5.A further increase of the mass ratio of BiOI weakened the redox abilities of the photogenerated charge carriers.A new photocatalytic mechanism for BiOI@La（OH）3 heterostructures is proposed,which is directly related to the efficient separation of photogenerated charge carriers by the heterojunction.Importantly,the as-prepared BiOI@La（OH）3 heterostructures exhibited a high photochemical stability after multiple reaction runs.Our findings demonstrate that BiOI is an effective component for the formation of a heterostructure with the properties of a wide bandgap semiconductor,which is of great importance for extending the light absorption and photocatalytic activity of wide bandgap semiconductors into visible light region.

Preparation, friction and wear properties of hydrophobic lanthanum borate nanorods in rapeseed oil

Oleic acid (denoted as OA) surface-caped lanthanum borate nanorods, abbreviated as OA/LaBO3·H2O, were prepared via hydrothermal method. The microstructures of the as-prepared OA/LaBO3·H2O nanorods were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The friction and wear properties of OA/LaBO3·H2O nanorods in rapeseed oil were evaluated with a four-ball tribo-tester. The results show that the as-prepared OA/LaBO3·H2O nanorods are hydrophobic and display nanorods morphology with uniform diameter of about 50 nm and length of up to 500 nm. In the meantime, OA/LaBO3·H2O nanorods can obviously improve the anti-wear and friction-reducing capacities of rapeseed oil, and the optimal anti-wear and friction-reducing properties of rapeseed oil were obtained at an OA/LaBO3·H2O content of 1% (mass fraction).

Synthesis and Characterization of GaN Nanorods by Ammoniating Ga_2O_3 /Co Films Deposited on Si(111) Substrates

GaN nanorods are successfully synthesized on Si（111） substrates with magnetron sputtering through ammoniating Ga2O3/Co films at 950℃. X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy,and Fourier-transform infrared spectroscopy are used to characterize the samples. The results demonstrate that the nanorods are single-crystal GaN with a hexagonal wurtzite structure and possess relatively smooth surfaces. The growth mechanism of GaN nanorods is also discussed.

Effect of KOH treatment on structural and photovoltaic properties of ZnO nanorod arrays

ZnO nanorod arrays （NRs） were synthesized on the fluorine-doped SnO2 transparent conductive glass （FTO） by a simple chemical bath deposition （CBD） method combined with alkali-etched method in potassium hydroxide （KOH） solution. X-ray diffraction （XRD）, scanning electron microscopy （SEM） and current-voltage （I-V） curve were used to characterize the structure, morphologies and optoelectronic properties. The results demonstrated that ZnO NRs had wurtzite structures, the morphologies and photovoltaic properties of ZnO NRs were closely related to the concentration of KOH and etching time, well-aligned and uniformly distributed ZnO NRs were obtained after etching with 0.1 mol/L KOH for 1 h. ZnO NRs treated by KOH had been proved to have superior photovoltaic properties compared with high density ZnO NRs. When using ZnO NRs etched with 0.1 mol/L KOH for 1 h as the anode of solar cell, the conversion efficiency, short circuit current and open circuit voltage, compared with the unetched ZnO NRs, increased by 0.71%, 2.79 mA and 0.03 V, respectively.

Preparation of MnxNi0.5-xZn0.5Fe2O4 Nanorods by the Co-precipitation Method

MnxNi0.5-xZn0.5Fe2O4 nanorods were successfully synthesized by the thermal treatment of rod-like precursors that were fabricated by the co-precipitation of Mn2＋, Ni2＋, and Fe2＋ in the lye. The phase, morphology, and particle diameter were examined by the X-ray diffraction and transmission electron microscopy. The magnetic properties of the samples were studied using a vibrating sample magnetometer. nanorods with a diameter of 35 nm and an The results indicated that pure Ni0.5-xZn0.5Fe2O4 aspect ratio of 15 were prepared. It was found that the diametei of the MnxNi0.5-xZn0.5Fe2O4（0≤x≤0.5） samples increased, the length and the aspect .ratio decreased, with an increase in x value. When x=0.5, the diameter and the aspect ratio of the sample reached up to 50 nm and 7-8, respectively. The coercivity of the samples first increased and then decreased with the increase in the x value. The coercivity of the samples again increased when the x value was higher than 0.4. When x=0.5, the coercivity of the MnxNi0.5-xZn0.5Fe2O4 sample reached the maximal value （134.3 Oe） at the calcination temperature of 600 ℃. The saturation magnetization of the samples first increased and then. decreased with the increase in the x value. When x=0.2, the saturation magnetizat：ion of the sample reached the maximal value （68.5 emu/g） at the calcination temperature of 800 ℃.

基于液滴反应器的图案化ZnO纳米棒阵列的合成和荧光检测性能

设计并制备了一种低成本的液滴反应器,通过半开放的微孔捕获液滴在衬底上合成图案化ZnO纳米材料。探究了不同液滴更新间隔时间合成的ZnO纳米棒形貌和尺寸的变化规律以及液滴蒸发过程中随着接触角的变化液滴内部流速的变化。利用扫描电子显微镜(SEM)对ZnO纳米棒的形貌进行表征。结果表明,ZnO纳米棒形貌在不同的液滴更新间隔时间下出现明显变化,当更新间隔时间为1~2min时(在液滴体积减小到20%前更新),纳米棒具有最大长径比。此外,以ZnO纳米棒为基底对羊抗牛免疫球蛋白G进行了检测,探究在不同的合成条件下制备的ZnO纳米棒阵列的荧光检测性能。结果表明,基于液滴反应器的合成方法有利于图案化ZnO纳米棒阵列的生长,为便捷、快速的高通量原位检测提供了新思路。