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.%.

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。

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。

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。

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。

面向可穿戴生理传感应用的氧化锌纳米棒阵列修饰蚕丝

蚕丝是天然蛋白质纤维,具有光滑、亲肤、机械强度高等优点,作为纺织纤维在我国已有数千年的使用历史。随着智能时代的到来,织物电子研究逐渐兴起,但是蚕丝纤维在智能可穿戴应用领域的研究还非常有限。该文提出了一种在单根蚕丝纤维表面原位修饰氧化锌(ZnO)纳米棒阵列的低成本方法,成功制备了基于单根蚕丝纤维的ZnO纳米棒阵列。研究表明,ZnO纳米棒致密且均匀地垂直排列于蚕丝表面,其直径为100~200 nm,长度约为2μm,其晶型为六方纤锌矿结构。结合ZnO纳米棒的压电性质,构建了基于ZnO纳米棒阵列修饰单根蚕丝的压电传感器。该传感器可有效地将机械能转换为电能,可对手指的敲击、按压、弯曲动作实时响应,将其固定于腹部或体表心脏部位可对人体呼吸、心跳等生理数据进行监测。此外,该传感器还可分辨木琴敲击过程中音调和音阶的变化。该文所构建的蚕丝基压电传感器在人体动作、生理参数实时监测方面展示了极大潜力,有望拓展蚕丝在可穿戴织物器件和智能传感领域的实际应用。

α-Fe_(2)O_(3)纳米棒的水热合成与阻变开关特性研究

采用水热法合成了沿[110]方向具有优先生长取向的α-Fe_(2)O_(3)纳米棒,设计了具有非易失性阻变开关性能的W/α-Fe2O_(3)/FTO阻变存储器。对W/α-Fe_(2)O_(3/)FTO器件的阻变开关特性进行分析发现,W/α-Fe_(2)O_(3)/FTO阻变存储器的电阻比(RHRS/RLRS)在一个数量级以上,可保持100 s以上而无明显下降。此外,器件的载流子运输特性分别由LRS下的欧姆传导机制和HRS下的陷阱控制的空间电荷限制电流传导机制决定。由氧空位的迁移引起的纳米导电细丝的部分形成与断裂可以解释W/α-Fe_(2)O_(3)/FTO阻变存储器的非易失性阻变开关行为。因此,基于α-Fe_(2)O_(3)纳米棒的阻变存储器件可能是下一代非易失性存储应用的潜在候选器件。

铬掺杂CdS纳米棒室温铁磁性及光学性质

用溶剂热法合成了具有室温铁磁性能Cr掺杂的CdS纳米棒。XRD分析表明产物为六方相CdS。TEM表明不同Cr含量的CdS均为纳米棒,CdS纳米棒长为100~350 nm,平均直径为20~30 nm, CdS纳米棒的形貌与Cr掺杂量的多少无关。EDS测试表明,合成产物由S、Cd和Cr三种元素组成。振动样品磁强计(VSM)表明,Cr掺杂CdS纳米棒在室温下有铁磁性,而未掺杂CdS纳米棒有弱铁磁性。Cr掺杂CdS纳米棒(Cr=4.17%,7.31%,均为原子分数)的饱和磁化强度Ms分别为3.907和8.798(×10^(-3)emu/g),矫顽力Hc分别为96.21和137.15 Oe(1 Oe=79.58 A/m)。CdS纳米棒室温铁磁性能的产生与CdS晶格中Cd原子被Cr的取代有着密切关系。

不同长径比的具有固定宽度金纳米棒的合成

金纳米棒在光学、电学、信息学和生物医学等领域具有广泛的应用。然而,一些具有特殊要求的金纳米棒还不能通过常规的方法制备。在本研究中,我们创新地将十二醇(LA)分子引入到传统种子生长方法中,成功实现了具有固定宽度的不同长径比(AR)金纳米棒(FW-Au NR)的按需制备。此外,通过合理地选择相应的反应条件(如氯金酸和硝酸银的浓度),可以在130–38.4,109–26.4和16–46 nm范围之间分别调节FW^(23)-Au NRs,FW^(14)-Au NRs和FW^(6.5)-Au NRs (右上角的标注数字表示金纳米棒的宽度)的长度。即,可在一个较大的长度范围内调节具有固定宽度的金纳米棒的长径比。并且,在合适浓度的十二醇,0.24–0.30 mmol·L^(-1)范围内调节硝酸银浓度,可以使这些金纳米棒的宽度固定在6.5–23 nm之间。另外,实现FW-Au NRs制备的关键是银离子和十二醇分子对分布在金种子晶面上的CTA-Br-Ag^(+)化合物的密度的协同影响。

基于聚多巴胺包覆金纳米棒的光热免疫层析法检测食品中喹诺酮兽药

该文采用种子介导生长法合成光热剂金纳米棒(Au nanorods,AuNRs),并在其表面包覆聚多巴胺制备复合光热纳米材料,偶联抗体制备免疫探针,建立一种便捷的光热免疫层析检测方法,并应用于动物源性食品中喹诺酮兽药的快速定量检测。结果表明,在最佳检测条件下,该方法喹诺酮兽药(以诺氟沙星计)的检出范围为0.22~18.84μg/L,检测限为0.14μg/L,脱脂牛奶和虾的加标回收率分别为88.62%~100.17%和90.20%~100.08%,变异系数分别为4.18%~8.50%和3.30%~6.24%,方法特异性良好。与高效液相色谱法相比,二者结果具有良好一致性,因此,该方法适用于食品中喹诺酮兽药快速定性及定量的检测。

基于ZnO纳米棒阵列的钙钛矿太阳电池研究

在钙钛矿太阳电池中利用水热法制备ZnO纳米棒阵列时,TiO_(2)薄膜一般是制备ZnO种子层以及后续生长ZnO纳米棒阵列的基础。因此TiO_(2)薄膜的致密和平滑程度对ZnO纳米棒阵列的生长及相应太阳电池的光伏性能有重要影响。本文通过使用水解-热解法以NbCl5为铌源在FTO导电基底上制备了Nb掺杂的TiO_(2)致密层,有效提升了TiO_(2)薄膜的致密程度,并在此基础上通过水热法成功沉积生长了具有不同长度、直径和面密度的ZnO纳米棒阵列。通过两步连续沉积法在所得ZnO纳米棒阵列上制备了摩尔比为CH3NH3I/CH3NH3Br=85/15的CH3NH3PbI3-xBrx钙钛矿薄膜。使用spiro–OMeTAD作为空穴传输层,组装了基于Nb掺杂TiO_(2)致密层的ZnO纳米棒阵列钙钛矿太阳电池,在相对湿度55%的空气中获得了13.97%的光电转换效率。

锐钛矿相TiO_(2)纳米棒阵列的制备及其在钙钛矿太阳电池中的应用

在钙钛矿太阳电池中,定向生长的TiO_(2)纳米棒阵列具有可控的排列结构,能够为电子的传输提供有序的径向传输通道,从而改善电子在界面间的分离与传输。本文通过水热法成功制备了长度为400 nm、直径为65 nm、面密度为160μ·m^(-2)的锐钛矿相TiO_(2)纳米棒阵列,使用摩尔比n(CH_(3)NH_(3)I):n(CH_(3)NH_(3)Br)=85:15的CH_(3)NH_(3)PbI_(3-x)Br_(x)薄膜作为钙钛矿光吸收层,spiro-OMeTAD作为空穴传输层组装了基于锐钛矿相TiO_(2)纳米棒阵列的钙钛矿太阳电池,研究了不同纳米棒阵列对钙钛矿太阳电池光伏性能的影响,结果表明,基于锐钛矿相TiO_(2)纳米棒阵列钙钛矿太阳电池在相对湿度为54%的空气环境下取得了14.35%的光电转换效率。