Miniaturized electrochemical sensors and their point-of-care applications

Most of the current analytical methods depend largely on laboratory-based analytical techniques that require expensive and bullky equipment,potentially incur costly testing,and involve lengthy detection processes.With increasing requirements for point-of-care testing(POCT),more attention has been paid to miniaturized analytical devices.Miniaturized electrochemical(MEC)sensors,including different material-based MEC sensors(such as DNA-,paper-,and screen electrode-based),have been in strong demand in analytical science due to their easy operation,portability,high sensitivity,as well as their short analysis time.They have been applied for the detection of trace amounts of target through measuring changes in electrochemical signal,such as current,voltage,potential,or impedance,due to the oxidation/reduction of chemical/biological molecules with the help of electrodes and electrochemical units.MEC sensors present great potential for the detection of targets including small organic molecules,metal ions,and biomolecules.In recent years,MEC sensors have been broadly applied to POCT in various fields,including health care,food safety,and environmental monitoring,owing to the excellent advantages of electrochemical(EC)technologies.This review summarized the state-of-the-art advancements on various types of MEC sensors and their applications in POCT.Furthermore,the future perspectives,opportunities,and challenges in this field are also discussed.     

Machine Learning towards Screening Solid-state Lithium Ion Conductors

Machine learning is an emerging method to discover new materials with specific characteristics.An unsupervised machine learning research is highlighted to discover new potential lithium ionic conductors by screening and clustering lithium compounds,providing inspirations for the development of solid-state electrolytes and practical batteries.     

Surface defect-rich ceria quantum dots anchored on sulfur-doped carbon nitride nanotubes with enhanced charge separation for solar hydrogen production

Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce³⁺ ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.     

Superfast and solvent-free core-shell assembly of sulfur/carbon active particles by hail-inspired nanostorm technology for high-energy-density Li-S batteries

The demand on low-carbon emission fabrication technologies for energy storage materials is increasing dramatically with the global interest on carbon neutrality.As a promising active material for metal-sulfur batteries,sulfur is of great interest due to its high-energy-density and abundance.However,there is a lack of industry-friendly and low-carbon fabrication strategies for high-performance sulfur-based active particles,which,however,is in critical need by their practical success.Herein,based on a hail-inspired sulfur nano-storm(HSN)technology developed in our lab,we report an energy-saving,solvent-free strategy for producing core-shell sulfur/carbon electrode particles(CNT@AC-S)in minutes.The fabrication of the CNT@AC-S electrode particles only involves low-cost sulfur blocks,commercial carbon nanotubes(CNT)and activated carbon(AC)micro-particles with high specific surface area.Based on the above core-shell CNT@AC-S particles,sulfur cathode with a high sulfur-loading of 9.2 mg cm^-2 delivers a stable area capacity of 6.6 mAh cm^-2 over 100 cycles.Furthermore,even for sulfur cathode with a super-high sulfur content(72 wt%over the whole electrode),it still delivers a high area capacity of 9 mAh cm^-2 over50 cycles in a quasi-lean electrolyte condition.In a nutshell,this study brings a green and industryfriendly fabrication strategy for cost-effective production of rationally designed S-rich electrode particles.     

Unraveling the stabilization mechanism of solid electrolyte interface on ZnSe by rGO in sodium ion battery

Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film.     

CXN天然沸石的研究2: 吸附性质

采用N~2,NH~3,CO~2,乙烯,丙烯,水,甲醇,乙醇,丙醇等作为吸附剂,研究了由我国CXN天然沸石改性制得的H-STI和Na-STI沸石的吸附性质,H-STI和Na-STI沸石的BET表面积及微孔孔体积约为420m^2/g和0.20m^3/g。根据NH~3和CO~2在H-STI沸石上的吸附等温线计算得到它们的吸附热分别为44.8和26.5kJ/mol。乙烯,丙烯,甲醇,乙醇,丙醇等在Na-STI沸石上的吸附等温线表明该沸石对有机分子的吸附具有链长选择性。在低分压下水相对于甲醇的吸附量表明沸石具有一定的疏水性质。     

常温常湿条件下Au/MeO~x催化剂上CO氧化性能

利用共沉淀法制备了Au/MeO~x催化剂(Me=Al,Co,Cr,Cu,Fe,Mn,Ni,Zn)。在常温常湿条件下,考察了不同氧化物负载的金基催化剂的CO氧化性能。结果表明,氧化物种类对催化剂的活性和稳定性均有较大的影响。Cu,Mn,Cr等氧化物负载的金基催化剂的活性较差,而Zn,Fe,Co,Ni,Al等金属氧化物负载的金基催化剂可将CO完全氧化,又具有一定的稳定性,在相同反应条件下,CO完全转化时的稳定性顺序为Au/ZnO>Au/α-Fe~2O~3>Au/Co~3O~4>Au/γ-Al~2O~3≈Au/NiO。还发现水对Au/MnO~x催化剂的活性和稳定性有负作用,而对180℃焙烧制备的Au/ZnO-180催化剂的活性和稳定性均有明显的湿度增强作用。     

Boost oxygen reduction reaction performance by tuning the active sites in Fe-N-P-C catalysts

Cost-effective atomically dispersed Fe-N-P-C complex catalysts are promising to catalyze the oxygen reduction reaction(ORR)and replace Pt catalysts in fuel cells and metal-air batteries.However,it remains a challenge to increase the number of atomically dispersed active sites on these catalysts.Here we report a highly efficient impregnation-pyrolysis method to prepare effective ORR electrocatalysts with large amount of atomically dispersed Fe active sites from biomass.Two types of active catalyst centers were identified,namely atomically dispersed Fe sites and Fe_xP particles.The ORR rate of the atomically dispersed Fe sites is three orders of magnitude higher than it of Fe_xP particles.A linear correlation between the amount of the atomically dispersed Fe and the ORR activity was obtained,revealing the major contribution of the atomically dispersed Fe to the ORR activity.The number of atomically dispersed Fe increases as the Fe loading increased and reaching the maximum at 1.86 wt%Fe,resulting in the maximum ORR rate.Optimized Fe-N-P-C complex catalyst was used as the cathode catalyst in a homemade Zn-air battery and good performance of an energy density of 771 Wh kgZn^-1,a power density of 92.9 m W cm^-2 at 137 m A cm^-2 and an excellent durability were exhibited.     

Regulation of carbon distribution to construct high-sulfur-content cathode in lithium-sulfur batteries

Lithium-sulfur(Li-S)battery is regarded as one of the most promising next-generation energy storage systems due to the ultra-high theoretical energy density of 2600 Wh kg^-1.To address the insulation nature of sulfur,nanocarbon composition is essential to afford acceptable cycling capacity but inevitably sacrifices the actual energy density under working conditions.Therefore,rational structural design of the carbon/sulfur composite cathode is of great significance to realize satisfactory electrochemical performances with limited carbon content.Herein,the cathode carbon distribution is rationally regulated to construct high-sulfur-content and high-performance Li-S batteries.Concretely,a double-layer carbon(DLC)cathode is prepared by fabricating a surface carbon layer on the carbon/sulfur composite.The surface carbon layer not only provides more electrochemically active surfaces,but also blocks the polysulfide shuttle.Consequently,the DLC configuration with an increased sulfur content by nearly 10 wt%renders an initial areal capacity of 3.40 mAh cm^-2 and capacity retention of 83.8%during 50 cycles,which is about two times than that of the low-sulfur-content cathode.The strategy of carbon distribution regulation affords an effective pathway to construct advanced high-sulfur-content cathodes for practical high-energy-density Li-S batteries.     

Confined Ni-In intermetallic alloy nanocatalyst with excellent coking resistance for methane dry reforming

Carbon dioxide and methane are two main greenhouse gases which are contributed to serious global warming.Fortunately,dry reforming of methane(DRM),a very important reaction developed decades ago,can convert these two major greenhouse gases into value-added syngas or hydrogen.The main problem retarding its industrialization is the seriously coking formation upon the nickel-based catalysts.Herein,a series of confined indium-nickel(In-Ni)intermetallic alloy nanocatalysts(In_xNi@SiO₂)have been prepared and displayed superior coking resistance for DRM reaction.The sample containing 0.5 wt.%of In loading(In_0.5Ni@SiO₂)shows the best balance of carbon deposition resistance and DRM reactivity even after 430 h long term stability test.The boosted carbon resistance can be ascribed to the confinement of core–shell structure and to the transfer of electrons from Indium to Nickel in In-Ni intermetallic alloys due to the smaller electronegativity of In.Both the silica shell and the increase of electron cloud density on metallic Ni can weaken the ability of Ni to activate C–H bond and decrease the deep cracking process of methane.The reaction over the confined InNi intermetallic alloy nanocatalyst was conformed to the Langmuir-Hinshelwood(L-H)mechanism revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS).This work provides a guidance to design high performance coking resistance catalysts for methane dry reforming to efficiently utilize these two main greenhouse gases.     

铜合金中铜的示波滴定—四苯硼钠法

本文报道了铜合金中铜的示波滴定方法。样品酸溶后，用抗坏血酸还的Ｃｕ＾２＋为Ｃｕ＾＋，加入过量的四苯硼钠，在ＰＨ５－６的ＨＡｃ－ＮａＡｃ缓冲溶液中，定量形成Ｃｕ－ＴＰＢ沉淀，过量的ＴＰＢ＾－，以Ｔｌ＾＋标准溶液进行示波滴定，铜合金中共存元素不干扰测定。铜的测定回收率９９．８％－１００．１％。进行了多种铜合金中铜含量的测定，结果令人满意。     

Electrodeposition of nanocrystalline Ni–Cu alloy from environmentally friendly lactate bath

A new environmentally friendly electroplating bath for Ni–Cu alloy deposition was developed. Lactic acid was used as a complexing agent. The influence of bath composition, current density, pH and temperature on cathodic polarization, cathodic current efficiency and alloy composition was studied. Different proportions of the two metals were obtained by using different deposition parameters, but at all [Ni²⁺] / [Cu²⁺] ratios studied, preferential deposition of Cu occurred and regular co‐deposition took place. The Ni content of the deposit increased with Ni²⁺ content and current density and decreased with temperature. The surface morphology of the deposited Ni–Cu alloy was investigated using scanning electron microscopy. The crystal structure was examined using the X‐ray diffraction technique. The results showed that the deposits consisted of a single solid solution phase with a face‐centered cubic structure. The crystallite size lies in the range of 12 to 25 nm for as‐plated alloys. Copyright © 2014 John Wiley & Sons, Ltd.     

Detection of binuclear copper-caffeine complexes under electrospray ionization condition

A number of copper salts, Cu(OOCCH(3))(2), Cu(ClO(4))(2), Cu(NO(3))(2), CuCl(2) and CuSO(4) have been tested for their ability to form binuclear copper-caffeine complexes. The electrospray ionization (ESI) mass spectra of methanol solution containing caffeine and CuCl(2) or CuSO(4) show signals of two copper atom containing ions, so the signals correspond to binuclear complexes: [2Caf + Cu(2)SO(4)](+), [2Caf + Cu(2)](+), [2Caf + Cu(2)Cl](+), [2Caf + Cu(2)Cl(2)](+) and [2Caf + Cu(2)Cl(3)](+). Sulfate and chloride anion are characterized by charge densities higher than those of the carboxylate, nitrate and perchlorate anion. Thus, due to the electrostatic forces, the binuclear complexes containing SO(4)(2-) or Cl(-) can survive the transfer from solution to the gas phase and then can successfully be observed on ESI mass spectra. The ion [2Caf + Cu(2)Cl(3)](+) is present in solution and could be detected when using methanol/chloroform as solvent. The ions [2Caf + Cu(2)](+), [2Caf + Cu(2)Cl](+) and [2Caf + Cu(2)Cl(2)](+) are formed from the [2Caf + Cu(2)Cl(3)](+) ion (by subsequent loss of Cl atoms) on transfer from the solution to the gas phase or in the gas phase. The ion [2Caf + Cu(2)](+) does not contain a bridging agent, thus it is reasonable to assume that it contains a Cu-Cu bond.     

新型薄膜扩散梯度装置定量测量水环境中重金属形态

采用以纤维素透析膜为扩散相, 0.05 mol/L羧甲基纤维素钠(CMC)溶液为结合相的薄膜扩散梯度(DGT)装置(CMC-DGT)定量累积和测量水溶液中Cu²⁺, Cd²⁺和Pb²⁺的有效态; 考察了pH值和离子强度对CMC-DGT累积Cu²⁺, Cd²⁺和Pb²⁺的影响以及不同配体(乙二胺四乙酸二钠、 单宁酸和黄腐酸)对重金属有效态的影响; 测量了外加标的天然水和工业废水中重金属的有效态浓度; 并比较了不同结合相DGT装置对同一水体中重金属的有效态浓度. 实验结果表明, 0.05 mol/L CMC溶液对Cu²⁺, Cd²⁺和Pb²⁺累积容量分别为0.24, 0.11和0.45 mg/mL; 定量累积的最佳pH值范围分别为3.7～8.0, 4.7～9.0和4.7～8.0; 随着离子强度的增大, CMC-DGT对Cu²⁺, Cd²⁺和Pb²⁺的累积容量下降; CMC-DGT能够定量地累积配制水中的游离Cu²⁺, Cd²⁺和Pb²⁺, 回收率分别为92.1%, 100.6%和96.4%; 当有配体存在时, 随着配体浓度的增大, CMC-DGT测量的Cu²⁺, Cd²⁺和Pb²⁺有效态的浓度随之下降; 在过滤工业废水、 河水和湖水中, 不同结合相DGT装置对重金属有效态的测量值不同. 结果表明, CMC可作为DGT技术新的液态结合相.     

高活性甲醇氧化羰基化CuY催化剂的结构及催化活性中心

采用硝酸铜溶液和NaY分子筛溶液离子交换制备了CuY催化剂,通过加入氨水提高交换溶液的pH值以及高温焙烧活化,显著提高了甲醇氧化羰基化合成碳酸二甲酯的催化活性,与固相离子交换、沉积和浸渍法制备的催化剂相比,虽负载的铜量较低,但催化活性较高. 通过元素分析、XRD、H2-TPR、XPS和AES等对CuY催化剂微观结构的表征表明,在Cu(NO3)2离子交换溶液中加入氨水,促进了Cu2+离子交换的进行,提高了CuY催化剂的Cu交换量,并且交换的Cu2+主要落位于分子筛的超笼中. 在惰性气氛中焙烧活化CuY催化剂,Cu2+自还原为Cu+,氨促进了自还原过程的进行,显著提高了催化剂的活性. 焙烧活化温度越高,越有利于超笼中Cu2+→Cu+的自还原过程,使超笼中Cu+的含量增加, CuY催化活性增加. 进一步研究表明Y分子筛超笼中的Cu+是主要的催化活性中心.     

Nafion化学修饰圆盘预富集-石墨炉 原子吸收联用法对牛血超氧化物歧化酶中铜、锌分布状态的研究

本文研究了Nafion化学修饰钨丝圆盘预富集-石墨炉原子吸收(GFAAS)方法测定牛血超氧化物歧化酶(SOD)中游离态Cu～(2+)及Zn～(2+)的方法,并用GFAAS法直接测定SOD中铜、锌的总量,证实了牛血SOD中金属辅基铜、锌原子个数比为1:1,初步探讨了一定浓度的牛血SOD中Cu～(2+)、Zn～(2+)的表观离解平衡常数。为提高SOD的活性和稳定性的研究,提供了一种有效的方法。     

H3PO4改性PS-EDTA树脂对水相中Cu2+、Zn2+和Cd2+的吸附性能研究

大孔氯甲基化聚苯乙烯小球先后与乙二胺、2-氯乙酸反应得EDTA型螯合树脂(PS-EDTA),再用磷酸在室温处理得PS-EDTA/P树脂。PS-EDTA/P树脂被用于水相中Cu2+、Zn2+和Cd2+的吸附净化处理,探讨了溶液的pH值、初始金属离子浓度、时间、温度等因素对吸附性能的影响,并研究了其对重金属离子的吸附动力学和热力学。结果表明,PS-EDTA/P树脂对Cu2+和Zn2+的吸附符合Langmuir等温式、对Cd2+的吸附符合Freundlich等温式,准二级吸附动力学方程能够很好地描述3种金属离子在树脂上的吸附动力学行为。同时,PS-EDTA/P树脂对重金属吸附的热力学参数表明,PS-EDTA/P树脂对Cu2+、Zn2+和Cd2+的吸附是一个自发的、吸热的过程。已吸附Cu2+、Zn2+和Cd2+的树脂可以用0.1mol/L HCl解吸,解吸后的树脂对Cu2+、Zn2+和Cd2+仍具有较高的吸附量。     

CdTe/CdS荧光探针测定痕量铜(Ⅱ)

以巯基乙酸为稳定剂,在水溶液中合成CdTe/CdS量子点,基于量子点与Cu2+混合后发生荧光猝灭作用,建立CdTe/CdS量子点作为荧光探针检测微量铜的新方法。在pH 4.60的HAc-NaAc缓冲溶液中,反应时间为10 min时,Cu2+质量浓度在0.01～1.00μg/mL范围与CdTe/CdS量子点的荧光猝灭程度呈良好的线性关系,相关系数为0.9978,检出限为9.90×10-3μg/mL。方法可以用于雨水、自来水和延河水中Cu2+的分析。     

Cu(Ⅱ)印迹壳聚糖交联多孔微球去除水溶液中金属离子

研究了以Cu2+为模板的壳聚糖交联多孔微球(Cu-CSCPM)对溶液中Cu2+的吸附性能,为该材料应用于去除废水、果蔬汁等有毒重金属铜离子提供理论基础。首先制备了Cu2+印迹壳聚糖交联多孔微球,并表征了微球的一些物理化学性质;其次采用静态吸附法研究了该微球对Cu2+的吸附行为。结果发现,制得的微球表面多孔,含有活性-NH2,其含水量为69.59%,树脂骨架密度为1.22g/cm3,孔度值为73.68%,交联度为82.42%。初始浓度为60mmol/L、吸附温度40℃、pH=4.0时,Cu-CSCPM对Cu2+的饱和吸附容量为1.89mmol/g。Cu-CSCPM再生5次对Cu2+仍然具有较高吸附容量。     

Ni对Cu/ZnO基甲醇裂解催化剂的促进机制

通过XRD,BET,In-situ XPS等表征技术对Cu/ZnO基甲醇裂解制氢催化剂进行 了详细的研究。XRD结果表明,Cu-Zn合金的生成是Cu/ZnO基催化剂在反应初期快速 失活的主要原因;XRD,BET和N_2O滴定实验结果表明,Ni助剂可能是通过提高 Cu~0活性物种的分散度并维持Cu~0活性物种在催化反应过程中的稳定性而使 Cu/Zn/Ni催化剂的活性及稳定性大幅度提高。In-situ XPS结果表明,Ni助剂的加 入可以诱导Cu/Zn/Ni催化剂表面在甲醇裂解反应过程中出现Cu~+,从而由 Cu~0/Cu~+共同构成催化剂的活性中心,并最终导致Cu/Zn/Ni催化剂的高活性。