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.     

Characterizations and Photocatalytic Activities of Nanocrystalline MTiO3 （M = Sr, Pb, Co） Prepared via a General Self-propagating Combustion Method

Nanocrystalline MTiO3 (M=Sr, Pb, Co) were prepared by a general self-pro- pagating combustion method. The samples were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption and UV-vis diffuse reflectance spectra (DRS). The photocatalytic activity of MTiO3 (M=Sr, Pb, Co) was evaluated by the photocatalytic degradation of methyl orange (MO). MTiO3 (M=Sr, Pb, Co) having the same core element showed distinctly different photocatalytic activity due to the different coordinating atoms. Factors affecting the photocatalytic activity of MTiO3 (M=Sr, Pb, Co) were discussed. It was suggested that the structures of TiO6 octahedra and the electronic property were the predominant factors of the photocatalytic behavior for MTiO3 (M=Sr, Pb, Co).     

Formation of multinary intermetallics from reduction of perovskites by aluminum flux: M(3)Au(6+)(x)()Al(26)Ti (M = Ca, Sr, Yb), a stuffed variant of the BaHg(11) type

New intermetallic phases were synthesized by reacting oxidic perovskites and gold metal in aluminum flux. The combination of MTiO(3) (M = Ca, Sr, Ba) and Au metal in excess molten aluminum produces quaternary compounds M(3)Au(6+)(x)()Al(26)Ti with a stuffed BaHg(11) structure type. An analogue with M = Yb was also synthesized; it shows mixed valent behavior.     

Quasi-linear dependence of cation filling on the photocatalysis of A(x)BO3-based tunnel compounds

A series of A(x)BO(3)-based oxides, (A1)(4)(A2)(2)(A3)(4)Nb(10)O(30) (A1 = Sr, Ba; A2 = Na, K; A3 = □) as deficient perovskites, ATiO(3) (A = Mg, Ca, Sr, Ba) as ideal perovskites are prepared by solid-state reaction method, and investigated as novel tunnel photocatalysts. The efficiency exhibits a high dependence on the cation filling in the respective tunnels of these compounds. Generally, lower cation filling contributes to a higher activity. The cation filling is rationalized by the crystal packing factor (PF), the photocatalytic efficiency decreases quasi-linearly with PF. Moreover, the linear correlation also exists in the literature involving tunnel photocatalysts of Bi(2)RNbO(7) (R = Y, rare earth element), MIn(2)O(4) (M = Ca, Sr, Ba), ATaO(3) (A = Li, Na, K), etc. Such linear correlation of photocatalysis with the crystal structure has not been reported in the literature. The study of structure-modification by controlling cation-filling for improving activity sheds light on the mechanism of photocatalysis and on developing new high-performance photocatalysts.     

钙钛矿型(La_(0.8)M_(0.2))MnO_3和(La_(0.8)Sr_(0.2))(Mn_(1-x)Fe_x)O_3的XRD和IR光谱的研究

合成了（La0.8M0.2）MnO3（M=Ca2+，Sr2+，Ba2+）和（La0.8Sr0.2）（Mn1-xFex）O3（x=0．1、0．2、0．3、0．4、0．5）两类氧化物，经XRD确认为钙铁矿型氧化物，应用FT－IR对其进行研究，对主要的红外特征振动υ（Mn-O）和δ（O-Mn-O）进行分析表征。这类化合物的υ（Mn-O）和δ（O-Mn-O）的FT－IR特征吸收峰十分相似，但在～608cm－1处出现较大差别，以Sr2+、Ca2+和Ba2+部分A位取代La3+的钙铁矿型氧化物和B位Fe取代Mn时，由于离子的溶解能不同，对晶格的有序排列的影响程度不一，导致了Mn－O键的键力场不同，引起了吸收峰向低波数移动。这种结构上的差异，导致对汽车尾气中的有害成份碳氢化合物（HC）和一氧化碳（CO）的催化氧化能力降低。借此可以用于研究结构与催化性能的关系。     

M5(PO4)3F (M=Ca, Sr, Ba)中Sm3+的电荷迁移态及Sm3+和Eu3+的电荷迁移能量关系

采用高温固相反应合成了M_5-2xSm_xNa_x(PO₄)₃F(M=Ca,Sr,Ba)荧光体,研究了其在真空紫外-可见光范围的发光特性。发现在Ca₅(PO₄)₃F中Sm³⁺的电荷迁移带约在191 nm,在Sr₅(PO₄)₃F中约在199 nm,而在Ba₅(PO₄)₃F中约在204 nm,随着被取代碱土离子半径的增大电荷迁移能量逐渐减小。比较了M₅(PO₄)₃F (M=Ca,Sr,Ba)中Sm³⁺和Eu³⁺电荷迁移能量的关系。     

Synthesis and Characterization of Polyether Adducts of Barium and Strontium Carboxylates and Their Use in the Formation of MTiO(3) Films

The synthesis, characterization, and reactivity of new polyether adducts of strontium and barium carboxylates of general composition M(O(2)CCF(3))(n)()(L) (M = Ba, L = 15-crown-5, (1); M = Ba (2), Sr (3), respectively, with L = tetraglyme are reported. The compounds were synthesized by reaction of BaCO(3) or MH(2) (M = Sr or Ba) with organic acids in the presence of the polyether ligands. These compounds have been characterized by IR and (13)C and (1)H NMR spectroscopies, elemental analyses, and thermogravimetric analysis. The species Ba(2)(O(2)CCF(3))(4)(15-crown-5)(2) (1) and [Ba(2)(O(2)CCF(3))(4)(tetraglyme)](infinity) (2), were also characterized by single-crystal X-ray diffraction. Ba(2)(O(2)CCF(3))(4)(15-crown-5)(2) (1) crystallizes in the orthorhombic space group Cccm with cell dimensions of a = 13.949(1) ?, b = 19.376(2) ?, c = 16.029(1) ?, and Z = 8. [Ba(2)(O(2)CCF(3))(4)(tetraglyme)](infinity) (2) crystallizes in the monoclinic space group C2/c with cell dimensions of a = 12.8673(12) ?, b = 16.6981(13) ?, c = 15.1191(12) ?, beta = 99.049(8) degrees, and Z = 4. Compounds 1-3 thermally decompose at high temperatures in the solid state to give MF(2). However, solutions of compounds 1-3 dissolved in ethanol with Ti(O-i-Pr)(4) give crystalline perovskite phase MTiO(3) films, or in the case of mixtures of 2 and 3, Ba(1)(-)(x)()Sr(x)()TiO(3) films below 600 degrees C when spin coated onto silicon substrates and thermally treated. The crystallinity, purity, and elemental composition of the films was determined by glancing angle X-ray diffraction and Auger electron spectroscopy.     

Characterization of metal binding properties of rhamnogalacturonan II from plant cell walls by size-exclusion HPLC/ICP-MS.

The binding properties of metal ions to a pectic polysaccharide, rhamnogalacturonan II (RG-II), from plant cell walls were analyzed by size-exclusion HPLC/ICP-MS. The dimeric RG-II borate complex (dRG-II-B) from sugar beet and red wine contained 0.8 - 1.1 mol/mol of B, 0.8 - 1.1 mol/mol of Ca, 0.1 - 0.3 mol/mol of Sr, and 0.03 - 0.07 mol/mol of Ba. The treatment of dRG-II-B with Sr2+, Ba2+, Pb2+ or La3+ exchanged the originally present Ca, Sr and Ba. In contrast, monomeric RG-II (mRG-II), which contained approximately 0.1 mol/mol of Ca, formed complexes with La3+, Eu3+, and Lu3+ added to the solution, but did not do so with Ca2+, Sr2+, Ba2+ and Pb2+. The HPLC/ICP-MS and HPLC/RI (refractive index detector) analysis of the partially hydrolyzed mRG-II that was treated with La3+ indicated that the side chains and backbone of mRG-II together form a lanthanoid binding site.     

Elaboration of nano titania-magnetic reduced graphene oxide for degradation of tartrazine dye in aqueous solution

In this paper, magnetic nanocomposites are synthesized by loading reduced graphene oxide (RG) with two components of nanoparticles consisting of titanium dioxide (TiO₂) and magnetite (Fe₃O₄) with varying amounts. The structural and magnetic features of the prepared composite photocatalysts were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectra (UV–vis/DRS), Raman and vibrating sample magnetometer (VSM). The resulting TiO₂/magnetite reduced graphene oxide (MRGT) composite demonstrated intrinsic visible light photocatalytic activity, on degradation of tartrazine (TZ) dye from a synthetic aqueous solution. Specifically, it exhibits higher photocatalytic activity than magnetite reduced graphene oxide (MRG) and TiO₂ nanoparticles. The photocatalytic degradation of TZ dye when using MRG and TiO₂ for 3 h under visible light was 35% and 10% respectively, whereas for MRGT it was more than 95%. The higher photocatalytic efficiency of MRGT is due to the existence of reduced graphene oxide and magnetite which enhances the photocatalytic efficiency of the composite in visible light towards the degradation of harmful soluble azo dye (tartrazine).     

Solvent Extraction of Alkaline Earths with 1-Phenyl -3-Methyl 4 Stearoylpyrazol - 5 - One and Topo

Abstract

The synergic extraction of Ca, Sr, and Ba ions from aqueous solutions into cyclohexane or benzene containing 1- pheny 1 - 3 - methyl - 4 - stearoylpyrazol - 5 - one (HPMSP) and TOPO has been studied. Quantitative extraction (log D>2) was attained at pH>5.4 for Ca, pH>6.5 for Sr, and pH>7.3 for Ba when cyclohexane containing 0.05 M HPMSP and 0.01 M TOPO was used, and the corresoponding values for benzene were 6.5, 7.8, and 8.4. Extracted species were M(PMSP)₂(TOPO)₃ (M=Ca, Sr, Ba) for cyclohexane and Ca(PMSP)₂(TOPO)₃ and Sr (or Ba) (PMSP)₂(TOPO)₂ for benzene.     

Eu3+在碱土金属卤磷酸盐中的格位对称性及电荷迁移态

在254nm紫外光激发下研究了Eu~(3+)在Sr_3Ca_2(PO_4)_3Cl基质中的发光光谱.以Eu~(3+)为结构探针测定了Eu~(3+)所处晶格的点对称性.研究了M_5(PO_4)_3X(M=Ca,Sr,Ba;X=F,Cl,Br)基质组成改变对Eu~(3+)电荷迁移态的影响,以及温度对Ca_5(PO_4)_3Cl:Eu~(3+)发光强度的影响.