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.     

原位反应法制备镍三乙烯四胺配合物/蒙脱土纳米复合体

将蒙脱土的硅酸盐晶层空间作为微反应场所,用微波加热先将钠基蒙脱土转化为镍基蒙脱土,再引入三乙烯四胺配体,使配体与镍离子在蒙脱土层间原位发生配位反应,制得配合物/蒙脱土纳米复合体.XRD结果表明蒙脱土的层间距在引入三乙烯四胺后明显变大.紫外可见漫反射光谱、热分析和元素分析结果表明三乙烯四胺与N i2+离子在蒙脱土层间形成了配合物.     

Mixed Al/Ce oxide pillaring of montmorillonite: XRD and UV-VIS diffuse reflectance study

Ce and Al pillared clays were prepared by (i) pillaring Ce³⁺-exchanged montmorillonite with Al₁₃ polycation (Ce-Al-PILC) and (ii) by pillaring Na-montmorillonite with an oligomer obtained from cohydrolysis of Ce³⁺ and Al³⁺ salts (Al-Ce-PILC). Cohydrolyzed oligomer gives larger intercalating species with Ce³⁺ incorporated in it. The UV-DRS spectrum of clay sample intercalated with this species shows four distinct absorption bands at 224, 263, 294 and 342 nm, which are attributed to the 4f-5d interconfigurational transitions of Ce³⁺ ions associated with alumina pillars.     

Adsorption of barium(II) on montmorillonite: an EXAFS study

Migration of radioactive radium, ²²⁶Ra, in soil is an environmental concern, especially in areas adjacent to uranium processing facilities. Barium(II), as Ba²⁺, was used as a Ra analog and reacted with a Na-montmorillonite to obtain mechanistic insights into the interaction of Ra with soil matrices. The majority of sorbed Ba is associated with the permanently charged surface sites on the montmorillonite basal surface. This is indicated by the facts that (1) sorption of Ba(II) on montmorillonite is not highly sensitive to solution pH, although an increase of sorption was observed at higher pH values; and (2) displacement of sorbed Ba increased with increased NaNO₃ concentration. As demonstrated by EXAFS, a small fraction of Ba also adsorbed on the montmorillonite edge, forming an inner-sphere surface complex through sharing of oxygen atom(s) from deprotonated –OH group of the Al octahedral layer. The EXAFS measured distances between Ba and O at the first shell, and Ba and Al of the second shell are 2.7–2.8 and 3.7–3.9 Å, respectively, consistent with the results from geometry of a inner-sphere complex at the edge site. Results from bulk experiments and spectroscopic analysis suggest a co-existence of outer- and inner-sphere surface complexes for Ba sorbed to the montmorillonite surface.     

TEM, XRD, and thermal stability of adsorbed paranitrophenol on DDOAB organoclay

Water purification is of extreme importance to modern society. Organoclays through adsorption of recalcitrant organics provides one mechanism for the removal of these molecules. The organoclay was synthesised through ion exchange with dimethyldioctadecylammonium bromide labeled as DDOAB of formula (CH3(CH2)17)2NBr(CH3)2. Paranitrophenol (pnp) was adsorbed on the organoclay at a range of concentrations according to the cation exchange capacity (CEC) of the host montmorillonite. The paranitrophenol in solution was analysed by a UV-260 spectrophotometer at 317 nm, with detection limits being 0.05 mg/L. The expansion of the montmorillonite was studied by a combination of X-ray diffraction and transmission electron microscopy. Upon adsorption of the paranitrophenol the basal spacing decreased. The thermal stability of the organoclay was determined by a combination of thermogravimetry and infrared emission spectroscopy. The surfactant molecule DDOAB combusts at 166, 244, and 304 degrees C and upon intercalation into Na-montmorillonite is retained up to 389 degrees C thus showing the organoclay is stable to significantly high temperatures well above the combustion/decomposition temperature of the organoclay.     

反应温度对蒙脱石载银量及其缓释性能的影响

以钠基蒙脱石(Na-MMT)为载体,氧化银与氨水反应形成的银氨络合物[Ag(NH₃)₂OH]为前驱体,通过离子交换和三乙醇胺(TEA)还原两步法制备了载银蒙脱石(Ag-MMT)。 用佛尔哈德法测定了载银蒙脱石(Ag-MMT)的载银量,探讨了反应温度对MMT 载银量及其缓释性能的影响,并用FI-IR、XRD等技术手段对Na-MMT和Ag-MMT的结构进行了表征。 结果表明,在蒙脱石与Ag⁺的质量比为20:1、离子交换时间为1 h、反应温度50 ℃,然后再加入三乙醇胺和聚乙烯吡咯烷酮,50 ℃下反应2 h,MMT的载银量最大,银的利用率达到86.89%,释放时间最持久,并且MMT的层状结构没有被破坏。     

Determination of structural modification in acid activated montmorillonite clay by FT-IR spectroscopy

The structural modifications and the Bronsted acid sites generated during the acid treatment of montmorillonite clay with varied concentration of sulphuric acid was determined using FT-IR spectroscopy. Octahedral sheet is affected at low acid concentration resulting into the dissolution of cations; among them Mg2+ cations are prone to dissolve than Fe2+/3+ and Al3+. Tetrahedral sheet is affected at higher acid concentration. The partial substitution of octahedral Al3+ by Mg2+ or Fe2+/3+ cations and the presence of other non-smectite minerals such as kaolinites was also been clearly identified, thus making FT-IR spectroscopy as a rapid technique for monitoring the structural features of montmorillonite clay.     

Swelling Capacity of Montmorillonite in the Presence of Electrolytic Ions

The aim of this study was to investigate the effect of inorganic cations (Na⁺, Ca²⁺, Ba²⁺, Fe³⁺, Al³⁺) with different valence and concentration on the swelling behaviors of montmorillonite. Na-montmorillonite, obtained from China, was chosen as experimental objective. It was first characterized through the measurements of swelling capacity and zeta potential. Then, swelling properties of Na-montmorillonite influenced by cation concentration, valence, and hydration analyzed were studied. The results showed that the swelling capacity was much inhibited by cations of higher concentrations, higher valences, or weaker hydration. This work also verified the conclusion that the decreased degree of potential is more significant caused by cations of higher valence.     

Sorption/desorption of radionickel on/from Na-montmorillonite: kinetic and thermodynamic studies

In this work, Na-montmorillonite was used as a novel adsorbent for the sorption of Ni(II) from aqueous solutions. The sorption and desorption of Ni(II) on Na-montmorillonite was investigated as the function of pH, ionic strength, Ni(II) concentrations and temperature. The results indicated that the sorption of Ni(II) on Na-montmorillonite was strongly dependent on pH, ionic strength and temperature. The sorption of Ni(II) increases slowly from 22.1 to 51.4% at pH range 2–6.5, abruptly at pH 6.5–9, and at last maintains high level with increasing pH at pH > 9 in 0.1 mol/L NaNO₃ solutions. The Ni(II) kinetic sorption on Na-montmorillonite was fitted by the pseudo-second-order model better than by the pseudo-first-order model and the experimental data implies that Ni(II) sorption on montmorillonite were mainly controlled by the film diffusion mechanism. The Langmuir, Freundlich and D–R models were used to simulate the sorption data at three different temperatures (298.15, 318.15 and 338.15 K) and the results indicated that Langmuir model simulates the experimental data better than Freundlich and D–R models. The sorption–desorption isotherm of Ni(II) on montmorillonite suggested that the sorption is irreversible. The irreversible sorption of Ni(II) on montmorillonite indicates that montmorillonite can be used to pre-concentration and solidification of Ni(II) from large volumes of solution and to storage Ni(II) ions stably.     

水化Na-蒙脱石和Na/Mg-蒙脱石的分子动力学模拟

利用分子动力学方法(MD)研究了Na-蒙脱石和Na/Mg-蒙脱石层间的补偿阳离子和水分子的结构及扩散性质. 模拟结果表明, 在一定水含量范围内Na-蒙脱石和Na/Mg-蒙脱石表现出不同的膨胀形式, 特别是层间水分子数目在48～72之间时, Na/Mg-蒙脱石的层间距比Na-蒙脱石有较为明显的增大. Na/Mg-蒙脱石两层水化物的层间水分子与Mg2+形成了明显的两层水合壳; 而与Na+只形成了一层平面的水合壳. 在Na/Mg-蒙脱石中, Na+和 Mg2+的扩散方式不同, Na+的扩散范围相对更广, 自扩散系数更大. Na/Mg-蒙脱石比相同水含量下的Na-蒙脱石层间水的自扩散系数小. 由于Mg2+和Na+对层间结构的强烈影响, 从而使有少量Mg2+取代Na+的Na/Mg-蒙脱石与Na-蒙脱石表现出不同的膨胀性质和层间物质的扩散性质.     

羟基铝溶液及铝交联蒙脱土的研究

本文用(27)~Al NMR法和8-羟基喹啉萃取法分别研究了羟基铝溶液中十三聚铝含量的变化规律,还用X-射线衍射法研究了铝交联蒙脱土d_(001)的变化。研究结果表明,铝离子的聚合情况主要由羟铝比决定,而浓度影响不大。随着羟铝比的增加,溶液中单核铝离子含量减少,十三聚铝离子相对含量增加,所得铝交联蒙脱土的d_(001)也随之增大。参照这些变化规律、控制羟基铝溶液的组成,可以制备各种层柱状铝交联蒙脱土复合物。