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.     

Designing a Perylene Diimide/Fullerene Hybrid as Effective Electron Transporting Material in Inverted Perovskite Solar Cells with Enhanced Efficiency and Stability

Electron transport materials (ETM) play an important role in the improvement of efficiency and stability for inverted perovskite solar cells (PSCs). This work reports an efficient ETM, named PDI‐C₆₀, by the combination of perylene diimide (PDI) and fullerene. Compared to the traditional PCBM, this strategy endows PDI‐C₆₀ with slightly shallower energy level and higher electron mobility. As a result, the device based on PDI‐C₆₀ as electron transport layer (ETL) achieves high power conversion efficiency (PCE) of 18.6 %, which is significantly higher than those of the control devices of PCBM (16.6 %) and PDI (13.8 %). The high PCE of the PDI‐C₆₀‐based device can be attributed to the more matching energy level with the perovskite, more efficient charge extraction, transport, and reduced recombination rate. To the best of our knowledge, the PCE of 18.6 % is the highest value in the PSCs using PDI derivatives as ETLs. Moreover, the device with PDI‐C₆₀ as ETL exhibits better device stability due to the stronger hydrophobic properties of PDI‐C₆₀. The strategy using the PDI/fullerene hybrid provides insights for future molecular design of the efficient ETM for the inverted PSCs.     

An Azaacene Derivative as Promising Electron‐Transport Layer for Inverted Perovskite Solar Cells

It is highly desirable to develop novel n‐type organic small molecules as an efficient electron‐transport layer (ETL) for the replacement of PCBM to obtain high‐performance metal‐oxide‐free, solution‐processed inverted perovskite solar cells (PSCs) because this type of solar cells with a low‐temperature and solution‐based process would make their fabrication more feasible and practical. In this research, the new azaacene QCAPZ has been synthesized and employed as non‐fullerene ETL material for inverted PSCs through a solution‐based process without the need for additional dopants or additives. The as‐fabricated inverted PSCs show a power conversion efficiency up to 10.26 %. Our results clearly suggest that larger azaacenes could be promising electron‐transport materials to achieve high‐performance solution‐processed inverted PSCs.     

TiO_2 nanoparticle-based electron transport layer with improved wettability for efficient planar-heterojunction perovskite solar cell

The electron transport layer(ETL) plays an important role in planar heterojunction perovskite solar cell(PSCs),by affecting the light-harvesting, electron injection and transportation processes, and especially the crystallization of perovskite absorber. In this work, we utilized a commercial TKD-TiO_2 nanoparticle with a small diameter of 6 nm for the first time to prepare a compact ETL by spin coating. The packing of small-size particles endowed TKD-TiO_2 ETL an appropriate surface-wettability, which is beneficial to the crystallization of perovskite deposited via solution-processed method. The uniform and high-transmittance TKD-TiO_2 films were successfully incorporated into PSCs as ETLs. Further careful optimization of ETL thickness gave birth to a highest power conversion efficiency of 11.0%, which was much higher than that of PSC using an ETL with the same thickness made by spray pyrolysis. This TKD-TiO_2 provided a universal solar material suitable for the further large-scale production of PSCs. The excellent morphology and the convenient preparation method of TKD-TiO_2 film gave it an extensive application in photovoltaic devices.     

Copper-copper iodide hybrid nanostructure as hole transport material for efficient and stable inverted perovskite solar cells

A CuI coated Cu hybrid nanostructure by partial iodation of Cu nanowires was used as hole transport material(HTM) to enhance the charge transfer in inverted perovskite solar cells(PSCs). The outer CuI achieved efficient charge extraction, and the inner copper facilitated the extracted charges to be rapidly transferred, further improving the overall cell performance. Furthermore,we employed a mixture of [6,6]-phenyl-C71-butyric acid methyl ester(PCBM) and ZnO nanoparticles as electron transport material(ETM) to achieve the fabrication of stable PSCs. The best efficiency was up to 18.8%. This work represents a fundamental clue for the design of efficient and stable PSCs using the chemical in-situ construction strategy for HTM and integration of PCBM and ZnO as ETM.     

Bowl-Assisted Ball Assembly for Solvent-Processing the C60 Electron Transport Layer of High-Performance Inverted Perovskite Solar Cell

Pristine fullerene C₆₀ is an excellent electron transport material for state-of-the-art inverted structure perovskite solar cells (PSCs), but its low solubility leaves thermal evaporation as the only method for depositing it into a high-quality electron transport layer (ETL). To address this problem, we herein introduce a highly soluble bowl-shaped additive, corannulene, to assist in C₆₀-assembly into a smooth and compact film through the favorable bowl-ball interaction. Our results show that not only corannulene can dramatically enhance the film formability of C₆₀, it also plays a critical role in forming C₆₀-corannulene (CC) supramolecular species and in boosting intermolecular electron transport dynamics in the ETL. This strategy has allowed CC devices to deliver high power conversion efficiencies up to 21.69 %, which is the highest value among the PSCs based on the solution-processed-C₆₀ (SP-C₆₀) ETL. Moreover, the stability of the CC device is far superior to that of the C₆₀-only device because corannulene can retard and curb the spontaneous aggregation of C₆₀. This work establishes the bowl-assisted ball assembly strategy for developing low-cost and efficient SP-C₆₀ ETLs with high promise for fully-SP PSCs.     

High-Efficiency Perovskite Solar Cells Enabled by Anatase TiO2 Nanopyramid Arrays with an Oriented Electric Field

One-dimensional (1D) nanostructured oxides are proposed as excellent electron transport materials (ETMs) for perovskite solar cells (PSCs); however, experimental evidence is lacking. A facile hydrothermal approach was employed to grow highly oriented anatase TiO₂ nanopyramid arrays and demonstrate their application in PSCs. The oriented TiO₂ nanopyramid arrays afford sufficient contact area for electron extraction and increase light transmission. Moreover, the nanopyramid array/perovskite system exhibits an oriented electric field that can increase charge separation and accelerate charge transport, thereby suppressing charge recombination. The anatase TiO₂ nanopyramid array-based PSCs deliver a champion power conversion efficiency of approximately 22.5 %, which is the highest power conversion efficiency reported to date for PSCs consisting of 1D ETMs. This work demonstrates that the rational design of 1D ETMs can achieve PSCs that perform as well as typical mesoscopic and planar PSCs.     

High‐Efficiency Perovskite Solar Cells Enabled by Anatase TiO2 Nanopyramid Arrays with an Oriented Electric Field

One‐dimensional (1D) nanostructured oxides are proposed as excellent electron transport materials (ETMs) for perovskite solar cells (PSCs); however, experimental evidence is lacking. A facile hydrothermal approach was employed to grow highly oriented anatase TiO₂ nanopyramid arrays and demonstrate their application in PSCs. The oriented TiO₂ nanopyramid arrays afford sufficient contact area for electron extraction and increase light transmission. Moreover, the nanopyramid array/perovskite system exhibits an oriented electric field that can increase charge separation and accelerate charge transport, thereby suppressing charge recombination. The anatase TiO₂ nanopyramid array‐based PSCs deliver a champion power conversion efficiency of approximately 22.5 %, which is the highest power conversion efficiency reported to date for PSCs consisting of 1D ETMs. This work demonstrates that the rational design of 1D ETMs can achieve PSCs that perform as well as typical mesoscopic and planar PSCs.     

Eliminating Hysteresis of Perovskite Solar Cells with Hollow TiO2 Mesoporous Electron Transport Layer

Current density-voltage(J-V) hysteresis issue caused by unbalanced charge transport has greatly limited the improvement of power conversion efficiency(PCE) of halide perovskite solar cells(PSCs). Herein, hollow TiO₂ mesoporous electron transport layer(ETL) was used to fabricate PSCs. The structure-dependent charge collection as well as its effect on PCE and hysteresis impactor(HI) of PSC were investigated. The results demonstrate that TiO₂ hollow spheres in a size of around 50 nm (HS-50) can form a high quality perovskite/ETL interface with a less trap density. Moreover, the hollow TiO₂ with the thin shell can help promote the extraction of electrons from perovskite layer to ETL, so as to reduce the charge accumulation and recombination at the perovskite/ETL interface and alleviate the hysteresis behavior. As a result, PSCs with HS-50 TiO₂ delivered a champion PCE of 16.81% with a small HI of 0.0297, indicating a better performance than the commercial P25(PCE of 15.87%, HI of 0.2571).     

Crystallographic Understanding of Photoelectric Properties for C60 Derivatives Applicable as Electron Transporting Materials in Perovskite Solar Cells

Hundreds of C₆₀ derivatives stand out as electrontransporting materials(ETMs), for example, in perovskite solar cells(PSCs), due to their properties on electron extraction or defect passivation. However, it still lacks of guidelines to update C₆₀-based ETMs with excellent photoelectric properties. In this work, crystallographic data of eight C₆₀-based ETMs, including pristine C₆₀ and the well-known PCBM as well as six newly synthesized fullerenes, are analyzed to establish the connections between derivatized structures and photoelectric properties for the typical carbon cluster of C₆₀. In terms of packing centroid-centroid distance between neighboring carbon cages, the crystallographic data are useful for probing photoelectric properties, such as electrochemical properties, electron mobility and photovoltaic performances, and therefore facilitate to design novel C₆₀-based ETMs for PSCs with high performances.     

A mini review: Constructing perovskite p-n homojunction solar cells

Organic metal halide perovskite materials have excellent photoelectric properties, and the power conversion efficiency(PCE) of the perovskite solar cells(PSCs) has increased from 3.8% to more than 25%. In the development of PSCs, innovative architectures were being proposed constantly. However, the use of the electron transport layer(ETL) and hole transport layer(HTL) increases manufacturing costs and process complexity. Perovskite material has ambipolar charge transport characteristics, so it c...