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The electrocatalytic reduction of nitrogen (N2) to ammonia (NH3) has broad prospects for green and sustainable NH3 production. Due to the electrocatalytic nitrogen reduction reaction (eNRR) performance of transition metal compound may be restricted with low yield rate, we develop transition metal interface engineering to improve the eNRR performance. Although the edge of MoS2 catalyst is active, the MoS2(0 0 1) surface is inert for N2 electroreduction. Through the hydrothermal and electrodeposition methods, Fe(OH)3 as N2 and H+ channels coated on MoS2 nanosheets array (MoS2@Fe(OH)3/CC) is synthesized. Such catalyst exhibits excellent eNRR performance in 0.1 M Na2SO4 with high Faradaic efficiency (2.76%) and NH3 yield rate (4.23 × 10−10 mol s−1 cm−2) at − 0.45 V (vs. RHE). This work may provide a new electrocatalyst synthesis pathway for artificial N2 fixation. Density functional theory calculations show that electrodeposition Fe(OH)3 can accelerate eNRR process rate of MoS2.

Electronics are becoming smaller and more versatile, and the size of solder joints has decreased to tens of microns, inducing obvious inhomogeneity among the phases in the solder matrix microstructure. In this study, the influence of phase inhomogeneity on the mechanical behavior of microscale Cu/Sn–58Bi/Cu solder joints was studied. Sn and Bi single-phase solid solution samples with the same composition as the Sn and Bi phases in the Sn58Bi microstructure were prepared, and their mechanical performances, elastic constants, and power-law constitutive models were measured, calculated, and identified. Based on the obtained mechanical performances, elastic constants, and power-law constitutive models, a three-dimensional finite element model of line-type Cu/Sn58Bi/Cu microscale solder joints, including their microstructure, was established. The results demonstrate that phase inhomogeneity increases the maximum value of von Mises stress, leading to stress concentration. When the Sn58Bi solder matrix transfers from the elastic deformation stage to the plastic deformation stage, the high σeq zone of the matrix gradually shifts from the Sn phase to the Bi phase. In addition, a study of the anisotropy reveals that the elastic anisotropic mechanical properties of Sn58Bi solder matrix are mainly affected by the anisotropic effect of Sn. The stress concentration is the lowest when the crystal orientation is π/2.

The development of stable, low-cost, and highly efficient electrocatalysts for the N2 reduction reaction (NRR) process is challenging but crucial for ammonia production. Herein, we demonstrate the synthesis of pyrite nanoparticles wrapped by graphene oxide (FeS2@GO) acting as a highly efficient NRR catalyst in a wide pH range. The FeS2 nanoparticles are uniformly dispersed across the GO nanosheet, thus leading to the fine exposure of active sites, the promotion of charge transfer, and the increment of a contact surface area, which are all beneficial for a desired catalyst. In the meantime, the low-coordinated Fe atoms are activated as highly active sites, which is in favor of the enhanced electrochemical performance for the NRR. Furthermore, density functional theory (DFT) calculations illustrated that the high activity of N2 reduction over the FeS2@GO catalyst arises from the well-exposed Fe active sites and the increment of charge density at the valence band edge. Benefiting from the well-optimized interface, the barrier of the addition of the first hydrogen atom to N2 forming *NNH species as the potential-determining step is as low as 0.93 eV in N2 electroreduction. The electrochemical test results reveal that, as expected, FeS2@GO exhibits high Faradaic efficiencies (4.7% in 0.1 M HCl solution and 6.8% in 0.1 M Na2SO4 solution) and advanced NH3 yields (78.6 and 27.9 μg h-1 mgcat.-1 in 0.1 M HCl and 0.1 M Na2SO4 solutions, respectively) in both acid and neutral conditions. This work offers a new avenue for exploring novel electrocatalysts, which has great promise to accelerate the practical application of the NRR.

The nitrogen reduction reaction (NRR) has become an ideal alternative to the Haber‐Bosch process, as NRR possesses, among others, the advantage of operating under ambient conditions and saving energy consumption. The key to efficient NRR is to find a suitable electrocatalyst, which helps to break the strong N≡N bond and improves the reaction selectivity. Molybdenum disulfide (MoS2) as an emerging layered two‐dimensional material has attracted a mass of attention in various fields. In this minireview, we summarize the optimization strategies of MoS2‐based catalysts which have been developed to improve the weak NRR activity of primitive MoS2. Some theoretical predictions have also been summarized, which can provide direction for optimizing NRR activity of future MoS2‐based materials. Finally, an outlook about the optimization of MoS2‐based catalysts used in electrochemical N2 fixation are given.

Developing non-noble-metal electrocatalyst with efficient and durable activity is a urgent task for addressing the sluggish reaction kinetics of electrochemical water oxidation. Structural evolution of the electrocatalyst is an important strategy for achieving enhanced performance. Herein, in situ evolution of surface Co2CrO4 to CoOOH/CrOOH (CoOOH/CrOOH-Co2CrO4) by an electrochemical method under alkaline conditions was designed for enhancing the electrocatalytic performance of water oxidation. The experiments demonstrated that the synergy between CoOOH/CrOOH and Co2CrO4 resulted in a marked increase in the number of active sites and improved the rate of charge transfer, which enhanced the activity for water oxidation. At a geometrical current density of 20 mA cm−2, the overpotential of the oxygen evolution reaction was 244 mV and the turnover frequency was 0.536 s−1 in 1.0 M NaOH.

A visible-light-driven self-powered photoelectrochemical (PEC) aptasensor was developed for ampicillin (AMP) detecting based on carbon dots (CDs) hybrid MIL-68(In)-derived In2O3 In2S3 hollow tubular heterojunction (CDs/In2O3 In2S3). In2S3 nanosheets uniformly grew in-situ on the surface of In2O3 hollow tubes, forming a close contact heterogeneous interface, which significantly promoted the transfer and separation of photo-generated carriers, and provided a large specific surface area and rich active sites for the PEC aptasensing platform. Furthermore, the CDs/In2O3 In2S3/ITO electrode, which was obtained by dipping assembly, showed remarkable and stable photoelectric signals at zero-bias under visible light irradiation. The amino-functionalized AMP aptamer was fixed on the working electrode as a biological recognition element, and the concentration of AMP was determined by observing the change in photocurrent intensity caused by the specific capture of AMP molecules in solution. Under optimized conditions, the developed PEC aptasensor displayed a relatively wide linear range from 0.001 ng mL−1 to 300 ng mL−1, as well as a low detection limit (LOD) of 0.06 pg mL−1. Besides, the novel self-powered PEC AMP-aptasensor exhibited excellent reproducibility, good stability and selectivity, which open a potential avenue for antibiotic residues detection in environmental media.

Surface engineering of electrochemiluminescence (ECL) emitters with capping agents is highly important, yet it remains a challenge. Herein, using N-acetyl-L-cysteine and cysteamine as model capping...

Computational simulations and high-temperature measurements of velocities near the surface of a mold were carried out by using the rod deflection method to study the effects of various operating parameters on the flow field in slab continuous casting (CC) molds with narrow widths for the production of automobile exposed panels. Reasonable agreement between the calculated results and measured subsurface velocities of liquid steel was obtained under different operating parameters of the CC process. The simulation results reveal that the flow field in the horizontal plane located 50 mm from the meniscus can be used as the characteristic flow field to optimize the flow field of molten steel in the mold. Increases in casting speed can increase the subsurface velocity of molten steel and shift the position of the vortex core downward in the downward circulation zone. The flow field of liquid steel in a 1040 mm-wide slab CC mold can be improved by an Ar gas flow rate of 7 L·min−1 and casting speed of 1.7 m·min−1. Under the present experimental conditions, the double-roll flow pattern is generally stable at a submerged entry nozzle immersion depth of 170 mm.

A novel ratiometric electrochemical (EC) sensing platform was established for sensitive immunoassay of target cytokeratin 19 fragment 21-1 (CYFRA21-1) biomarker by combining competitive immunoreact...

Inverted perovskite solar cells (i-PSCs) manifest negligible hysteresis and potential to construct tandem solar cells attracting much attention, but their power conversion efficiency (PCE) still lags behind those of conventional ones due to non-radiative recombination from defect states and mismatched energy-level alignment for electron transport. Herein, we report on employing a hydroxylated non-fullerene acceptor (NFA), termed IT-DOH, to modify the interface between the perovskite and the electron transport layer (ETL) for reduced defects and improved electron transport. Compared with –CN and –CO groups in the parent molecule ITIC, additional –OH groups in IT-DOH can further suppress defect states by interacting with undercoordinated Pb2+. More importantly, the conjugated planes of IT-DOH can be elongated by intermolecular hydrogen-bonding interactions, leading to a long-range-ordered molecular arrangement and face-on orientation, which facilitates the electron transport from the perovskite to the ETL through IT-DOH molecules. Consequently, a record PCE of 22.09% among reported i-PSCs modified by NFAs is achieved from IT-DOH-treated i-PSCs. Our work highlights the importance of molecular ordering and orientation of the NFAs as interfacial materials, and provides a guideline to design NFAs by hydroxylation for highly efficient and stable i-PSCs.

Herein, a label-free electrochemical immunosensor based on differential pulse voltammetry (DPV) and amperometric i-t curve (i-t) dual-mode analysis is proposed for early quantitative detection of procalcitonin (PCT). Due to the advantages of high chemical stability and biocompatibility, graphite carbon nitride (g-C3N4) was adopted as a high-capacity sensing interface to carry signal indicators. As an effective indicator of chronoamperometry, nickel cobalt sulfide (NiCo2S4) was uniformly dispersed on the surface of g-C3N4 through in-situ hydrothermal synthesis, which not only promotes the activation of bimetallic activity, but also effectively prevents the aggregation of NiCo2S4. At the same time, in order to establish a dual-mode analysis platform to improve accuracy and sensitivity, highly conductive carbon nanotubes (CNTs) were hybridized with composite materials to load Ag nanoparticles (Ag NPs), which have excellent oxidizing properties and are used as indicators of DPV. On account of this advanced sensing strategy, a wide linear response (DPV: 0.05 ng mL-1-50 ng mL-1 and i-t: 1.00 pg mL-1-10.00 ng mL-1) and a low detection limit (DPV: 16.70 pg mL-1 and i-t: 0.33 pg mL-1) are demonstrated. The immunosensor synthesized by this method has good stability and sensitivity, which could be applied in clinical diagnosis and treatment.

The development of photocatalysts with high catalytic activity that are capable of full utilization of solar energy is a challenge in the field of photocatalysis. Accordingly, in the present study, an efficient Z-scheme cage-structured Co9S8/g-C3N4 (c-CSCN) photocatalyst was constructed for the degradation of tetracycline antibiotics under visible-light irradiation. The Z-scheme charge-transfer mechanism accelerates the separation of photogenerated charge carriers and effectively improves photocatalytic activity. Moreover, c-CSCN has a hollow structure, allowing light to be reflected multiple times inside the cavity, thereby effectively improving the utilisation efficiency of solar energy. As a result, the photocatalytic activity of c-CSCN is 1.5-, 2.5-, and 5.8-times higher than those of sheet-type Co9S8/g-C3N4 (s-CSCN), c-Co9S8, and g-C3N4, respectively, for the degradation of tetracycline. c-CSCN maintains favourable photocatalytic activity over five consecutive degradation cycles, demonstrating its excellent stability. In addition, c-CSCN performs efficient tetracycline removal in different water substrates. Moreover, c-CSCN exhibits excellent ability to remove tetracycline under direct natural sunlight. This work fully demonstrates that c-CSCN has high catalytic activity and the potential for practical application as a wastewater treatment material.

Electrocatalytic nitrogen reduction reaction (NRR), as a green and sustainable method for ammonia synthesis, has become one of the candidates to substitute industrial Haber-Bosch ammonia synthesis in the near future. In this work, gold nanoparticles (Au NPs) were successfully anchored on bismuth sulfide nanorods (Bi

Two novel two-dimensional metal-organic frameworks (2D MOFs), 2D-M2 TCPE (M=Co or Ni, TCPE=1,1,2,2-tetra(4-carboxylphenyl)ethylene), which are composed of staggered (4,4)-grid layers based on paddlewheel-shaped dimers, serve as heterogeneous photocatalysts for efficient reduction of CO2 to CO. During the visible-light-driven catalysis, these structures undergo in situ exfoliation to form nanosheets, which exhibit excellent stability and improved catalytic activity. The exfoliated 2D-M2 TCPE nanosheets display a high CO evolution rate of 4174 μmol g-1 h-1 and high selectivity of 97.3 % for M=Co and Ni, and thus are superior to most reported MOFs. The performance differences and photocatalytic mechanisms have been studied with theoretical calculations and photoelectric experiments. This study provides new insight for the controllable synthesis of effective crystalline photocatalysts based on structural and morphological coregulation.

Photoanode sensing platforms with remarkable photoelectrochemical (PEC) response and satisfying visible-light absorption have become the most promising detection systems. Nevertheless, their inevitable electrophilic character limits their expansion in the bioassay because of reductive substances in serum or other body fluids that can severely interfere with the photocurrent to be read. To solve it, a PEC platform-assembled dual-active electrode is designed to realize the separation of biological monitoring from the photoanode. The ferricyanide ([Fe(CN)6]3-)-mediated redox cycle is first proposed to meet the gain and loss electron requirements of the PEC system. It can avoid the self-reaction in the electrolyte caused by the addition of a traditional electron donor and acceptor, for instance, ascorbic acid and hydrogen peroxide. As a consequence, the traditional counter electrode (Pt wire) is replaced by Fe2O3/AgInS2 heterojunction, which can amplify the PEC response of the cathode to meet the requirement of trace analysis. An aptasensor fabricated by the above strategies exhibits convincing data for 17β-estradiol (E2) detection from which a wide detection range is obtained in 10 fg/mL to 1 μg/mL with a detection limit of 2.74 fg/mL (S/N = 3). These advanced elements show a rosy prospect for environmental monitoring and point-of-care biomarker diagnosis.

Anisotropic magnetic exchange is of great value for the design of high performance molecular nanomagnets. In the present work, enhanced single-chain magnet (SCM) behavior is observed for a MoIII -MnII chain that exhibits anisotropic magnetic exchange. Self-assembly of the pentagonal bipyramidal [Mo(CN)7 ]4- anion and the MnII unit with a tridentate ligand results in a neutral double zigzag 2,4-ribbon structure which exhibits SCM behavior with a high relaxation barrier of 178(4) K. Open magnetic hysteresis loops are observed below 5.2 K, with a coercive field of 1.5 T at 2 K. Interestingly, this SCM can be considered to be a result of a step-wise process based on our previously reported Mn2 Mo single-molecule magnets (SMMs).

The carbon layer with good electrical conductivity and outstanding mechanical stability are essential in designing high-performance silicon/carbon (Si/C) anodes to replace the commercial graphite in lithium-ion batteries (LIBs). In terms of solving the two inherent defects of poor conductivity and big volume change of silicon, we fabricate a spongy carbon matrix derived from ZIF-8 to anchor saclike silicon synthesized by molten salt magnesiothermic reduction method. This spongy matrix can anchor saclike silicon to provide a stable reaction interface and support fast electronic transmission. At the same time, buffer space in saclike Si nanoparticles and spongy matrix can synergistically accommodate the volume change of Si to maintain the integrity of the electrode. The resulting composite with a high Si content of 77.58% exhibits good capacities of 1448 mAh g−1 at 2 A g−1 and 848 mAh g−1 at 4 A g−1 after 500 cycles. High initial coulombic efficiency of 84% at 0.2 A g−1 is also exhibited in the first three activation cycles. Therefore, this novel multifunctional N-doped spongy matrix can supply multifaceted benefits in accommodation of volumetric variation, enhancement of conductivity, and integrity of structure during cycling.

This study proposes a competitive photoelectrochemical (PEC) immunosensor for detecting diethylstilbestrol (DES). The PEC sensing platform uses a zinc and molybdenum codoped BiVO4 nanoarray ((Zn,Mo):BiVO4) as the photoactive matrix and manganese hexacyanoferrate hydrate loading silicon dioxide layer composite nanocubes (MHCF@SiO2 NCs) as the signal quencher. The (Zn,Mo):BiVO4 nanoarray demonstrated brilliant PEC behavior, by virtue of the local electric field formed by the codoped Zn and Mo. This doping accelerated the electron transfer and improved the photoelectric conversion efficiency in BiVO4 nanoarray under visible light. Furthermore, the nanoarray structure with its large surface area provided abundant binding sites for the immune response. As the MHCF@SiO2 NCs-anti-DES competitively bonded with either free DES or bovine serum albumin conjugated DES (BSA-DES), hydrogen peroxide (H2O2) as electron donor was competitively consumed and meanwhile steric resistance blocked electrons transfer. For the above reasons, the photocurrent signal was reduced. Thus, the standard sample free DES was accurately detected, and the fabricated PEC immunosensor displayed an outstanding photocurrent response from 0.1 pg/mL to 50 ng/mL with a detection limit of 0.05 pg/mL. Simultaneously, the acceptable stability, selectivity, and reproducibility of the designed dual-competitive sensing platform suggest its applicability to small molecule detection.

Dual-functional NiCo2S4 polyhedral architectures with outstanding electrochemical performance for supercapacitors and lithium-ion batteries (LIBs) have been rationally designed and successfully synthesized by a hydrothermal method. The as-synthesized NiCo2S4 electrode for supercapacitor exhibits an outstanding specific capacitance of 1298 F g−1 at 1 A g−1 and an excellent rate capability of ~80.4% at 20 A g−1. Besides, capacitance retention of 90.44% is realized after 8000 cycles. In addition, the NiCo2S4 as anode in LIBs delivers high initial charge/discharge capacities of 807.6 and 972.8 mAh g−1 at 0.5 C as well as good rate capability. In view of these points, this work provides a feasible pathway for assembling electrodes and devices with excellent electrochemical properties in the next generation energy storage applications.

In this work, a triple-amplified biosensor with a bioactivity-maintained peculiarity was constructed for quantitative procalcitonin (PCT) detection. As everyone knows, a strong electrochemiluminescence (ECL) signal is the premise to ensure high sensitivity for trace target detection. Hence, a valid tactic was developed to achieve signal amplification of luminophor by using Co2+-based metal-organic frameworks (ZIF-67) and silver-cysteine (AgCys). The ZIF-67 particles, which have more atomically dispersed Co2+, could play the role of a co-reaction accelerator to catalyze S2O82- to generate abundant Co3+ and sulfate radical anions (SO4•-). Afterward, a mass of Co3+ was reduced to more hydroxyl radicals (OH•) by H2O, thus ulteriorly reducing S2O82- to generate more SO4•-. Remarkably, S2O82- was reduced to SO4•- continuously with the recycling of Co2+ and Co3+, which realized an effective signal amplification. Meanwhile, the AgCys complex with superior catalysis and biocompatibility was prepared to further improve the ECL signal and maintain the bioactivity of the biomolecule. Furthermore, HWRGWVC, a heptapeptide that was used for combining the Fc fragments of an antibody by Au-S bonding to achieve the fixed point fixation, could not only maintain bioactivity of an antibody but also improved its incubation efficiency, thus further enhancing biosensor sensitivity. Under optimum conditions, the proposed biosensor realized highly sensitive assay for PCT with a wide dynamic range from 10 fg/mL to 100 ng/mL and a detection limit as low as 3.67 fg/mL. With superior stability, selectivity, and repeatability, the prepared biosensor revealed immense potential application of ultrasensitive assay for PCT in human serum.

Thrombin is a marker of blood-related diseases, and its detection is of great significance in the fields of medical and biological research. Herein, a novel chemiluminescence (CL) sensor for thrombin detection was prepared based on dual-aptamer biorecognition and mesoporous silica encapsulated with iron porphyrin. Mesoporous silica encapsulated with hematin by aptamer1 (Apt1/hematin/M-SiO2) and magnetic microspheres modified with aptamer2 (Apt2/NH2-MS) were successfully prepared, and the two materials were used to construct a CL sensor to detect thrombin. Primarily, Apt2/NH2-MS is used for pretreatment separation of thrombin samples by the biorecognition effect between the aptamer (Apt2) and target (thrombin). Then, thrombin/Apt2/NH2-MS is again recognized with Apt1 on the surface of Apt1/hematin/M-SiO2 and Apt1/thrombin/Apt2/NH2-MS is formed, so dual-aptamer biorecognition is realized. Meanwhile, the generated Apt1/thrombin/Apt2/NH2-MS makes Apt1 shed off the surface of M-SiO2 and release hematin. The released hematin can catalyze the luminol-H2O2 CL reaction. Therefore, a sandwich-type CL sensor was constructed based on dual-aptamer biorecognition and hematin catalysis for the detection of thrombin. The sensor has a linear range of 7.5 × 10-15 to 2.5 × 10-10 mol·L-1 and a detection limit of 2.2 × 10-15 mol·L-1 and also exhibits excellent selectivity, reproducibility, and stability. The sensor was successfully used for the detection of thrombin in serum samples, which makes it possible to apply the sensor in the detection of thrombin in actual samples.

Field-induced slow magnetic relaxation was observed in two interpenetrated cobalt(II) metal–organic framework (MOF) isomers constructed from a dual-functional ligand 1H-benzimidazole-5-carboxylic acid, which represent the first example of MOF isomers showing field-induced single-ion magnet behavior.

Developing dopant-free hole transporting materials (HTMs) and passivating defects in perovskite films are two significant themes to realize efficient and stable perovskite solar cells (PSCs). Compared to various individual endeavors for either of them, enabling both via a single material is more interesting but certainly challenging. In this report, we develop dopant-free polymer HTMs bearing amino pendants as passivating groups for improved efficiency and stability of PSCs. The bifunctional polymers present simultaneous main-chain (donor–acceptor conjugated backbone) hole extraction/transport and side-chain (amino group) defect passivation at the perovskite/HTM interface. Moreover, with an increased content of amino pendants, the polymers exhibit enhanced hole mobility and defect passivation ability, advancing device efficiency and stability. As a result, PSCs using the dopant-free polymer HTM achieve an efficiency approaching 19%, with impressive stability when testing at a relative humidity of 85%, by heat at 80 °C, or under continuous light illumination. This work demonstrates that amino functionalization at the side chain of polymers is a promising method to develop dopant-free HTMs accompanied by defect passivation effects for high-performance and durable PSCs.

Herein, a smart competitive-type photoelectrochemical (PEC) sensor based on an antigen-down (Ag-down) format for procalcitonin (PCT) detection is proposed. A fullerene sensitized flower-like Sn3O4 nano-structure is used as the photoactive platform, and FeS2 is labeled on the secondary antibody as a signal adjusting element. The sensor exhibits excellent sensitivity and great stability.

Graphical abstract Osteoinductive and persistent antibacterial PLLA/HA/PDA/PPy/Ag composite fiber was successfully synthesized through the self-polymerization of Dopamine on the surface of PLLA/HA and electrochemical deposition of PPy-controlled Ag-NPs., Highlights • Stable silver-nanoparticles coating layer using electrochemical method. • Dopamine self-polymerized on the surface of electrospun fibers. • Steady and slow release of Ag for long-term antibacterial property. • Calcium phosphate surface for bioactivity and osteoinductivity., Bone implant materials cause the most common complication of bone infections in orthopedic surgery, resulting in implant failure. Antibiotic treatment of bone infections leads to problems such as bacterial resistance and reduced osteogenic capacity. In this study, dopamine (DA) was self-polymerized on the surface of Polylactic acid (PLLA)/Hydroxyapatite (HA) nanowire composite fibers to form an adhesive polydopamine (PDA) membrane, and a stable silver-nanoparticles (Ag-NPs) coating layer was constructed on it by electrochemically driven Ag+ coordination and chelation through Polypyrrole (PPy) mediation, achieving steady and slow release of Ag-NPs. With optimized DA soaking time of 24 h and soaking concentration of 0.5 g·L−1, nanoparticles were uniformly distributed on PLLA/HA/PDA/PPy/Ag composite fibers and the hydrophilicity of the composite fibers was well-behaved. Besides, the composite fibers possessed good physiological stability and 100% antibacterial rate against Escherichia coli (E. coli) as well as Staphylococcus aureus (S. aureus). In addition, the composite fibers had promoted apatite nucleation and growth on surface and good cytocompatibility with osteoblasts, indicating ability of inducing osteogenic differentiation. In summary, a multi-functional PLLA/HA/PDA/PPy/Ag composite fiber with long-term antibacterial property, bioactivity and osteoinductivity was successfully constructed by electrospinning and electrochemical deposition.

Serum-soluble folate binding protein (FBP) is an important tumor marker, and the development of a simple biosensing method is highly needed. In this work, a photoelectrochemical (PEC) biosensor for the detection of FBP was proposed based on the construction of an antifouling interface and the unique ligand-protein recognition. The PEC sensing platform was prepared by the biomimetic polydopamine (PDA) coating on TiO2 nanotubes arrays (NTAs). A significant PEC enhancement effect was obtained due to the macroporous structures. Excellent antifouling performance was achieved by conjugation of amino-group-terminated 8-arm poly(ethylene glycol) (PEG). The incorporation of folic acid (FA) retains the antifouling property and shows recognition abilities toward FBP. The fabricated PEC biosensor shows good analytical performance. The combination of ligand-protein recognition and a PEC antifouling interface provides a good consideration for the development of FBP biosensors.

For the first time, we report the formation of a chiral MOF-based helical nanomaterial (h-HDGA@ZIF-67) through arranging zeolitic imidazolate framework (ZIF-67) nanocrystals on helical l-glutamic acid terminated bolaamphiphile (h-HDGA) via a facile process at room temperature. The self-assembly leads to the chiral function of the ZIF-67 from an achiral ligand. The h-HDGA@ZIF-67 served as a new type of electrochemical sensing interface for recognizing and quantifying Pen enantiomers that realize significant enantioselectivity, satisfactory stability, and reproducibility. The synergetic effect from ZIF-67 nanocrystals on h-HDGA and stereoselectivity of h-HDGA@ZIF-67 lead to the excellent enantioselectivity. The present strategy showed the first example of a chiral MOF-based supramolecule helical nanomaterial, presenting high enantioselectivity for electrochemical enantiomeric determination.

Nowadays, the electrochemiluminescence (ECL) immunosensor with the unique superiority of tunable luminescence and ultrahigh sensitivity has become one of the most promising immunoassay techniques, especially for low-abundance biomarkers analysis. However, the use of signal probes with high excited potential and applied emitters which owned good intensity but biotoxicity limited its application. Herein, an ECL resonance energy transfer strategy was developed based on protein bioactivity protection utilizing europium-doped phosphoric acid gadolinium (GdPO4:Eu) as novel low-potential luminophor (donor) and Pd@Cu2O as the quenching probe (acceptor). Specifically, GdPO4:Eu was first prepared by using the hydrothermal synthesis method to apply in ECL, and when it coexisted with K2S2O8, cathode, a strong ECL signal would be generated at a low potential of -1.15 V (vs Ag/AgCl), where the immunocompetence of antigens and antibodies can be maintained well. Electrical pair Eu3+/Eu2+, as the coreactant promoter, produced by potential excitation could produce more SO4•- to accelerate the oxidation process of GdPO4:Eu. Meanwhile, Cu2O coated onto Pd (Pd@Cu2O), as a dual-quencher, enhanced the quenching effect of Pd alone and controlled the ECL intensity of the "signal on" state within a reasonable range. As a result, the proposed biosensor for detection of trace procalcitonin, a biomarker of systemic inflammatory response syndrome, exhibited a far low detection limit, 0.402 fg/mL (S/N = 3). Importantly, this work not only utilized a promising ECL emitter for biosensing platform construction but also had momentous potential in biomarker detection of disease diagnosis and clinical analysis.

This research put forward a novel split-type electrochemical (EC) immunosensor which integrated the controlled-release strategy with EC detection for application in the field of biosensing. Concretely, ascorbic acid (AA) was packaged in a cadmium sulfide (CdS)-capped spherical mesoporous bioactive glass (SBG) nanocarrier (SBGCdS) on account of encapsulation technology. To reduce the complexity of the bioanalysis, the detection antibody-labeled SBGCdS-AA bioconjugate was applied in a 96-well microplate for the immunoreaction process, which is independent of the EC determination procedure. Thus, the immune interference and steric hindrance caused by the accumulation of nanomaterials on the electrode could be minimized. Subsequently, AA was released efficiently via the destruction effect of dithiothreitol on the disulfide bond. In addition, for the as-prepared FcAI/l-Cys/gold nanoparticles (GNPs)/porous BiVO4 (p-BVO)/ITO EC sensing platform in the detection solution, the synergetic catalysis of Fc and GNPs/p-BVO toward the oxidation of the released AA could be realized, which triggered AA-mediated significant signal magnification throughout this study. In particular, p-BVO with an ordered nanoarray structure could accelerate the electron transfer to assist in sensitivity improvement of this system. This novel biosensor was capable of assaying the neuron-specific enolase (NSE) biomarker sensitively, from which a linear range of 0.001-100 ng/mL was derived along with a low detection limit of 1.08 pg/mL. An innovative way could be paved in the bioanalysis of NSE and other biomarkers.

The design and synthesis of highly efficient and durable non-noble metal electrocatalysts have become a top priority for the hydrogen evolution reaction (HER). Thus, this study describes a straightforward synthesis of nickel-doped cobalt phosphide nanowire clusters on carbon cloth (Ni-CoP/CC) via a simple hydrothermal-phosphating process. Owing to the unique nanowire cluster structure together with the use of current collector, such binder-free three-dimensional electrode of Ni-CoP/CC displays efficient HER activity, achieving the low overpotential of 53 mV at a geometric current density of 10 mA cm−2, with a Tafel slope of 57 mV dec−1 and superior stability (100 h) in 1.0 M KOH.

Gold modified thiol graphene (Au@HS-rGO) was prepared and applied as sensing platform for constructing the electrochemical aptasensor. While gold-palladium modified zirconium metal-organic frameworks (AuPd@UiO-67) nanozyme was employed as signal enhancer for detecting mercury ions (Hg2+) sensitively. Herein, gold nanoparticles (Au NPs) were modified on HS-rGO to form the thin Au@HS-rGO layer. Then the substrate strand (Apt1) was modified on the platform through Au-S bond. The signal strand (Apt2) was further decorated on the platform in the presence of Hg2+. Herein, the Apt2 was labeled with AuPd@UiO-67 nanozyme, which exhibited catalase-like properties to catalyze H2O2, thereby generating the electrical signal. With the concentration of Hg2+ increased, the amount of modified Apt2-AuPd@UiO-67 increased, leading to the rise of current response. Since the current responses were linear with concentration of Hg2+, the detection of Hg2+ can be achieved. Under the optimum conditions, the prepared electrochemical aptasensor exhibited wide linear range from 1.0 nmol/L to 1.0 mmol/L, along with a low detection limit of 0.16 nmol/L. Moreover, the electrochemical aptasensor showed excellent selectivity, reproducibility and stability, together with superior performance in actual water sample analysis. Therefore, this proposed electrochemical aptasensor may have promising applications and provide references for environmental monitoring and management.

There dimensional (3D) metallic nanohybrids have attracted attentions for the applications in nanophotonic devices, catalysis and biosensor. Here, the 3D suspended Ag nanoparticles/Carbon nanotubes (AgNPs/CNTs) nanohybrids, obtained by self-aggregating AgNPs onto the suspended CNT networks, are synthesized and used for the SERS application. The electric field distribution with the near-field and far-field coupling can be obtained by the optimization of the nanogaps of the AgNPs. Such suspended AgNPs/CNTs nanohybrids are studied to be used as the ultra-sensitive SERS biosensor, benefiting from the bio-compatibility and chemical absorption of the CNT networks and the EM enhancement of the 3D denser “hotspots”. R6G molecules with a concentration as low as 10−15 M can be clearly detected, demonstrating their excellent Raman enhancement.

Silicon (Si) has been regarded as one of the next-generation anode materials due to its ultrahigh theoretical capacity, low equilibrium potential, abundant resources and superior safety performance. Herein, we fabricated a novel honeycomb Si composed of many Si nanoparticles (NPs), which can be refined from the urchin-like crude product obtained through the magnesiothermic reduction process. Via the electrostatic attraction, rapid freeze-drying process and further thermal treatment, the honeycomb Si can be tightly encapsulated in a thin layer composed of reduced graphene oxide and carbon nanotube (indicating as Si-rGO/CNT) to avoid direct exposure to the electrolyte. Si NPs with the wrinkled rGO/CNT wrapping layer containing mesopores can not only shorten the pathway of Li+ ions and electrons but also accommodate the unavoidable expansion/contraction and buffer the excessive stress. Meanwhile, the CNT intertwined throughout the electrode can effectively repair those areas that lost conductivity during long-term cycling. Therefore, the self-supported Si-rGO/CNT electrode having a high Si content of 76 wt% exhibits capacities of 1304 mAh g−1 at 2 A g−1 and 1053 mAh g−1 at 5 A g−1 in rate performance, and maintain a capacities of 1899 mAh g−1 at 0.5 A g−1 after 250 cycles and 1003 mAh g−1 at 4 A g−1 after 1000 cycles accompanying with a stable coulombic efficiency (CE) up to 99.5%.

The shuttle effect from the dissoluble polyselenide intermediates in lithium-selenium (Li-Se) battery is a critical problem. In order to explore the effective solution, a specific composite ceramic separator including a covalent organic framework prepared by the polymerization of 2,5-Dimethoxy-1,4-Dicarboxaldehyde and Tetrakis(4-aminophenyl)ethane (DMTA-COF) was used to enhance electrochemical performance of Li-Se battery for the first time. It should be noted that the cathode with pure selenium of 80% by weight leads to a high selenium loading of ∼3 mg/cm2 for the simply-made cells. Due to the small pore channel of the DMTA-COF-coated separator, the dissolution of the polyselenide LiSen (n > 4) can be effectively restrained. As a consequence, the cells delivered a long cycling performance of up to 700 cycles with high capacity of 126 mA h/g at 6 C and good capacity of 51 mA h/g at 20 C. Obviously, our study elucidates the COF-integrated separator is a promising pathway to improve the capacity and stability of the lithium-selenium battery.

The serum level of soluble CD44 is directly associated with several clinicopathological parameters of malignant diseases. There is a great need for the development of an easy and cost-effective detection method for soluble CD44 for both the diagnosis and the treatment of cancers. In this work, a simple photoelectrochemical (PEC) method for the sensitive detection of serum-soluble CD44 is proposed based on the construction of a hybrid antifouling coating on the TiO2 substrate. Hyaluronic acid (HA) and poly(ethylene glycol) (PEG) are co-immobilized using a biomimetic one-step surface functionalization approach. The immobilized HA shows strong recognition abilities toward soluble CD44, and the synergistic antifouling effect achieved by the combination of PEG and HA improves the sensing specificity. Based on the inhibitory effect of CD44 recognition on the PEC signal of the TiO2 substrate, a PEC biosensor is developed with a wide response range and a low detection limit. The development of antibody-free biosensors may promote the application of soluble CD44 as a biomarker for the diagnosis and treatment of malignant diseases.

It is essential to develop a highly efficient detection platform for tetracycline (Tc). Herein, based on well-designed hierarchical MIL-68(In)-NH2/MWCNT/CdS composites as a highly efficient transducer, a label-free visible light driven photoelectrochemical (PEC) aptasensor was systematically fabricated. Characterization results indicate that the forming of MIL-68(In)-NH2/CdS heterojunction remarkable facilitated the transfer and inhibited the recombination of charge carriers. Moreover, the transfer properties of multiwalled carbon nanotubes (MWCNTs) further improved the photoelectric conversion efficiency by adjusting electron transport routes. The aptamer as a biorecognition unit was grafted on the modified electrode by chemical bonding effect, and Tc molecules could be captured through the specific interaction of aptamer and Tc in solution. The concentration of Tc was detected by observing the fluctuation of photocurrent signals. Under optimized conditions, the proposed aptasensor showed the broad linear range from 0.1 nmol L−1 to 1 μmol L−1 with a low detection limit (LOD) of 0.015 nmol L−1. Furthermore, the high sensitivity, excellent reproducibility and favorable stability of the PEC sensing platform indicated the potential applications for antibiotic residues detecting in environmental media.

Ultrafine Ni2P/Co2P nanoparticles encapsulated in hollow porous N-doped carbon nanospheres are synthesized through a facile two-step access. Firstly, metallic Ni and Co coated by hollow N-doped spheres as precursors are obtained through a high temperature calcination route of organic polymer and inorganic Ni and Co salts. Then bimetal Ni2P/Co2P supported on N-doped carbon nanospheres are acquired by a facile phosphorization process. It is worth to note that aniline-pyrrole polymer can prevent fast growth and severe aggregation of Ni2P/Co2P, which implies more exposed active sites. Moreover, the calcination of hollow polymer spheres lead to the formation of ultrathin NC shell on the surface of Ni2P/Co2P hybrids, which can tune electronic structures, improve the conductivity and protect active sites from corrosion in harsh conditions. When used as HER catalyst, it displays remarkable catalytic activity in both acidic and alkaline solutions, which needs an onset potential of only 164 mV and 168 mV, respectively. Therefore, this work may propose a new strategy to design unique inorganic-organic heterostructures to combine ultrafine metal phosphides with porous carbon for efficient HER.

A sensitive electrochemical aptasensor was designed based on gold modified graphene nanocomposite with different morphologies for the detection of lead ion (Pb2+). Specifically, a sulfydryl-labeled substrate strand (Apt1) and a sulfydryl-labeled catalytic strand (Apt2) were devised in fabricating the electrochemical aptasensor. Gold modified porous reduced graphene oxide (Au@p-rGO) was synthesized and applied as support for immobilizing the Apt1. And gold modified graphene oxide (Au NPs@GO) was employed as signal probe and connected with Apt2 to realize the immobilization of it on the electrode by means of the principle of complementary base pairing. The current signal can be obtained by recording the electrocatalytic conditions toward H2O2. The Pb2+-dependent DNAzyme could play a role when Pb2+ existed. With the increase of the concentration of Pb2+, the current response revealed a diminishing signal, thus realizing the sensitive detection of Pb2+. Under the optimal conditions, the fabricated electrochemical aptasensor exhibited a linear response toward Pb2+ ranging from 5 pmol/L to 1 μmol/L, together with a low limit of detection of 1.67 pmol/L. Moreover, the prepared aptasensor displayed outstanding selectivity, acceptable stability and superior reproducibility for detecting Pb2+. This proposed tactics may provide reference and potential applications for detecting some other heavy metal ions.

To develop a robust method for the detection of disease biomarkers is always the pursued goal in the field of biomedical research. Multi-modal immunoassay strategy will bring tremendous potential for the purpose. In this study, a kind of robust nanozyme-linked immunosorbent assay has been presented, which can achieve ratiometric fluorescent and colorimetric dual-modal sensing performance. Here, o-phenylenediamine (OPD) as an organic substrate can be oxidized and converted into 2,3-diaminophenazine (oxOPD) by the robust nanozyme of nanoceria with peroxidase-like properties in the present of H2O2. An exogenous fluorescence signal source of graphitic carbon nitride quantum dots (g-C3N4 QDs) is introduced, and the corresponding fluorescence can be efficiently quenched by oxOPD owing to the hydrogen bonding and π-π stacking interactions, yielding a fluorescence spectral line with dual emission peaks while only irradiated by an excitation wavelength. Meanwhile, a visible color change was derived from the oxOPD formation, which can be recorded by colorimetric method. As a proof-of-study demonstration, the detection of human cardiac troponin I was done. This method affords robust, reliable and sensitive detection performance due to the combination of the merits of ratiometric fluorescent assay and colorimetric assay. It is no doubt that our proposed approach will bring remarkable inspirations for biomedical researchers.

Molecularly imprinted polymer (MIP) electrochemical sensor (MIP-EC sensor) has great potential in the electroanalytical chemistry field, especially in detection of small molecular contaminants, but still remains severe challenges, such as low reproducibility and low sensitivity. To overcome these difficulties, nanoarray electrodes as sensitive sensor platforms is an excellent selection for fabricating MIP-EC sensors. In this communication, Ni(OH)2nanoarrays in situ grown on nickel foam (Ni(OH)2/NF) was prepared and used as sensing platform. The MIPs in situ adsorbed on Ni(OH)2/NF (MIP/Ni(OH)2/NF) was prepared and used as the specific identification part to the template molecule. Accompanied with [Fe(CN)6]3−/[Fe(CN)6]4- as the redox probe and differential pulse voltammetry (DPV) as the detection method, the MIP-EC sensor for sensitive detection of sulfapyridine was simply developed. Under optimized conditions, the presented MIP-EC sensor exhibits the linear range of 5.9 × 10-7–1.34 × 10-3mol L-1 and the low limit of detection (LOD) of 3.57 × 10-7mol L-1 (S/N = 3). Furthermore, due to the good electric properties of Ni(OH)2/NF electrode and specific recognition properties of MIPs, the MIP-EC sensor shows a high imprinting efficiency, exhibits excellent selectivity, sensitivity, stability and reproducibility. This study provided an efficient and simple approach for detection of sulfapyridine in fish products, and provided a promising and potential approach for detecting small molecular contaminants in many fields.

In this study, a sandwich-type photoelectrochemical (PEC) immunosensor was designed for ultrasensitive detection of carcinoembryonic antigen (CEA) by using Cu doped TiO2 compositing with carbon nitride (Cu:TiO2/g-C3N4). The strategy of signal enhancement was based on Cu:TiO2/g-C3N4 as photosensitizer and the employed alkaline phosphatase (ALP) could catalyze ascorbic acid 2-phosphate (AAP) to be ascorbic acid (AA) as electron donor. Thanks to the functionalized Cu:TiO2/g-C3N4 nanocomposites, large degree enhancement of photocurrent response could be obtained under illumination of 430 nm wavelength. Furthermore, the characterization and mechanism of the detection procedure were discussed in depth. This exquisite sandwich protocol was successfully constructed for CEA detection based on the photocurrent signals corresponding to the concentration of in situ generated electron donor, which was directly proportional to the amount of CEA. The current response of the fabricated PEC immunosensor was linear with CEA in the range of 0.005–1000 ng mL−1, together with low detection limit of 1 pg mL−1 (S/N = 3). And high selectivity, reproducibility and stability were acquired. In addition, the proposed method may find promising applications in detecting other tumor markers in clinical analysis.

As a newly emerged photoactive material, Cu2MoS4 has motivated wide research interests in the field of photoelectrochemistry. Based on manganese doped CdS (CdS:Mn) sensitized graphene (G)/Cu2MoS4 composite, we developed a label-free photoelectrochemical (PEC) immunosensor for the detection of cardiac troponin I (cTnI). G as an excellent 2D conductive material, combined with Cu2MoS4 could improve its charge transfer efficiency. CdS:Mn nanoparticles (NPs) loaded on G/Cu2MoS4 further enlarged the light absorption range of Cu2MoS4 and restrained the electron-hole pairs recombination. Under optimal conditions, the proposed PEC immunosensor responded sensitively to cTnI with a low detection limit of 0.18 pg/mL and a wide linear range (0.005–1000 ng/mL). Moreover, as-fabricated immunosensor also exhibited high sensitivity, excellent selectivity and good stability. This work also was extended to real samples analysis and obtained satisfied results.