Soil application of graphitic carbon nitride nanosheets alleviate cadmium toxicity by altering subcellular distribution, chemical forms of cadmium and improving nitrogen availability in soybean (Glycine max L.).

Cadmium (Cd)-contamination impairs biological nitrogen fixation in legumes (BNF), threatening global food security. Innovative strategies to enhance BNF and improve plant resistance to Cd are therefore crucial. This study investigates the effects of graphitic carbon nitride nanosheets (g-C3N4 NSs) on soybean (Glycine max L.) in Cd contaminated soil, focusing on Cd distribution, chemical forms and nitrogen (N) fixation. Soybean plants were treated with 100 mg kg-1 g-C3N4 NSs, with or without 10 mg kg-1 Cd for 4 weeks. Soil addition of g-C3N4 NSs alleviated Cd toxicity and promote soybean growth via scavenging Cd-mediated oxidative stress and improving photosynthesis. Compared to Cd treatment, g-C3N4 NSs increased shoot and root dry weights under Cd toxicity by 49.5% and 63.4%, respectively. g-C3N4 NSs lowered Cd content by 35.7%-54.1%, redistributed Cd subcellularly by increasing its proportion in the cell wall and decreasing it in soluble fractions and organelles, and converted Cd from high-toxicity to low-toxicity forms. Additionally, g-C3N4 NSs improved the soil N cycle, stimulated nodulation, and increased the N-fixing capacity of nodules, thus increasing N content in shoots and roots by 12.4% and 43.2%, respectively. Mechanistic analysis revealed that g-C3N4 NSs mitigated Cd-induced loss of endogenous nitric oxide in nodules, restoring nodule development. This study highlights the potential of g-C3N4 NSs for remediating Cd-contaminated soil, reducing Cd accumulation, and enhancing plant growth and N fixation, offering new insights into the use of carbon nanomaterials for soil improvement and legume productivity under metal(loid)s stress.

Label-free "signal-off" PEC aptasensor for determination of kanamycin based on 3D nanoflower-like FeIn2S4/CdS Z-scheme heterostructures.

Highly photoactive 3D nanoflower-like FeIn2S4/CdS heterostructures were synthesized by hydrothermal treatment and low-temperature cation exchange. The FeIn2S4/CdS displayed 14.5 times signal amplification in contrast to FeIn2S4 alone. It was applied as a photoactive substrate to construct a label-free photoelectrochemical (PEC) aptasensor for ultrasensitive determination of kanamycin (KAN). Under the optimal conditions, the constructed PEC aptasensor displayed a wide linear range (5.0 × 10-4 ~ 5.0 × 101 ng mL-1) and a low detection limit (S/N = 3) of 40.01 fg mL-1. This study provides some constructive insights for preparation of advanced photoactive materials and exhibits great potential for quantitative determination of antibiotics in foods and environmental samples.

T porous PtIr bimetallic nanotubes with core shell structure for enhanced electrocatalysis on methanol oxidation.

Sluggish methanol oxidation brings challenges to the commercialization of the direct methanol fuel cells (DMFCs). Herein, porous PtIr bimetallic nanotubes were prepared via galvanic replacement using Ag nanowires as template. These PtIr catalysts show a core-shell nanostructure with a tunable Pt-rich surface. The mass activity of methanol oxidation reaction (MOR) at these porous PtIr nanotubes can reach up to 1.42 A mg-1based on Pt loading, which is better than the commercial Pt/C catalysts and can be comparable with most of one-dimensional Pt-based MOR catalysts reported recently. In addition, these PtIr catalysts can maintain structural integrity after long-term durability test. The superior catalytic performance of the novel porous PtIr nanotubes will make it possible used in the commercial DMFCs as advanced MOR catalysts at industrial scale.

Environmentally relevant concentrations of arsenic induces apoptosis in the early life stage of zebrafish.

Arsenic (As) in the aquatic environment is a considerable environmental issue, previous studies have reported the toxic effects of low concentrations (≤ 150 µg/L) of As on fish. However, limited information is available regarding the impact of low levels of As on apoptosis. To evaluate this, zebrafish embryos were exposed to different concentrations (0, 25, 50, 75, and 150 µg/L) of As (arsenite [AsIII] and arsenate [AsV]) for 120 h. Our results indicated that low concentrations of AsIII exposure significantly inhibited the survival of zebrafish larvae, and significantly increased the transcription of Caspase-9 and Caspase-3, the ratio of Bax/Bcl-2 transcription, and protein levels of Caspase-3. In contrast, AsV decreased the ratios of Bax/Bcl-2 transcription and protein levels, as well as protein levels of Caspase-3. Our data demonstrated that AsIII and AsV exert different toxic effects, AsIII induced apoptosis via the mitochondrial pathway and the extrinsic pathway, while AsV induced apoptosis only via the mitochondrial pathway.

Green synthesis of peptide-templated fluorescent copper nanoclusters for temperature sensing and cellular imaging.

A simple and green approach was developed for the preparation of fluorescent Cu nanoclusters (NCs) using the artificial peptide CLEDNN as a template. The as-synthesized Cu NCs exhibited a high fluorescence quantum yield (7.3%) and good stability, along with excitation and temperature dependent fluorescent properties, which could be employed for temperature sensing. Further investigations demonstrated low toxicity of Cu NCs for cellular imaging.

Low Rh doping accelerated HER/OER bifunctional catalytic activities of nanoflower-like Ni-Co sulfide for greatly boosting overall water splitting.

Facile synthesis of high-efficiency and stable bifunctional electrocatalyst is essential for producing clean hydrogen in energy storage systems. Herein, low Rh-doped flower-like Ni3S2/Co3S4 heterostructures were facilely prepared on porous nickel foam (labeled Rh-Ni3S2/Co3S4/NF) by a hydrothermal method. The correlation of the precursors types with the morphological structures and catalytic properties were rigorously investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in the control groups. The low Rh doping within the catalyst played important role in boosting the catalytic characteristics. The resulting catalyst showed the smaller overpotentials of 197 and 78 mV to drive a current density of 10 mA cm-2 for the OER and HER in alkaline electrolyte, respectively. And the potential only required 1.71 V to drive a current density of 100 mA cm-2 in a water splitting device. It reflects excellent overall water splitting of the home-made Rh-Ni3S2/Co3S4/NF. This strategy shed some constructive light for preparing transition metal sulfide-based electrocatalysts in water splitting devices.

Atomically dispersed ternary FeCoNb active sites anchored on N-doped honeycomb-like mesoporous carbon for highly catalytic degradation of 4-nitrophenol.

In the last decades, 4-nitrophenol is regarded as one of highly toxic organic pollutants in industrial wastewater, which attracts great concern to earth sustainability. Herein, atomically dispersed ternary FeCoNb active sites were incorporated into nitrogen-doped honeycomb-like mesoporous carbon (termed FeCoNb/NHC) by a two-step pyrolysis strategy, whose morphology, structure and size were characterized by a set of techniques. Further, the catalytic activity and reusability of the as-prepared FeCoNb/NHC were rigorously examined by using 4-NP catalytic hydrogenation as a proof-of-concept model. The influence of the secondary pyrolysis temperature on the catalytic performance was investigated, combined by illuminating the catalytic mechanism. The resultant catalyst exhibited significantly enhanced catalytic features with a normalized rate constant (kapp) of 1.2 × 104 min-1g-1 and superior stability, surpassing the home-made catalysts in the control groups and earlier research. This study provides some constructive insights for preparation of high-efficiency and cost-effectiveness single-atom nanocatalysts in organic pollutants environmental remediation.

Heterostructured CoP·CoMoP nanocages as advanced electrocatalysts for efficient hydrogen evolution over a wide pH range.

A sustainable and environmental-friendly method to produce hydrogen with high purity is the electrochemical water splitting, but its commercialization is challenged due to lack of cost-effective electrocatalysts for hydrogen evolution reaction (HER) over a wide pH range. Herein, a series of CoP·xCoMoP heterostructured nanocages (NCs) were prepared via a dissolution-regrowth and subsequent phosphorization process using metal-organic frameworks (MOFs) as template. The three-dimensional (3D) architecture of CoP·xCoMoP is constituted by the heterostructured nanosheets composed with CoP and CoMoP phase. These noble-metal-free earth-abundant transition metal phosphide (TMP) catalysts show a pH-universal HER activity with high efficiency. Under the optimal atom ratio of Co and Mo (6:5), CoP·5CoMoP NC catalysts can deliver a current density of 10 mA cm-2 at the overpotential of 72 mV with a Tafel slope of 60.3 mV dec-1 in 1.0 M KOH solution. The same current output requires overpotential of 44 mV in 0.5 M H2SO4 solution and 151 mV in1.0 M phosphate buffered solution (PBS), respectively. The superior HER activity of CoP·5CoMoP NC catalysts can be comparable to or even better than most of noble metal-free HER electrocatalysts reported recently. In addition, CoP·5CoMoP NC catalysts also show a fairly high HER stability over a wide pH range, and their HER activity can be well kept without significant loss for long-term electrolysis. The 3D CoP·5CoMoP heterostructured catalysts hold promise as efficient and low-cost catalysts for water splitting devices over a wide pH range.

In situ produced Co9S8 nanoclusters/Co/Mn-S, N multi-doped 3D porous carbon derived from eriochrome black T as an effective bifunctional oxygen electrocatalyst for rechargeable Zn-air batteries.

Construction of high-efficiency, low cost and stable non-noble metal catalyst on air cathode is of great importance for design and assembly of rechargeable Zn-air battery. Eriochrome black T (EBT) has phenolic hydroxyl and -N=Ν- groups, which provides multiple coordination sites for metal ions. Herein, Co9S8 nanoclusters implanted in Co/Mn-S,N multi-doped porous carbon (Co9S8@Co/Mn-S,N-PC) are fabricated with the mixture (i.e. EBT, metal precursors and dicyandiamide) by a coordination regulated pyrolysis strategy. Specifically, EBT effectively chelates with the Co and Mn ions, resulting in multiple incorporation and fine modulation of the carbon electronic structures. Meanwhile, its sulfonic acid groups are reduced at such high temperature, accompanied by simultaneously embedding S element in the carbon, ultimately in situ forming Co9S8 nanoclusters. The Co9S8@Co/Mn-S,N-PC performs as an effective bifunctional oxygen catalyst, displaying a positive half-wave potential of 0.85 V and a large limiting current density of 5.89 mA cm-2 for oxygen reduction reaction (ORR) in alkaline media, coupled with a small overpotential of 320 mV at 10 mA cm-2 towards oxygen evolution reaction (OER), outperforming commercial Pt/C and RuO2 catalysts, respectively. Furthermore, the assembled rechargeable Zn-air battery with Co9S8@Co/Mn-S,N-PC exhibits the much better charge/discharge performance and long-term durability (210 h, 630 cycles). This research opens an instructive avenue to develop high-efficient and stable bifunctional oxygen electrocatalysts in energy transformation and storage devices.

Ecotoxicological assessment of spent battery extract using zebrafish embryotoxicity test: A multi-biomarker approach.

Water environmental pollution caused by spent batteries is a nonignorable environmental issue. In this study, the early life stage of zebrafish was employed to assess the environmental risk of spent batteries after exposure to 0, 1%, 2%, 5% and 10% spent battery extract for 120 h. Our results clearly indicated that spent battery extract can significantly decrease the survival rate, hatching rate and body length and increase heart rate. Moreover, spent battery extract exposure-induced zebrafish larvae generate oxidative stress and inhibit the mRNA transcriptional levels of heat shock protein (HSP70) and metallothionein (MT) genes. These results showed that the spent batteries not only affected the survival and development performance of zebrafish at an early life stage but also caused oxidative stress and interfered with the detoxification of zebrafish. This study provided novel insight into spent battery induced toxicity in the early life stage of fish.

Study on adsorption of Co(II) and Ni(II) onto mesoporous Ti-containing MCM-48.

Ti-containing MCM-48 (Ti-MCM-48) material with mesoporous structure was synthesized and characterized, and the absorption processes of Co(II) and Ni(II) on the material were investigated in detail in the present study. The Ti- MCM-48 was synthesized by hydrothermal reaction and characterized by XRD, FT-IR and nitrogen sorption methods. Optimum pH value for maximum adsorption rate is 8.0, and the saturated adsorption capacities of Ti-MCM-48 for Co(II) and Ni(II) are 9.870 and 22.94 mg g(-1) respectively, which are greater than those of the reported materials Adsorption isotherms of Co(II) and Ni(II) on Ti-MCM-48 accord well with the Langmuir adsorption models. Kinetic data of adsorption reactions and the adsorption equilibrium parameters were also determined, and the obtained data correlated linearly with the pseudo-second order equation.

One-step pyrolysis synthesis of nitrogen, manganese-codoped porous carbon encapsulated cobalt-iron nanoparticles with superior catalytic activity for oxygen reduction reaction.

Replacing precious metal catalysts with low-price and abundant catalysts is one of urgent goals for green and sustainable energy development. It is imperative yet challenging to search low-cost, high-efficiency, and long-durability electrocatalysts for oxygen reduction reaction (ORR) in energy conversion devices. Herein, three-dimensional low-cost Co3Fe7 nanoparticles/nitrogen, manganese-codoped porous carbon (Co3Fe7/N, Mn-PC) was synthesized with the mixture of dicyandiamide, cobalt (II) tetramethoxyphenylporphyrin (Co(II)TMOPP), hemin, and manganese acetate by one-step pyrolysis and then acid etching. The resultant Co3Fe7/N, Mn-PC exhibited excellent durability and prominent ORR activity with more positive onset potential (Eonset, 0.98 V) and half-wave potential (E1/2, 0.87 V) in 0.1 M KOH electrolyte, coupled with strong methanol resistance. The pyrolysis temperature and optimal balance of graphite with pyridine-nitrogen are of significance for the ORR performance. The prepared Co3Fe7/N, Mn-PC displayed excellent ORR performance over commercial Pt/C in the identical environment. It was ascribed to the uniform 3D architecture, Mn- and N-doping effects by finely adjusting the electronic structures, coupled with the synergistic catalytic effects of multi-compositions and multi-active sites. This work provides some constructive guidelines for preparation of low-cost and high-efficiency ORR electrocatalysts.

Engineering 3D hierarchical thorn-like PtPdNiCu alloyed nanotripods with enhanced performances for methanol and ethanol electrooxidation.

Developing efficient and stable electrocatalysts with three-dimensional (3D) hierarchical nanostructures is extremely important in practical applications of direct alcohol fuel cells. Herein, 3D hierarchical thorn-like multi-metallic PtPdNiCu alloyed nanotripods (PtPdNiCu TNTPs) were efficiently fabricated by a one-pot aqueous method, in which Pluronic F127 performed as the structure-director and dispersing agent. The as-prepared PtPdNiCu TNTPs exhibited distinct electrocatalytic activity for methanol oxidation reaction (MOR) with a mass activity (MA) of 1.465 A mg-1Pd, which is superior to commercial Pt/C (0.925 A mg-1Pd) in 1.0 M KOH solution, along with the greater MA (1.019 A mg-1Pd) for ethanol oxidation reaction (EOR) than Pt/C (0.712 A mg-1Pd). This work would provide an impetus for rationally constructing multimetal nanomaterials to commercial implementation of advanced alcohol fuel cells.

3D highly branched PtCoRh nanoassemblies: Glycine-assisted solvothermal synthesis and superior catalytic activity for alcohol oxidation.

Advanced Pt-based ternary nanocatalysts display dramatically enhanced utilization efficiency of Pt alternative to mono- and bi-counterparts, owing to the synergistic effects of the tri-metals. Herein, multicomponent uniform 3D PtCoRh highly branched nanoassemblies (HBNAs) were prepared by glycine-assisted one-pot solvothermal method in oleylamine (OAm). The effects of the precursor types, reaction time and amount of glycine were critically investigated in this synthesis. The as-prepared PtCoRh HBNAs displayed outstanding electrocatalytic activity and improved stability towards ethanol oxidation reaction (EOR) and methanol oxidation reaction (MOR) in 1 M KOH electrolyte, whose mass/specific activities were 1.75 A mg-1/4.03 mA cm-2 and 0.98 A mg-1/2.34 mA cm-2, respectively, which were remarkably higher than commercial Pt/C (0.85 A mg-1/4.03 mA cm-2 and 0.47 A mg-1/0.89 mA cm-2). This study provides some novel guidelines to fabricate advanced multimetallic electrocatalysts for practical applications in direct alcohol fuel cells (DAFCs).

Melamine-assisted solvothermal synthesis of PtNi nanodentrites as highly efficient and durable electrocatalyst for hydrogen evolution reaction.

Rational design of highly efficient and durable electrocatalysts for hydrogen evolution reaction (HER) is of prime importance for renewable and sustainable energy. Herein, PtNi nanodentrites (PtNi NDs) were facilely synthesized in oleylamine (OAm) by a one-pot solvothermal method, using melamine and cetyltrimethylammonium chloride (CTAC) as co-structure-directing agents. The obtained catalyst showed superior catalytic activity and enhanced durability for HER relative to commercial Pt/C, home-made PtNi3 nanocrystals (NCs) and Pt3Ni NCs both in alkaline and acidic media. The enhanced HER activities are attributed to bimetallic synergies and interface structures in PtNi NDs. This work provides an effective strategy to prepare highly efficient and durable electrocatalysts for HER.

One-pot aqueous fabrication of reduced graphene oxide supported porous PtAg alloy nanoflowers to greatly boost catalytic performances for oxygen reduction and hydrogen evolution.

Herein, reduced graphene oxide supported porous PtAg alloy nanoflowers (PtAg NFs/rGO) were synthesized by a simple one-pot aqueous method using pyridinium-based dicationic ionic liquid (1,4-bis(pyridinium)butane dibromide, Bpb-2Br) as the new structure-director and stabilizing agent. The products were characterized by a series of techniques. The obtained nanocomposite had more positive onset potential (1.03 V) for oxygen reduction reaction (ORR) in alkaline electrolyte than those of commercial Pt/C (50 wt%, 0.96 V) and home-made Pt nanoparticles (NPs)/rGO (Pt NPs/rGO, 0.97 V), showing the enhanced catalytic performance for hydrogen evolution reaction (HER) with the positive onset potential (-26 mV) and a small Tafel slope (31 mV dec-1) relative to Pt/C (-18 mV, 31 mV dec-1) and Pt NPs/rGO (-42 mV, 36 mV dec-1) in 0.5 M H2SO4.

Facile synthesis of bimetallic gold-palladium nanocrystals as effective and durable advanced catalysts for improved electrocatalytic performances of ethylene glycol and glycerol oxidation.

In this work, well-defined bimetallic AuPd alloyed nanocrystals (AuPd NCs) were facilely synthesized by a straightforward and controllable one-step wet-chemical strategy, using a biomolecule (L-hydroxyproline, L-Hyp) as the green stabilizer and the structure-directing agent. Their morphology, size, composition, crystal structures and growth mechanism were investigated by a series of techniques. The synthesized architectures exhibited enlarged electrochemically active surface area (ECSA), improved catalytic activity, enhanced durability and stability towards ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR) in alkaline electrolytes in comparison with commercial Pd black catalyst.

Immobilization of Prussian Blue nanoparticles onto thiol SAM modified Au electrodes for electroanalytical or biosensor applications.

Poly(vinylpyrrolidone) (PVP)-protected Prussian Blue (PB) nanoparticles were prepared by simply mixing FeCI3 and K4Fe(CN)6 with absence or presence of HCI or/and KCI in water solution. The obtained PB nanoparticles were immobilized onto thiol self-assembled monolayer (SAM) modified Au electrodes. L-cysteine (Cys) and 1,8-octanedithiol (ODT) were compared as a bridge between the gold surface and the PB nanoparticles. The results show that PB prepared from the initial solution with KCI gives preferred electrochemical response and that Cys/Au shows improved immobilization effect of PB than ODT/Au. The obtained PB/Cys/Au electrodes exhibit electrocatalytic activity toward H2O2 reduction and DL-homocysteine (HCys) oxidation. Glucose oxidase (GOX) was immobilized onto PB modified electrode to explore the potentials for the design of oxidase-based biosensors. It is possible to anchor PB nanoparticles and develop their application on electroanalysis and biosensing.

Simple one-pot aqueous synthesis of AuPd alloy nanocrystals/reduced graphene oxide as highly efficient and stable electrocatalyst for oxygen reduction and hydrogen evolution reactions.

Herein, we develop a simple one-pot aqueous method to prepare AuPd alloy nanocrystals on reduced graphene oxide (AuPd NCs/rGO), by using 1-acetyl-4-(p-hydroxyphenyl) piperazine (AHPP) as the reductant, stabilizing agent and structure-director, without any other additives (e.g., seed, surfactant or polymer). The product is mainly characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and thermogravimetric analysis. The obtained AuPd NCs/rGO displays enlarged electrochemically active surface area and superior catalytic performances toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) relative to Pt/C, Pd/C, Pd/rGO and Au/rGO catalysts, showing promising applications in energy storage and conversion.

One-pot synthesis of hollow AgPt alloyed nanocrystals with enhanced electrocatalytic activity for hydrogen evolution and oxygen reduction reactions.

Herein, a simple one-pot aqueous method was developed for the fabrication of uniform hollow bimetallic AgPt alloyed nanocrystals (H-AgPt NCs) by using 5-aminoorotic acid (5-amino-2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid) as a growth-directing agent, without any seed, organic solvent or template involved. The prepared H-AgPt NCs displayed enhanced electrocatalytic activity for hydrogen evolution reaction (HER) with a more positive onset overpotential (ηonset) of -28mV and a smaller Tafel slope of 40mVdec-1 relative to commercial Pt black (-34mV, 50mVdec-1) and Pt/C (20wt.%, -33mV, 33mVdec-1) in 0.5M H2SO4. Meanwhile, the obtained catalyst exhibited improved catalytic features toward oxygen reduction reaction (ORR) with a positive ηonset (0.916V) and enhanced kinetic current density (243.23mAmg-1Pt) in 0.1M HClO4 at 0.850V compared with Pt black (0.876V, 25.85mAmg-1Pt).