Crystal defect engineering of Bi_(2)Te_(3)nanosheets by Ce doping for efficient electrocatalytic nitrogen reduction

Electrochemical nitrogen reduction reaction(NRR)is a promising method for the synthesis of ammonia(NH3).However,the electrochemical NRR process remains a great challenge in achieving a high NH3 yield rate and a high Faradaic efficiency(FE)due to the extremely strong N≡N bonds and the competing hydrogen evolution reaction(HER).Recently,bismuth telluride(Bi_(2)Te_(3))with two-dimensional layered structure has been reported as a promising catalyst for N_(2)fixation.Herein,to further enhance its NRR activity,a general doping strategy is developed to introduce and modulate the crystal defects of Bi_(2)Te_(3)nanosheets by adjusting the amount of Ce dopant(denoted as Ce_(x)-Bi_(2)Te_(3),where x represents the designed molar ratio of Ce/Bi).Meanwhile,the crystal defects can be designed and controlled by means of ion substitution and charge compensation.At−0.60 V versus the reversible hydrogen electrode(RHE),Ce_(0.3)-Bi_(2)Te_(3)exhibits a high NH_(3) yield(78.2μg·h^(−1)·mgcat^(−1)),a high FE(19.3%),excellent structural and electrochemical stability.Its outstanding catalytic activity is attributed to the tunable crystal defects by Ce doping.This work not only contributes to enhancing the NRR activity of Bi_(2)Te_(3)nanosheets,but also provides a reliable approach to prepare high-performance electrocatalysts by controlling the type and concentration of crystal defects for artificial N_(2)fixation.

A revisiting of transition metal phosphide(Cu_(3)P and FeP)nanozymes for two sugar-related reactions

Transition metal phosphides(TMPs)are essential catalysts for some general catalytic reactions.However,their potentials for biological catalysis have seldom been explored.Herein,we investigated the enzyme-like properties of four TMPs(FeP,CoP,Ni_(2)P,and Cu_(3)P)towards two sugar-related reactions.Among the four TMPs,Cu_(3)P nanoparticles(NPs)efficiently catalyzed the hydrolysis of glycosidic bonds as glycoside hydrolase mimics,and FeP NPs possessed both glucose oxidase-like(GOx-like)and peroxidase-like activities,which combined into a cascade reaction for glucose’s simple and one-step colorimetric biosensor without GOx.Cu_(3)P and FeP NPs with distinctive enzyme-like activities have shown unique biological catalysis potentials for further applications with an attractive and challenging goal of developing nanomaterials to mimic natural enzymes,which encourages more efforts to reveal TMP’s capabilities towards biocatalysis.

Critical evaluation of the glucose oxidase-like activity of gold nanoparticles stabilized by different polymers

Polymer stabilizers are widely used to synthesize gold nanoparticles(Au NPs)to prevent their aggregation and improve their stability.Although stabilizers are known to greatly influence both the structure and size of Au NPs,limited efforts explore their effects on the activity of Au NPs for biocatalysis.Herein,different polymers are used as stabilizers to synthesize Au NPs.For the glucose oxidase-like activity,we find that without the spatial barrier from stabilizers,naked Au NPs show significantly high catalytic activity as well as the worst stability.Among the polymers,polyacrylic acid-stabilized Au NPs exhibit the highest activity,whose Vmax(0.74μM·s^(−1))is higher than that of the natural glucose oxidase(0.37μM·s^(−1))due to the smallest particle size(<2 nm)and the weak spatial resistance of polyacrylic acid.These variable catalytic results derive from the comprehensive effects including size,steric hindrance,and electronic effect.However,further selectivity and activity tests have exposed shortcomings.They possess universal activities for aldose oxidation,whereas cannot retain activities in typical physiological environments.Our findings highlight the role of polymer stabilizers in imposing effects on the glucose oxidase-like activity of Au NPs and provide a basis for further Au NPs engineering and applications.

Ultrastable and ultrasensitive pH-switchable carbon dots with high quantum yield for water quality identification,glucose detection,and two starch-based solid-state fluorescence materials

It is attractive and encouraging to develop new fluorescent carbon dots(CDs)with excellent optical properties and promising applications prospects.Herein,highly-efficient green emissive CDs(m-CDs)with a high quantum yield(QY)of 71.7%in water are prepared through a facile solvothermal method.Interestingly,the m-CDs exhibit excellent fluorescence stability in the pH range of 1–9.However,the fluorescence intensity of the m-CDs is almost completely quenched as the pH is increased from 9 to 10.The mechanism of the unique pH-responsive behavior is discussed in detail and a plausible mechanism is proposed.Owing to the unique pH-responsive behavior,the m-CDs are used as a on-off fluorescent probe for water quality identification.By combining the reversible pH-ultrasensitive optical properties of the m-CDs in the pH range of 9–10 with the glucose oxidase-mimicking(GOx-mimicking)ability of Au nanoparticles(AuNPs),glucose can be quantitatively detected.Finally,two environment-friendly starch-based solid-state fluorescence materials(powder and film)are developed through green preparation routes.