The Role of an Inert Electrode Support in Plasmonic Electrocatalysis

Plasmonic nanostructures loaded onto catalytically inert conductive support materials are believed to be advantageous for maximizing photocatalytic effects in photoelectrochemical systems due to the increased efficiency of Schottky barrier-free architectures in collecting hot charge carriers. However, the systematic mechanistic investigation and description of the inert electrode support contribution to plasmonic electrocatalysis is missing. Herein, we systematically investigated the effect of the supporting electrode material on the observed photocatalytic enhancement by comparing photoelectrocatalytic properties of AuNPs supported on highly oriented pyrolytic graphite (HOPG) and on indium tin oxide (ITO) electrodes using electrocatalytic benzyl alcohol (BnOH) oxidation as a model system. Upon illumination, only ~(3 ± 1)% enhancement in catalytic current was recorded on the AuNP/ITO electrodes in contrast to ~(42 ± 6)% enhancement on AuNP/HOPG electrodes. Our results showed that the local heating due to light absorption by the electrode material itself independent of localized surface plasmon effects is the primary source of the observed significant photo-induced enhancement on the HOPG electrodes in comparison to the ITO electrodes. Moreover, we demonstrated that an increased interfacial charge transfer at elevated temperatures, and not faster substrate diffusion is the main source of the enhancement. This work highlights the importance of systematic evaluation of contributions of all parts, even if they are catalytically inert, to the light-induced facilitation of catalytic reactions in plasmonic systems.

An Electrochemical Enzyme Biosensor for Ammonium Detection in Aquaculture Using Screen-Printed Electrode Modified by Gold Nanoparticle/Polymethylene Blue

A SPEC/AuNPs/PMB modified electrode was prepared by electrodeposition and electro-polymerization. The electrochemical behavior of reduced nicotinamide adenine dinucleotide (NADH) on the surface of the modified electrode was studied by cyclic voltammetry. A certain amount of substrate and glutamate dehydrogenase (GLDH) were coated on the modified electrode to form a functional enzyme membrane. The ammonia nitrogen in the water sample could be calculated indirectly by measuring the consumption of NADH in the reaction. The results showed that the strength of electro-catalytic current signal was increased by two times; the catalytic oxidation potential was shifted to the left by 0.5 V, and the anti-interference ability of the sensor was enhanced. The optimum substrate concentration and enzyme loading were determined as 1.3 mM NADH, 28 mM α-Ketoglutarate and 2.0 U GLDH, respectively. The homemade ceramic heating plate controlled the working electrode to work at 37 °C. A pH compensation algorithm based on piecewise linear interpolation could reduce the measurement error to less than 3.29 μM. The biosensor exhibited good linearity in the range of 0~300 μM with a detection limit of 0.65 μM NH4+. Compared with standard Nessler’s method, the recoveries were 93.71~105.92%. The biosensor was found to be stable for at least 14 days when refrigerated and sealed at 4 °C.

Calibrating SECCM measurements by means of a nanoelectrode ruler. The intrinsic oxygen reduction activity of PtNi catalyst nanoparticles

Scanning electrochemical cell microscopy (SECCM) is increasingly applied to determine the intrinsic catalytic activity of single electrocatalyst particle. This is especially feasible if the catalyst nanoparticles are large enough that they can be found and counted in post-SECCM scanning electron microscopy images. Evidently, this becomes impossible for very small nanoparticles and hence, a catalytic current measured in one landing zone of the SECCM droplet cannot be correlated to the exact number of catalyst particles. We show, that by introducing a ruler method employing a carbon nanoelectrode decorated with a countable number of the same catalyst particles from which the catalytic activity can be determined, the activity determined using SECCM from many spots can be converted in the intrinsic catalytic activity of a certain number of catalyst nanoparticles.

Operando tracking of oxidation-state changes by coupling electrochemistry with time-resolved X-ray absorption spectroscopy demonstrated for water oxidation by a cobalt-based catalyst film

Transition metal oxides are promising electrocatalysts for water oxidation, i.e., the oxygen evolution reaction (OER), which is critical in electrochemical production of non-fossil fuels. The involvement of oxidation state changes of the metal in OER electrocatalysis is increasingly recognized in the literature. Tracing these oxidation states under operation conditions could provide relevant information for performance optimization and development of durable catalysts, but further methodical developments are needed. Here, we propose a strategy to use single-energy X-ray absorption spectroscopy for monitoring metal oxidation-state changes during OER operation with millisecond time resolution. The procedure to obtain time-resolved oxidation state values, using two calibration curves, is explained in detail. We demonstrate the significance of this approach as well as possible sources of data misinterpretation. We conclude that the combination of X-ray absorption spectroscopy with electrochemical techniques allows us to investigate the kinetics of redox transitions and to distinguish the catalytic current from the redox current. Tracking of the oxidation state changes of Co ions in electrodeposited oxide films during cyclic voltammetry in neutral pH electrolyte serves as a proof of principle. Graphical abstract

ZIF-12/Fe-Cu LDH Composite as a High Performance Electrocatalyst for Water Oxidation

Layered double hydroxides (LDH) are being used as electrocatalysts for oxygen evolution reactions (OERs). However, low current densities limit their practical applications. Herein, we report a facile and economic synthesis of an iron-copper based LDH integrated with a cobalt-based metal-organic framework (ZIF-12) to form LDH-ZIF-12 composite (1) through a co-precipitation method. The as-synthesized composite 1 requires a low overpotential of 337 mV to achieve a catalytic current density of 10 mA cm−2 with a Tafel slope of 89 mV dec−1. Tafel analysis further demonstrates that 1 exhibits a slope of 89 mV dec−1 which is much lower than the slope of 284 mV dec−1 for LDH and 172 mV dec−1 for ZIF-12. The slope value of 1 is also lower than previously reported electrocatalysts, including Ni-Co LDH (113 mV dec−1) and Zn-Co LDH nanosheets (101 mV dec−1), under similar conditions. Controlled potential electrolysis and stability test experiments show the potential application of 1 as a heterogeneous electrocatalyst for water oxidation.

Immobilization of Pt nanoparticles on hydrolyzed polyacrylonitrile-based nanofiber paper

The electrochemical activity of catalysts strongly depends on the uniform distribution of monodisperse Pt nanoparticles without aggregates. Here, we propose a new hydrolysis-assisted smearing method for Pt loading on a free-standing paper-type electrode. Polyacrylonitrile (PAN)-based nanofiber paper was used as the electrode, and it acted as a Pt support. Hydrolysis of the electrode tripled the number of active nucleation sites for Pt adsorption on the PAN nanofibers, thereby significantly enhancing the wettability of the nanofibers. This facilitated the uniform distribution of Pt nanoparticles without aggregate formation up to 40 wt% (about 0.8 mg/cm2) with a particle size of about 3 nm. The catalytic current of the hydrolyzed Pt electrode in CH3OH/H2SO4 solution exceeded 213 mA/cm2 Pt mg, which was considerably greater than the current was 148 mA/cm2 Pt mg for an unhydrolyzed electrode.

Development of Highly Sensitive Immunosensor for Detection of Staphylococcus aureus Based on AuPdPt Trimetallic Nanoparticles Functionalized Nanocomposite

The rapid and sensitive detection of Staphylococcus aureus (S. aureus) is essential to ensure food safety and protect humans from foodborne diseases. In this study, a sensitive and facile electrochemical immunosensor using AuPdPt trimetallic nanoparticles functionalized multi-walled carbon nanotubes (MWCNTs-AuPdPt) as the signal amplification platform was designed for the label-free detection of S. aureus. The nanocomposite of MWCNTs-AuPdPt was prepared by an in situ growth method of loading AuPdPt trimetallic nanoparticles on the surface of MWCNTs. The synthesized MWCNTs-AuPdPt featured good conductivity and superior catalytic performance for hydrogen peroxide. The nanocomposite of MWCNTs-AuPdPt with good biocompatibility and high specific surface area was further functionalized by anti-S. aureus antibodies. The immobilized antibodies could efficiently capture S. aureus to the modified electrode by an immune reaction, which resulted in the change of catalytic current intensity to realize the sensitive detection of S. aureus. The designed immunosensor could detect S. aureus in a linear range from 1.1 × 102 to 1.1 × 107 CFU mL−1 with a low detection limit of 39 CFU mL−1. Additionally, the proposed immunosensor was successfully applied to determine S. aureus in actual samples with acceptable results. This strategy provided a promising platform for highly sensitive determination of S. aureus and other pathogens in food products.

A Novel Nonenzymatic Hydrogen Peroxide Sensor Based on Magnetic Core-Shell Fe3O4@C/Au Nanoparticle Nanocomposite

Fe3O4@C/Au nanoparticle (AuNP) nanocomposites were prepared through electrostatic adsorption of AuNPs onto PDDA-functionalized core/shell Fe3O4@C magnetic nanospheres, which had been synthesized by a facile solvothermal method. The morphology and composition of the nanocomposites were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), etc. Moreover, highly electrocatalytic activity to the reduction of hydrogen peroxide (H2O2) was also exhibited on the Fe3O4@C/AuNP-modified indium tin oxide (ITO) electrode. The effect of solution pH and the modification amount of Fe3O4@C/AuNPs on the performance of electrocatalytic H2O2 reduction was investigated. Under the optimal conditions, the catalytic current showed a linear relationship with the increase of H2O2 concentration in the range of 0.007–15 mM and a detection limit of 5 μM. The H2O2 sensor showed high selectivity for H2O2 detection, which could effectively resist the interference of ascorbic acid (AA), uric acid (UA), and citric acid (CA). Finally, the H2O2 sensor was used in the real fetal bovine serum to detect H2O2 and obtained satisfactory results with the recovery values ranging from 95.14 to 103.6%.

Na3[Ru2(µ-CO3)4] as a Homogeneous Catalyst for Water Oxidation; HCO3− as a Co-Catalyst

In neutral medium (pH 7.0) [RuIIIRuII(µ-CO3)4(OH)]4− undergoes one electron oxidation to form [RuIIIRuIII(µ-CO3)4(OH)2]4− at an E1/2 of 0.85 V vs. NHE followed by electro-catalytic water oxidation at a potential ≥1.5 V. When the same electrochemical measurements are performed in bicarbonate medium (pH 8.3), the complex first undergoes one electron oxidation at an Epa of 0.86 V to form [RuIIIRuIII(µ-CO3)4(OH)2]4−. This complex further undergoes two step one electron oxidations to form RuIVRuIII and RuIVRuIV species at potentials (Epa) 1.18 and 1.35 V, respectively. The RuIVRuIII and RuIVRuIV species in bicarbonate solutions are [RuIVRuIII(µ-CO3)4(OH)(CO3)]4− and [RuIVRuIV(µ-CO3)4(O)(CO3)]4− based on density functional theory (DFT) calculations. The formation of HCO4− in the course of the oxidation has been demonstrated by DFT. The catalyst acts as homogeneous water oxidation catalyst, and after long term chronoamperometry, the absorption spectra does not change significantly. Each step has been found to follow a proton coupled electron transfer process (PCET) as obtained from the pH dependent studies. The catalytic current is found to follow linear relation with the concentration of the catalyst and bicarbonate. Thus, bicarbonate is involved in the catalytic process that is also evident from the generation of higher oxidation peaks in cyclic voltammetry. The detailed mechanism has been derived by DFT. A catalyst with no organic ligands has the advantage of long-time stability.