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Recently Ni–Co mixed oxide nanoparticles have received tremendous attention for their application potential in electrochemical devices, biosensing, and biomedical treatments. However, the biomedica...

Surface activation of catalysts is known to be an efficient process to enhance their activity in catalytic processes. The activation process includes the generation of oxygen vacancies, changing the nature of the catalyst surface from acidic to basic and vice versa, and the reduction of catalyst surface by H2. On the other hand, magnetically separable catalysts are highly beneficial for their utilization in water or biological fluid-based catalytic processes, as they can be easily guided to the target site and recovered. Here, we present the fabrication of CoFe2O4 and composites of Co3O4/CoFe2O4/α-Fe2O3 and Co/CoFe2O4/α-Fe2O3 through solution combustion process to utilize them as catalysts for 4-nitrophenol (4-NP) reduction. Although none of the as-prepared CoFe2O4 and Co3O4/CoFe2O4 was seen to be active in 4-NP reduction reaction, the surface of the composite gets activated by borohydride (NaBH4) treatment to act as a highly active catalyst for 4-NP reduction. X-ray photoelectron spectroscopy of the composite revealed the formation of metal-hydroxide (M–O–H) species of both Co and Fe at its surface due to borohydride treatment. The mechanism of the surface activation and the dynamics of 4-NP reduction of the surface-activated composite have been studied, proposing a possible pathway for the reduction of 4-NP.

Interest in nanostructured partially substituted bismuth oxides has been increasing over the last years. Research on new synthesis methods, properties, and possible uses for these oxides is needed. The objective of this paper is to synthesize β-Bi2O3, β-Bi2O3:Eu3+, β-Bi2O3:Mn4+, Bi12Bi0.8O19.2, Bi12Bi0.8O19.2/Li+, Bi12MnO20, and Bi12SiO20 nanoparticles and to investigate their structural, spectroscopic, and optical changes. Some of the causes that generated their properties are also discussed. These materials are important because the doping or partial substitution of bismuth oxide with these cations (Eu3+, Mn4+, and Si4+) modifies some properties such as optical absorption, reactivity toward CO2, among others. X-ray diffraction (in powders), high-resolution transmission electron microscopy, Fourier transform infrared (FTIR), resonance Raman scattering, diffuse reflectance, and solid-state magic-angle-spinning 29Si NMR were used for the characterization of the synthesized materials. We found that partial ...

Main text The CCQM-K152 key comparison in parallel with CCQM-P192 pilot comparison were organised jointly by the Inorganic Analysis (IAWG) and Electrochemical Analysis and Classical Chemical methods (EAWG) working groups of CCQM to test the abilities of the metrology institutes to measure the amount content of the non-metallic elements in high purity salts as well as assaying high purity salts to be used as primary standards. Eight NMIs participated in the key comparison CCQM-K152. Ural Research Institute for Metrology (UNIIM) (since 2020 it has been called Affiliated Branch of D.I.Mendeleev Institute for Metrology (VNIIM-UNIIM)), Russian Federation, acted as the coordinating laboratory of the comparison. There were two measurands: the amount content of oxidants expressed as potassium iodate, mol/kg, and the mass fraction of iodine, kg/kg. The measurement methods used by participants for the amount content of oxidants expressed as potassium iodate were constant current coulometry and titrimetry. For the mass fraction of iodine results were provided by 5 NMIs, 3 of them used the direct approach (recalculation from coulometric or titrimetric results) and 2 NMIs implemented the indirect approach based on impurities assessment using combination of the instrumental methods (ion chromatography, ICP OES, ICP MS). In general, good overlap of results was observed for both measurands. Direct and indirect approaches for purity determination of pure salt provide overlapping results when impurities are summarized in ionic form. The suitability of coulometry for assay of high purity materials was demonstrated again, and some possible technical problems were highlighted. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Main text This key comparison is being performed to evaluate the degree of equivalence of measurement procedures to support the participants' claims of Calibration and Measurement Capabilities (CMCs) and to evaluate the capabilities of participants for the determination of the pH of carbonate buffer solutions. This is the fourth APMP key comparison on pH measurement following APMP.QM-K9/P16 (phosphate), APMP.QM-K19/P25 (borate) and APMP.QM-K91/P29 (phthalate). The results have the linkage to CCQM-K18.2016 (carbonate buffer) and were evaluated by comparing the results of the Physikalisch-Technische Bundesanstalt (PTB) and the National Metrology Institute of Japan (NMIJ) performing Harned cell method. The results of PTB and NMIJ were used for the definition of the Key Comparison Reference Value (KCRV). The ensuing pH value was calculated based on the Bates-Guggenheim convention to compare the results of primary and secondary methods. In this comparison measurements of pH were performed only at the temperature of 25 °C. The results demonstrated by most participants are in better agreement than those in CCQM-K18.2016. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Main text The CCQM-K34.2016.1 was organized as a subsequent key comparison of CCQM-K34.2016 assay of potassium hydrogen phthalate to demonstrate the improved capability of the laboratories which did not perform well in the original CCQM-K34.2016. The key comparisons were organized jointly by the working groups of inorganic analysis and electrochemistry analysis. National Institute of Metrology P. R. China (NIM) acted as the coordinating laboratory, and NIM and SMU (Slovak Institute of Metrology) served as linking laboratories to link to the CCQM-K34.2016 key comparison reference value (KCRV). CENAM, NIST and VNIIFTRI registered in K34.2016.1, however, VNIIFTRI gave up participating in the comparison due to failure to get the samples through the customs clearance in Russia. All participants used constant current coulometry for measurement, and improved capabilities were demonstrated. The scope is same as in CCQM-K34.2016. The comparison tested the capabilities and methods used for assay of high purity materials. Good result indicates good performance in assaying the purity （amount content）of solid weak acids. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

La1-xSrxMnO3 perovskites are of enormous current interest due to their superior magnetoresistance and application as cathode material for solid oxide fuel cells. However, practical applications of these perovskites critically depend on size, composition, and concentration of La3+ vacancies at their surfaces. Here we present the fabrication of size controlled (90–255 nm average size), highly crystalline La1-xSrxMnO3 (x = 0, 0.3, 0.5, and 1) nanoparticles, simply by ball-milling of metal acetylacetonate precursors in NaCl and subsequent air-annealing. The size of the nanoparticles increased in the order LaMnO3+ δ

Key comparison (KC) CCQM-K18.2016 was performed to evaluate the degree of equivalence between pH measurement results on an unknown carbonate buffer reported by participating National Metrology Institutes and Designated Institutes (NMI/DIs). The participants used the highest metrological method existing at their institution. The nominal buffer pH was 10.0 and was determined only at 25 °C. Good agreement of the results is demonstrated by most participants. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

The CCQM-K34.2016 key comparison for determination of the purity of potassium hydrogen phthalate was organized jointly by the inorganic analysis and electrochemical analysis working groups of CCQM to repeat CCQM-K34 for supporting CMC claims of participating metrology institutes in assaying the amount content of monoprotic weak acid. National Institute of Metrology P.R.China (NIM) acted as the coordinating laboratory of this comparison. Twelve NMIs participated in this key comparison. With the exception of one laboratory that used NaOH-titration, all participants used coulometry. In general a good overlap of results was observed, the suitability of coulometry for assay of high purity materials was demonstrated again, and some possible technical problems were highlighted. The comparison tested the capabilities and methods used for assay of high purity materials. Good result indicates good performance in assaying the purity (amount content) of solid weak acids. KEY WORDS FOR SEARCH CCQM-K34.2016; potassium hydrogen phthalate; coulometry Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

International audience; This work reports the effects of four organic compounds (referred to as levelers) on the electrodeposition of Zn on steel from alkaline free-cyanide electrolytes. The additives tested included polyvinylalcohol (PVA) and the condensation products of epichlorhydrin with amines, called polyamines (PAs), that were synthesized using an aliphatic amine (PA-I, from diethylamine and PA-II from diethylamine-triethylamine), and a heterocyclic quaternary imidazolium molecule (PA-Imid, from imidazole). These compounds were evaluated in the absence and in addition to a quaternary ammonium brightener, N-benzyl-3-carboxylpyridinium chloride (3NCP). The imidazole derivative-based polyamine (PA-Imid) causes greater inhibition of the zinc reduction process than the aliphatic polyamine, and more cathodic overpotential is necessary to promote massive metal deposition. The morphology of the deposits is modified when polyamines are added to the bath; more compact and smaller crystals are obtained with PVA as well as with polyamine PA-I. The addition of PA-II as well as PA-Imid yields crystals growing perpendicular to the substrate. The addition of 3NCP with PVA, PA, or PA-Imid increased the deposition overpotential and modified the morphology by diminishing the grain size. In the absence of additives, crystallographic orientation favored the basal Zn(002) with high atomic packing. The addition of the levelers favored the high-angle pyramidal Zn(101) with low atomic packing. The combination of the levelers with (3NCP) favored the prismatic Zn(100) crystallographic orientation. Additives decrease the size of zinc crystals and tend to increase the energy of lattice favoring the growth of pyramidal and prismatic planes.

International audience; The influence of cobalt on the electrodeposition of zinc onto AISI 1018 steel was studied in weakly alkaline glycine solutions. Thermodynamic calculations were performed to construct predominance-zone diagrams to identify the stability of the zinc and cobalt glycine complexes, and experimental studies of electrochemical behavior and deposit properties were conducted. When zinc is present, cobalt deposition shifts to more negative potentials, producing ZnCo alloys. Two main reduction steps were observed for electrodeposition from the ZnCo bath: the first at low potentials was due to ZnCo electrodeposition. In the second, at more negative potentials, cobalt content in the deposit increased forming a range of intermediate phases, and the hydrogen-evolution reaction became significant. The presence of Co(II) in the bath modified the morphology of the deposits as well as reducing the faradaic metal-deposition efficiency. ZnCo-deposit morphology was modified by the applied current density as well as the metal composition of the coating. X-ray diffraction studies revealed that cobalt oxide or hydroxide is formed during ZnCo electrodeposition, indicating that an elevation of the interfacial pH plays a role in the alloy deposition process.

International audience; The effects of several quaternary ammonium compounds on electrodeposition of zinc onto AISI 1018 carbon steel were studied in an alkaline zincate electrolyte. Tetraethylammonium, tetrabutylammonium, N-benzyltriethylammonium and N-benzyl-3-carboxyl pyridinium cations were examined. The electrochemical behavior and the inhibition of dendrite formation are related to the structure of the ammonium compounds. The presence of either long-chain aliphatic groups or aromatic groups, i.e., with tetrabutylammonium hydroxide (TBAOH) or N-benzyltriethylammonium chloride (NBT) exerts a more effective inhibition of dendrite formation. N-benzyl-3-carboxylpyridinium (3NCP) and tetraethylammonium hydroxide (TEAOH) additives lead to slightly deformed deposit morphology. Crystallographic measurements of the zinc deposits revealed a highly oriented deposit formed in the presence of 3NCP, which favors the dense atomic packing basal plane (002). The presence of TEAOH diminishes slightly the peak of plane (002) and introduces some pyramidal (101) orientation. Addition of NBT or TBAOH favors the formation of low-atomic packing prismatic planes. Additives that increase the overpotential for Zn(II) reduction tend to promote the formation of high-energy low-atomic packing crystallographic planes. Comparison of the effects of these ammonium compounds indicates that the observed effects are related to the hydrophobic and steric interactions introduced to the interface by the size and structure of the ammonium compounds.

Phosphate esters are employed in some agrochemical formulations and have long life time in the Environment. They are neurotoxic to mammals and it is very difficult to hydrolyze them. It is easy to find papers in the literature dealing with transition metal complexes used in the hydrolysis processes of organophosphorous compounds. However, there are few reports related with degradation of phosphate esters with inorganic nanoparticles. In this work bis-4-nitrophenyl phosphate (BNPP) was used as an agrochemical agent model. The BNPP interaction with zero-valent iron nanoparticles (ZVI NPs), in aqueous media, was searched. The concentration of BNPP was 1000 times higher than the ZVI NPs concentration. The average size of the used iron nanoparticles was 10.2 ± 3.2 nm. The BNPP degradation process was monitored by means of UV-visible method. Initially, the BNPP hydrolysis happens through the P-O bonds breaking-off under the action of the ZVI NPs. Subsequently, the nitro groups were reduced to amine groups. The overall process takes place in 10 minutes. The reaction products were identified employing standard substances in adequate concentrations. The iron by-products were isolated and characterized by X-RD. These iron derivatives were identified as magnetite (Fe3O4) and/or maghemite (γ-Fe2O3) and lepidocrocite (γ-FeOOH). A suggested BNPP degradation mechanism will be discussed.

International audience; The effects of vanillin and anisaldehyde on electrodeposition of zinc–cobalt alloys onto AISI 1018 carbon steel were studied in an alkaline gluconate zincate electrolyte. The influence of an additive on the metal discharge depends on the structure of the added molecule and on the nature of the substrate. The composition of the deposit varies during the electrodeposition process. Maximum cobalt content is observed close to the steel–ZnCo interface for ZnCo formed with or without vanillin, but the composition profile becomes more uniform when anisaldehyde is added to the bath. The morphology of Zn-rich Co-alloy coatings was evaluated: Cobalt ions produce porous ZnCo alloys; vanillin induces slightly porous deposits, whereas uniform and more compact deposits were observed with anisaldehyde. Furthermore, a crystallographic study showed that the orientation of the lattice planes changes, with highly oriented deposits produced in the presence of anisaldehyde.