Ultrasensitive determination of selenium in food samples and its speciation in water and beverages using thiosemicarbazide-incorporated graphene and total-reflection X-ray fluorescence spectrometry.

The paper presents a new analytical procedure for the determination and speciation of trace and ultratrace selenium in water, beverages, seafood, milk, and vegetables. The developed method is based on the dispersive micro-solid phase extraction with the use of new thiosemicarbazide-incorporated graphene as a solid sorbent, in combination of the total-reflection X-ray fluorescence spectrometry (TXRF). As a result, we have created an auspicious analytical tool for fast and sensitive analysis of samples with a complex matrix. Regardless of the specimen type, the method is characterized by a very low detection limit of 1.7 pg mL-1 and high precision. The developed strategy allowed us to solve common problems associated with selenium loss during the sample preparation for the TXRF measurement and also improve its performance toward the analysis of beverages and high saline/solid samples, which may even be impossible to perform using standard sample preparation procedures for a TXRF measurement.

Spatially Formed Tenacious Nickel-Supported Bimetallic Catalysts for CO2 Methanation under Conventional and Induction Heating.

The paper introduces spatially stable Ni-supported bimetallic catalysts for CO2 methanation. The catalysts are a combination of sintered nickel mesh or wool fibers and nanometal particles, such as Au, Pd, Re, or Ru. The preparation involves the nickel wool or mesh forming and sintering into a stable shape and then impregnating them with metal nanoparticles generated by a silica matrix digestion method. This procedure can be scaled up for commercial use. The catalyst candidates were analyzed using SEM, XRD, and EDXRF and tested in a fixed-bed flow reactor. The best results were obtained with the Ru/Ni-wool combination, which yields nearly 100% conversion at 248 °C, with the onset of reaction at 186 °C. When we tested this catalyst under inductive heating, the highest conversion was observed already at 194 °C.

Long-Term Isothermal Phase Transformation in Lead Zirconate.

Lead zirconate PbZrO3 has been the subject of research interest for several dozen years. Recently, even its antiferroelectric properties have started to be questioned, and many researchers still deal with the so-called intermediate phase below Curie temperature (TC), whose existence is not fully understood. It turns out that PbZrO3 doped with Nb exhibits below TC phases with complex domain structures. One of them undergoes self-organization taking place at a constant temperature, and transforms, after several minutes, into a lower phase. This isothermal transition was investigated through dielectric, pyroelectric current and Raman scattering measurements. Discontinuities accompanied it in the permittivity and pyroelectric current. The obtained Raman spectra proved that those discontinuities are strictly linked with the isothermal transition between two intermediate phases. The ordering process in lead sublattice stimulated by thermal fluctuations is discussed as a driving force for this peculiar phenomenon.

Ultrasensitive and selective determination of mercury in water, beverages and food samples by EDXRF and TXRF using graphene oxide modified with thiosemicarbazide.

The paper presents novel analytical methods for sensitive mercury determination in various samples, i.e., waters, beverages, seafood, plants, and biological samples. The procedure is based on selective preconcentration/separation of Hg(II) ions using graphene oxide/thiosemicarbazide in dispersive micro-solid phase extraction (DMSPE) and detection by energy-dispersive (EDXRF) and total-reflection X-ray fluorescence spectrometry (TXRF). The DMSPE/EDXRF and DMSPE/TXRF procedures are characterized by very high enrichment factors and low detection limits (LODs). DMSPE/TXRF allows obtaining LODs of 2.1 pg mL-1 for liquids and 1.8 ng g-1 for solid samples. In the case of DMSPE/EDXRF, the LODs are higher, 60 pg mL-1 for liquid and 73 ng g-1 for solid samples, due to the worse sensitivity of EDXRF measurement. The method was validated using spiked samples (water, apple juice, beer, wine) and certified reference materials (seawater, groundwater, wastewater, herring, cormorant and cod tissues, pig kidney, lobster, tobacco, scallion, celery, and spinach).

Sensitive determination of uranium using ß-cyclodextrin modified graphene oxide and X-ray fluorescence techniques: EDXRF and TXRF.

ß-cyclodextrin/graphene oxide (GO-ß-CD) was applied for dispersive micro-solid phase extraction (DMSPE) of uranyl ions (UO22+) from water samples and their determination by energy-dispersive (EDXRF) and total-reflection X-ray fluorescence spectrometry (TXRF). The structure of GO-ß-CD was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The results of batch adsorption experiment indicate that the maximum recoveries for UO22+ ions are observed at pH 4.5. The Langmuir isotherm model fits the adsorption data, which stands for the chemisorption mechanism. The obtained adsorption capacity of 87.7 mg g-1 indicates a great potential of the synthesized adsorbent in the UO22+ ions preconcentration. The GO-ß-CD exhibits high resistance to high ionic strength (up to 2 mol L-1), indicating that high salinity samples can be treated with the evaluated preconcentration procedure. The obtained limit of detection values were 0.40 µg L-1 for the EDXRF and only 0.014 µg L-1 for TXRF analysis. The accuracy of the method was verified by analyzing certified reference material (spring water NIST-SRM 1640a) and spiked water samples (mineral, lake, river, and artificial sea water).

Determination of ultra-trace gold in cosmetics using aluminum-magnesium layered double hydroxide/graphene oxide nanocomposite.

A new solid-phase microextraction method for preconcentration and determination of ultra-trace Au(III) and AuNPs was developed. For this purpose, a nanosized aluminum-magnesium layered double hydroxide (AlMg-LDH)/graphene oxide (GO) nanocomposite was synthesized. X-ray diffraction, Raman spectroscopy, and scanning electron microscopy confirmed the successful synthesis of the nanocomposite AlMg-LDH/GO with a well-crystallized hexagonal structure. The synthesized nanomaterial allows sorption with 100% recovery of AuNPs at pH 1-5 or AuNPs and Au(III) ions at pH 1-2. Therefore, gold ions and corresponding gold nanoparticles can be together or separately determined. The maximum sorption capacity of the nanocomposite is 12 mg g-1 for Au(III). After adsorption, gold was directly determined on the AlMg-LDH/GO by energy-dispersive X-ray fluorescence spectrometry with a detection limit of 0.06 ng mL-1, precision ca. 4%, and recovery >90%. According to the Green Chemistry rule, the method has significant advantages, such as reducing the amount of sorbent required and eliminating solvent. The elution of analytes from the nanosorbent is completely eliminated in the developed method. The developed method was successfully used to extract and determine ultra-trace gold in cosmetics products.

Cellulose mini-membranes modified with TiO2 for separation, determination, and speciation of arsenates and selenites.

Sorptive and selective mini-membranes based on TiO2 directly synthesized onto cellulose filters (TiO2@cellulose) have been developed. The in situ synthesis of TiO2@cellulose applied is simple and economically advantageous. The obtained membranes can be useful for (1) separating arsenic(V) and selenium(IV) from other ions and organic matter, (2) speciation of arsenic and selenium, and (3) determining ulratraces of these ions in water samples. The membranes exhibit good stability and high maximum adsorption capacities for Se(IV) (71 mg g-1) and As(V) (41 mg g-1). A monolayer chemical adsorption of analytes on the membranes was confirmed. The structure of membranes was examined with scanning electron microscopy, x-ray diffractometry, and micro energy-dispersive x-ray fluorescence spectrometry (µ-EDXRF). The membranes were characterized by homogenous distribution of TiO2 onto cellulose. The TiO2@cellulose was used as a new sorbent in micro-solid phase extraction for determination of Se(IV) and As(V) by EDXRF. Using direct analysis of mini-membranes after sorption of analytes avoids the elution step. Thus, the proposed procedure is an attractive and solvent-free option for quantitative monitoring of Se(IV) and As(V) in different materials. Both analytes were quantitatively and simultaneously separated/determined from samples at pH 2 with very good recovery (close to 100%), precision (4.5%), and detection limits (0.4 ng mL-1 Se and 0.25 ng mL-1 As). TiO2@cellulose membranes were applied to water analysis. Graphical-abstract Effective method for determination of ultra trace arsenates and selenites using cellulose-based sorbent.

Graphene Oxide/Carbon Nanotube Membranes for Highly Efficient Removal of Metal Ions from Water.

Graphene oxide (GO) has an excellent adsorption capacity toward metal ions. Therefore, it is widely recognized as an auspicious material for fabrication of membranes applied in metal ion separation. However, GO membranes are not stable in aqueous solution because of electrostatic repulsion between GO nanosheets which are negatively charged. This paper shows that stable GO membranes can be easily obtained by the noncovalent interaction of GO with oxidized carbon nanotubes (CNTs). The experiment also shows that the GO/CNTs membranes can be used for the effective adsorption of metal ions. The kinetic data, adsorption isotherms, competitive adsorption experiment, and X-ray photoelectron spectroscopy indicate that the adsorption of metal ions is based on chemisorption. The membranes are remarkably durable in acidic, neutral, and basic solutions. Although the significant stabilization of the membranes by CNTs is observed, they strongly influence the adsorption process. Our study reveals that even a small amount of CNTs (GO/CNTs in the ratio 8:1) significantly reduces adsorption capacities of the membranes which were as follows: 37, 40, 50, 42, 48, and 98 mg g-1 for Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II), respectively. The reduction of the membrane adsorption capacities results from the creation of micro- and nanochannels formed by entangled CNTs. Durability and adsorptive properties of studied membranes indicate their potential use for the removal of metals from water.

A Study of Catalytic Oxidation of a Library of C2 to C4 Alcohols in the Presence of Nanogold.

The classical stoichiometric oxidation of alcohols is an important tool in contemporary organic chemistry. However, it still requires huge modifications in order to comply with the principles of green chemistry. The use of toxic chemicals, hazardous organic solvents, and the large amounts of toxic wastes that result from the reactions are a few examples of the problems that must be solved. Nanogold alone or conjugated with palladium were supported on different carriers (SiO2, C) and investigated in order to evaluate their catalytic potential for environmentally friendly alcohol oxidation under solvent-free and base-free conditions in the presence H2O2 as a clean oxidant. We tested different levels of Au loading (0.1⁻1.2% wt.) and different active catalytic site forms (monometallic Au or bimetallic Au⁻Pd sites). This provided new insights on how the structure of the Au-dispersions affected their catalytic performance. Importantly, the examination of the catalytic performance of the resulting catalysts was oriented toward a broad scope of alcohols, including those that are the most resistant to oxidation-the primary aliphatic alcohols. Surprisingly, the studies proved that Au/SiO2 at a level of Au loading as low as 0.1% wt. appeared to be efficient and prospective catalytic system for the green oxidation of alcohol. Most importantly, the results revealed that 0.1% Au/SiO2 might be the catalyst of choice with a wide scope of utility in the green oxidation of various structurally different alcohols as well as the non-activated aliphatic ones.

Alumina/nano-graphite composite as a new nanosorbent for the selective adsorption, preconcentration, and determination of chromium in water samples by EDXRF.

Obtaining new nanocomposites with sorption properties towards chromium is highly important not only from the environmental point of view but also for developing eco-friendly methods of chromium determination. The potential use of aluminum oxide-coated nano-graphite (Al2O3/nano-G) as a new nanosorbent in ultrasound-assisted dispersive micro-solid-phase extraction (DMSPE) for rapid speciation of trace chromium(III) and chromium(VI) ions in natural water was evaluated. In the developed method, the crucial issue is the new nanocomposite synthesized by coating alumina on a nano-graphite surface with sorption properties. Structural researches of the nanocomposite were carried out by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), and Raman spectroscopy. Maximum adsorption capacity of Al2O3/nano-G towards Cr(III) was 32.8 mg g-1. The influence of the method's factors like pH, sample volumes, contact time, coexisting ions, and humic acid on the recovery of chromium was examined. The nanocomposites have been found to be stable and effective as a sorbent in water with high concentrations of selected cations and anions present in water as well as in water of various pH. Al2O3/nano-G is selective for Cr(III) in presence of Cr(VI). Cr(III) was determined by the developed method, total Cr after reduction of Cr(VI) to Cr(III), and Cr(VI) was calculated as the difference between total Cr and Cr(III). After sorption, the nanocomposite with chromium was collected on 5-mm diameter filters and analyzed by energy-dispersive X-ray fluorescence spectrometry (EDXRF) to determine the chromium concentration. The method was characterized by correlation coefficient 0.999, limit of detection (LOD) 0.04 ng mL-1, and relative standard deviation (RSD) 3.5%. Al2O3/nano-G combined with proposed DMSPE/EDXRF was verified by analysis of certificate reference material of natural water (NIST 1640a). Graphical abstract ᅟ.

Determination and speciation of ultratrace arsenic and chromium species using aluminium oxide supported on graphene oxide.

Alumina supported on graphene oxide (Al2O3/GO) nanocomposite as new nanosorbent in dispersive micro-solid phase extraction (DMSPE) for As(V) and Cr(III) preconcentration is described. The crucial issue of the study is synthesis of novel nanocomposite suitable for sorption of selected species of arsenic and chromium. Al2O3/GO demonstrates selectivity toward arsenates in the presence of arsenites at pH 5 and chromium(III) ions in the presence of chromate anions at pH 6. The Al2O3/GO nanocomposite was characterized by scanning electron microscopy (SEM) transmission electron microscopy (TEM), powder X-ray diffraction (XRD) and the Raman spectroscopy. The maximum adsorption capacity calculated based on the Langmuir adsorption model were 43.9 mg g-1 and 53.9 mg g-1 for As(V) and Cr(III), respectively. The nanocomposite was used as solid sorbent in preconcentration of As(V) and Cr(III)_ions from water samples and their determination using energy dispersive X-ray fluorescence spectrometry (EDXRF). The As(V) and Cr(III) ions can be quantitatively preconcentrated from 25 to 100 mL aqueous samples within 5 min using DMSPE procedure and 1 mg of Al2O3/GO. The nanocomposite was also used for preparation of Al2O3/GO membrane. Then, As(V) and Cr(III)_ions can be retained under flow condition by passing analyzed solution through Al2O3/GO membrane. Under the optimized conditions, As(V) and Cr(III) ions can be determined with very good recovery (92-108%), precision (RSD 2.7-4.0%) and excellent limit of detection (0.02 ng mL-1 As and 0.11 ng mL-1 Cr). The accuracy of the method was studied by analyzing certified reference materials (NIST 1640a) and spiked real water samples.

Ceria nanoparticles deposited on graphene nanosheets for adsorption of copper(II) and lead(II) ions and of anionic species of arsenic and selenium.

A nanocomposite prepared from graphene nanosheets and cerium nanoparticles (G/CeO2) was applied to the extraction of Se(IV), As(V), As(III), Cu(II) and Pb(II). The structure of G/CeO2 was investigated by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The optimal pH values for extraction are 4.0 for As(V), 3.0 for Se(IV), and 6.0 for both Cu(II) and Pb(II). The maximum adsorption capacity of G/CeO2 (expressed as mg·g-1) were calculated by the Langmuir model and are found to be 8.4 for As(V), 14.1 for Se(IV), 50.0 for Cu(II) and 75.6 for Pb(II). The sorbent was applied to dispersive solid phase microextraction prior to direct quantitation by energy-dispersive X-ray fluorescence spectrometry without the need for prior elution. The limits of detection (in ng·mL-1 units) are 0.10 for As(V), 0.11 for Se(IV), 0.19 for Cu(II) and 0.21 for Pb(II). The precisions (RSDs) are <4.5%. The accuracy of the method (1 - 4%) was verified by analysis of the certified reference material (CRM 1640a - natural water). The method was successfully applied in ultratrace element determination and to the speciation of selenium in environmental waters. Graphical abstract The method gives possibility of simultaneous preconcentration and determination in environmental waters of both anionic (As(V) and Se(IV)) and cationic (Cu(II) and Pb(II)) forms of selected metals using graphene nanosheets and cerium nanoparticles. Se(IV) can be selective determined in the presence of Se(VI).

Electrolytic copper as cheap and effective catalyst for one-pot triazole synthesis.

Electrolytic copper is a well-known form of pure, oxygen free copper that is used for industrial applications. In this work, the catalytic potential of this relatively cheap material was studied. The addition of less than 0.015 mol equivalent of copper powder effectively catalysed the one-pot synthesis of triazoles from a diverse range of organic halides and alkynes. Quantitative conversions in aqueous solvents can be achieved within minutes. The heterogenous nature of the catalyst afforded a low level of copper contamination in the products, thus meeting the rigorous criteria of the pharmaceutical industry.

Graphene Oxide Decorated with Cerium(IV) Oxide in Determination of Ultratrace Metal Ions and Speciation of Selenium.

Graphene oxide decorated with cerium(IV) oxide (GO/CeO2) was synthesized and applied in adsorption of several metal ions such as As(III), As(V), Se(IV), Cu(II), and Pb(II) from aqueous samples. The important feature of GO/CeO2 nanocomposite is also its selectivity toward selenite in the presence of selenate. The structure of GO/CeO2 has been proven by microscopic and spectroscopic techniques. The maximum adsorption capacities of GO/CeO2 calculated by Langmuir model toward arsenic, selenium, copper, and lead ions are between 6 and 30 mg g-1. An interesting feature of this adsorbent is its excellent dispersibility in water. Thus, GO/CeO2 nanocomposite is ideal for fast and simple determination of heavy metal ions using dispersive microsolid phase extraction (DMSPE). Moreover, coupling DMSPE with energy-dispersive X-ray fluorescence spectrometry (EDXRF) is extremely beneficial because it allows direct analysis of adsorbent. Thus, the analyte elution step, as needed in many analytical techniques, was obviated. The influence of sample volume and the sorption time as well as the influence of foreign ions and humic acid on the recovery of determined elements are discussed in the paper. The results showed that developed methodology provided low limits of detection (0.07-0.17 µg/L) and good precision (RSD < 4%). The GO/CeO2 nanocomposite was applied to analysis of real water samples and certified reference materials (CRM) groundwater (BCR-610) and pig kidney (ERM-BB186).

Highly selective determination of ultratrace inorganic arsenic species using novel functionalized miniaturized membranes.

A simple method for highly selective determination of trace and ultratrace arsenic ions, i.e. arsenite and arsenate, was developed. The method is based on new miniaturized membranes, 5 mm diameter and 4.4 mg weight, which are prepared by synthesis of amorphous silica coating on cellulose fibers followed by the modification with (3-mercaptopropyl)-trimethoxysilane. The batch adsorption experiments show that membranes have high selectivity toward arsenite in the presence of heavy metals and anions that usually exist in natural water. Arsenite can be quantitatively adsorbed at pH 1 from 50 mL sample within 60 min using the miniaturized membrane with maximum adsorption capacity of 60 mg g-1. The excellent adsorptive properties of membranes open the path to simple and selective determination of trace and ultratrace arsenite in water. Moreover, the membranes can be applied in the arsenic speciation due to their selectivity toward arsenite in the presence of arsenate. After adsorption, the arsenite retained onto the membrane is directly measured by energy-dispersive X-ray fluorescence spectrometry, avoiding elution step usually required in other spectroscopy techniques. The method is characterized by excellent enrichment factor of 972, detection limit of 0.045 ng mL-1 and can be successfully applied in analysis of high salinity water, which is difficult to analyze by other spectroscopy techniques. The proposed method is a solvent-free approach based on the use of miniaturized membranes as sorbent followed by the direct measurement using a low-power X-ray spectrometer without either elution step or gas consumption during measurement. It can be considered as environmentally friendly and meets the standards of green analytical chemistry principles.

Selective adsorption and determination of hexavalent chromium ions using graphene oxide modified with amino silanes.

Novel adsorbents are described for the preconcentration of chromium(VI). Graphene oxide (GO) was modified with various amino silanes containing one, two, or three nitrogen atoms in the molecule. These include 3-aminopropyltriethoxysilane (APTES), N-(3-trimethoxysilylpropyl)ethylenediamine (TMSPEDA), and N1-(3-trimethoxysilylpropyl)diethylenetriamine (TMSPDETA). The resulting GO derivatives were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and energy-dispersive X-ray fluorescence spectrometry (EDXRF). Adsorption studies show that these GO based sorbents are highly selective for Cr(VI) in the presence of Cr(III) at pH 3.5. Although the amino silanes applied in modification of GO contain different numbers of nitrogen atoms, the maximum adsorption capacities of GO derivatives are very similar (13.3-15.1 mg·g-1). Such results are in accordance with spectroscopy studies which show that the amount of amino silanes attached to GO decreases in the order of APTES > TMSPEDA > TMSPDETA. The APTES-modified GO was applied to selective and sensitive extraction of Cr(VI) ions prior to quantitation by low-power EDXRF using the Cr Kα line. The Cr(VI) ions need not be eluted from the solid adsorbent. The method has a 0.17 ng·mL-1 detection limit, and the recovery is 99.7 ± 2.2% at a spiking level of 10 ng·mL-1. The method was successfully applied to the determination of Cr(VI) in water samples. Graphical abstractGraphene oxide adsorbents modified with various amino silanes are described for the preconcentration and speciation of trace and ultratrace levels of chromium ions.

Method for the determination of Pb, Cd, Zn, Mn and Fe in rice samples using carbon nanotubes and cationic complexes of batophenanthroline.

Among cereals, rice is the second most cultivated staple crop in the world. It may be contaminated by toxic heavy metals present in water or soil. Therefore, monitoring the presence of heavy metals in rice and its products is a matter of a great importance from the nutritional and toxicological view. In this paper, a simple and effective analytical procedure based on dispersive micro solid-phase extraction with the use of oxidized multiwalled carbon nanotubes and batophenanthroline was developed for the determination of lead, cadmium, zinc, manganese and iron in white and wild rice samples. Due to the high preconcentration factor of 200, the optimized procedure allows obtaining detection limits between 0.13 and 0.35 ng mL-1 using flame atomic absorption spectrometry (FAAS). Novel preconcentration method can successfully be applied in food analysis with accuracy better than 7% rel. and repeatability lower than 3%.

Preconcentration of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) with ethylenediamine-modified graphene oxide.

We describe a novel solid phase sorbent that was synthesized by coupling graphene oxide (GO) to ethylenediamine (EDA). This nanomaterial (referred to as GO-EDA) is capable of adsorbing the ions of iron, cobalt, nickel, copper, zinc and lead. The ethylenediamine-modified graphene oxide was characterized by X-ray photoelectron spectroscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. The analytical procedure relies on (a) sorption of metal ions on GO-EDA dispersed in aqueous samples; (b) filtering, and (c) direct submission of the filter paper to energy-dispersive X-ray fluorescence spectrometry. This kind of dispersive micro-solid phase extraction was optimized with respect to pH values, concentration of GO-EDA, contact time, and the effects of interfering ions and humic acid on recovery of determined elements. Under optimized conditions, the recoveries of spiked samples range from 90 to 98 %. The detection limits are 0.07, 0.10, 0.07, 0.08, 0.06 and 0.10 ng mL-1 for Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Pb(II), respectively. The method has a relative standard deviation of <6 %, and its accuracy was verified by analysis of two standard reference materials [LGC6016 (estuarine water) and BCR-610 (groundwater)]. It was successfully applied to the determination of trace amounts of these metal ions in water samples. Graphical AbstractGraphene oxide was coupled to ethylenediamine in order to obtain an effective sorbent (GO-EDA) for preconcentration of Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Pb(II) from environmental water samples.

Catalytic Gas-Phase Glycerol Processing over SiO2-, Cu-, Ni- and Fe- Supported Au Nanoparticles.

In this study, we investigated different metal pairings of Au nanoparticles (NPs) as potential catalysts for glycerol dehydration for the first time. All of the systems preferred the formation of hydroxyacetone (HYNE). Although the bimetallics that were tested, i.e., Au NPs supported on Ni, Fe and Cu appeared to be more active than the Au/SiO2 system, only Cu supported Au NPs gave high conversion (ca. 63%) and selectivity (ca. 70%) to HYNE.

Ni-Supported Pd Nanoparticles with Ca Promoter: A New Catalyst for Low-Temperature Ammonia Cracking.

In this paper we report a new nanometallic, self-activating catalyst, namely, Ni-supported Pd nanoparticles (PdNPs/Ni) for low temperature ammonia cracking, which was prepared using a novel approach involving the transfer of nanoparticles from the intermediate carrier, i.e. nano-spherical SiO2, to the target carrier technical grade Ni (t-Ni) or high purity Ni (p-Ni) grains. The method that was developed allows a uniform nanoparticle size distribution (4,4±0.8 nm) to be obtained. Unexpectedly, the t-Ni-supported Pd NPs, which seemed to have a surface Ca impurity, appeared to be more active than the Ca-free (p-Ni) system. A comparison of the novel PdNPs/Ni catalyst with these reported in the literature clearly indicates the much better hydrogen productivity of the new system, which seems to be a highly efficient, flexible and durable catalyst for gas-phase heterogeneous ammonia cracking in which the TOF reaches a value of 2615 mmolH2/gPd min (10,570 molNH3/molPd(NP) h) at 600°C under a flow of 12 dm3/h (t-Ni).