Supported Platinum Nanoparticles Research Articles

NaCl-Templated Ultrathin 2D-Yttria Nanosheets Supported Pt Nanoparticles for Enhancing CO Oxidation Reaction.

Morphology of support is of fundamental significance to the fabrication of highly efficient catalysts for CO oxidation reaction. Many methods for the construction of supports with specific morphology and structures greatly rely on controlling general physical and chemical synthesis conditions such as temperature or pH. In this paper, we report a facile route to prepare yttria nanosheet using NaCl as template to support platinum nanoparticles exhibiting higher CO oxidation activity than that of the normally prepared Pt/Y2O3. With the help of TEM and SEM, we found that Pt NPs evenly distributed on the surface of NaCl modified 2D-nanosheets with smaller size. The combination of XAFS and TEM characterizations demonstrated that the nano-size Pt species with PtxOy structure played an essential role in the conversion of CO and kept steady during the CO oxidation process. Moreover, the Pt nanoparticles supported on the NaCl templated Y2O3 nanosheets could be more easily reduced and thus exposed more Pt sites to adsorb CO molecules for CO oxidation according to XPS and DRIFTS results. This work offers a unique and general method for the preparation of potential non-cerium oxide rare earth element oxide supported nanocatalysts.

Optimization of platinum loading on partially fluorinated carbon catalysts for enhanced proton exchange membrane fuel cell performance

The role of partially fluorinated carbon (CFx) supported platinum nanoparticles as proton exchange membrane fuel cell (PEMFC) electrodes in a hydrogen fuel cell is investigated. CFx is employed as a platinum catalyst support via impregnation for oxygen reduction reaction (ORR) at various platinum loadings to determine the optimal loading for ORR and compared to the widely used (non-fluorinated) Vulcan Carbon (XC-72R). In half-cell testing, CFx catalysts display greater ORR kinetics at lower Pt loadings while XC-72R display higher kinetics at higher Pt loadings. PEMFC tests utilizing 30% wt-platinum on carbon supports as the cathode material reveal a 20% increase in fuel cell performance and an 11% decrease in charge transfer resistance for the CFx supported catalysts compared to that of the XC-72R supported catalysts. PEMFCs tests utilizing 10% wt-platinum on CFx supports as the anode catalyst display a 20% increase in power density compared to the XC-72R supported catalyst. Furthermore, utilizing CFx as the support for both anode and cathode electrodes display a 15% power density increase compared to XC-72R supported catalysts.

Carbon Monoxide Oxidation on Model Planar Titania Supported Platinum Nanoparticles Catalyst

A high-throughput (parallel) thermographic screening methodology was developed to enable the measurements of the particle size and support influence on heterogeneous catalysts. A high throughput screening chip has been used to establish the catalytic activity of titania supported platinum nanoparticles catalyst for CO oxidation reaction. The catalytic activity of Pt nanoparticles between 1.3 to 7.8 nm has been investigated for CO conversion at a pressure of 0.11 and 1.1 mbar with O2:CO ratio of 1:1 at 80 °C and 0.6, 1.1 and 2.4 mbar at O2:CO ratio of 1:1 at 240 °C. At these experimental conditions, there was an increase in the TOF with decreasing particle size for instance, at 80 °C and O2:CO ratio of 1:1, total pressure of 0.11 and 1.1 mbar, the TOF increased from 0.01 s–1 to 0.171 s–1 with decreasing Pt particle size from 7.8 to 1.3 nm, respectively. However, Pt nanoparticles catalyst displayed higher activity at higher temperature, for example, the TOF increased from 3.312 s–1 to 4.355 s–1 at O2:CO ratio of 1:1, total pressure of 0.6 and 1.1 mbar, respectively, for Pt particle size of 1.3 nm in agreement with the previous reports. Results show that CO oxidation on titania supported Pt nanoparticles catalyst is particle size dependent. On the other hand, findings from XPS measurements show no major change in the particle size after the reaction thus, reflecting the stability of Pt particles. While there is no apparent consensus in the literature reports on the activity trend with particle size for this system, these findings are consistent with most of the previously reported findings.
 Keywords: platinum; titania; nanoparticles; thermography; CO oxidation.

A template approach to designing and synthesizing hierarchical porous carbon with tri-modal pore structure and its application for high performance oxygen reduction electrocatalyst support

A new type of hierarchical porous carbon with tri-modal pore structure (Tri-PC), i.e., ordered micropores (1.3 nm), uniformly distributed mesopores (2–10 nm) and “earthworm-shaped” mesochannels (with a diameter of 20 nm) running through the whole particle was successfully realized via a novel and facile template approach, in which zeolite Y was firstly gone through a pore expansion using oxalic acid-ammonium fluoride mixture to prepare hierarchical porous zeolite. The hierarchical porous zeolite was subsequently used as the template to catalytically grow carbon via CVD technique. Tri-PC was then obtained after the removal of the template. The as synthesized Tri-PC showed great potential as the catalyst support. We evaluated the ORR catalytic activity of Tri-PC supported platinum nanoparticles (Pt/Tri-PC) in alkaline electrolyte, which exhibits 20 mV higher onset potential (0.95 V) and 30 mV higher half-wave potential (0.87 V) than commercial 10 wt% Pt/C catalyst. Meanwhile, the electrochemical impedance spectroscopy measurement showed that Pt/Tri-PC had lower charge transfer resistance. High performance benefits from a collaborative hierarchical architecture. Micropores offer a large specific surface area and sufficient active sites, mesopores increase the accessibility of active sites and shorten the diffusion path of fuels and products, and mesochannels further enhance the connectivity of the entire pore network. The present work highlights the significance of the hierarchical porous structure for enhancing the catalytic performance of catalysts and suggests that Tri-PC could be used as an advanced catalyst support in many fields.

Modification of the Electrochemical Surface Oxide Formation and the Hydrogen Oxidation Activity of Ruthenium by Strong Metal Support Interactions

A major hurdle for the wide spread commercialization of proton exchange membrane based fuel cells (PEMFCs) and water electrolyzers are the durability and high cost of noble metal catalysts. Here, alternative support materials might offer advantages, as they can alter the properties of a catalyst by means of a strong metal support interaction (SMSI) that has been shown to prevent platinum oxidation and suppress the oxygen reduction reaction on titanium oxide supported platinum nanoparticles deposited on a carbon support (Pt/TiOx/C). Herein, we report a novel Ru/TiOx/C catalyst that according to tomographic transmission electron microscopy analysis consists of partially encapsulated Ru particles in a Ru/TiOx-composite matrix supported on a carbon support. It is shown by cyclic voltammetry and X-ray photoelectron spectroscopy that ruthenium oxidation is mitigated by an SMSI between Ru and TiOx after reductive heat-treatment (Ru/TiOx/C400°C,H2 ). As a result, the catalyst is capable of oxidizing hydrogen up to the onset of oxygen evolution reaction, in stark contrast to a Ru/C reference catalyst. PEMFC-based hydrogen pump measurements confirmed the stabilization of the hydrogen oxidation reaction (HOR) activity on Ru/TiOx/C400°C,H2 and showed a ≈3-fold higher HOR activity compared to Ru/C, albeit roughly two orders of magnitude less active than Pt/C.

Hydrogen Adsorption/Desorption Isotherms on Supported Platinum Nanoparticles Determined by in‐situ XAS and ΔXANES Analysis

AbstractHydrogen atoms on supported metal nanoparticles (NPs) play a significant role in heterogeneous catalysis. Despite the extensive previous research, however, the adsorption of hydrogen onto practical supported NP catalysts is still unclear especially in the atmospheric pressure conditions. In this study, adsorption/desorption isotherms of hydrogen on Pt NPs supported on alumina (Al2O3) were obtained in gas‐flow conditions using the analysis of the difference spectra of Pt LIII‐edge X‐ray absorption spectroscopy (XAS) at 303 K. From the analysis of extended X‐ray absorption fine structure (EXAFS), a positive linear relationship was observed between the hydrogen coverage and Pt−Pt bond distance. Additionally, the re‐adsorption experiment of hydrogen after the first adsorption/desorption cycle and the transient change of dispersive XAS spectra in the hydrogen adsorption suggests that the hydrogen adsorption induces the surface reconstruction of Pt NPs on Al2O3 at around room temperature and atmospheric pressure.

Comments on “Size dependence of the lattice parameters of carbon supported platinum nanoparticles: X-ray diffraction analysis and theoretical considerations,” RSC Adv., 2014, 4, 35959–35965

Leontyev and colleagues presented the results of an experiment and of its theoretical consequences. The interpretations were based on model-fits to that experiment. Unfortunately, they used two demonstrably incorrect parameters in their models. When the correct parameters are used, the best fits, and the corresponding theoretical implications, are interchanged. Specifically, they deduced an inapplicability of the Laplace–Young equation to the compression of nanoparticles. After their faulty parameters are corrected, this is no longer proven. An equation based on Laplace–Young pressure was dismissed by Leontyev et al., but when recalculated with corrected parameters, it fits their experimental data points.

Fabrication of Platinum/ Polypyrol-Carbon Nanofiber Nanocomposite Electrocatalyst for Direct Methanol Fuel Cells

A novel electrocatalyst has been developed based on polypyrol-carbon nanofiber (PPy-CNF) support material to increase the stability of Pt/ PPy-CNF/GDL electrocatalyst in direct methanol fuel cell (DMFC). A novel conducting polymer (PPy)-CNF nanocomposites was prepared by a solution dispersion technique and used to support platinum nanoparticles. For preparation of catalyst ink, 20 wt.% Pt/PPy-CNF electrocatalyst with a platinum loading of 0.4 mg cm-2 was prepared by ethylene glycol (EG) method. Physical and electrochemical properties were analyzed by X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) imaging and cyclic voltammetry (CV) experiments. FTIR results prove the existence of PPy in the support. SEM images showed that the one–dimensional CNFs were efficaciously covered by PPy. The TEM characterization revealed that the fine Pt nanoparticles prepared by polyol method were dispersed on the surface of the electrocatalyst successfully. XRD patterns also revealed that the mean size of Pt crystal nanoparticles was about 3.69, 6.51 and 2.91 nm for Pt/PPy-CNF, Pt/CNF and Pt/C electrocatalyst respectively. The size of the PPy on carbon paper has been measured in the range of 35-40nm by AFM. Based on the electrochemical properties and acceleration tests evaluated by cyclic voltammetry measurements and Chronoamperometric experiments it was found that the as prepared Pt/PPy-CNF/GDL electrode exhibited a comparable electrochemical surface are (ECSA), MOR activity and so stability (in the presence of methanol) with respect to the Pt/CNF /GDL and Pt/C/GDL commercial one. A rather significant reduction in the peak potential of methanol electro-oxidation from 0.69V for Pt/C/GDL to 0.76V for Pt/PPy-CNF/GDL electrode indicates that an increase in the activity for MOR is achieved by replacing the C by PPy-CNF. The corresponding ECSA values for the Pt/PPy-CNF/GDL, Pt/CNF/GDL and Pt/C/GDL electrodes were 108.69, 53.93 and 17.98 m2g-1 respectively.

Strengthening oxygen reduction activity and stability of carbon-supported platinum nanoparticles by fluorination

By combining experimental and theoretical aspects, this study focuses on exploring and enhancing the activity and stability towards oxygen reduction reaction (ORR) of fluorinated carbon supported platinum nanoparticles in the acidic electrolyte. Physical characterization results revealed that fluorinated carbon support generates a C-F bonding. The interaction between Pt and fluorinated-carbon allows for a strong charge transfer from Pt to the support. This phenomenon is consistent with the density functional theory (DFT) analysis. Because of the fluorination, the electronic structure of Pt is changed, which is an advantage for improving the catalytic activity and stability of the catalyst towards ORR.

Prediction Descriptor for Catalytic Activity of Platinum Nanoparticles/Metal-Organic Framework Composites.

Supported metal nanoparticles (MNPs) have exhibited superior catalytic performance in various heterogeneous catalysis applications, which is usually influenced or even determined by the physicochemical properties of their porous supports. It is well acknowledged that understanding the regulation mechanism of supports is an important prerequisite to predict the catalytic performance of supported MNPs as well as the development of advanced catalysts. Here, we demonstrated that different transition-metal clusters (from Group IIIB to Group IIB) within metal-organic frameworks (MOFs) could accurately regulate the surface electronic status of supported platinum nanoparticles (Pt NPs), and the Pt/MOF composites showed a periodic activity trend in hydrogenation of 1-hexene. A strong correlation was found between the catalytic activity of Pt/MOF composites and the number of electrons in their outmost d orbitals of the transition-metal species, suggesting that the latter could play the role of prediction descriptor. Furthermore, this descriptor can be extended to predict the hydrogenation activity of more Pt/MOF composites and provide an important guiding principle for the design of supported MNPs catalysts.

Oxygen-Enriched Biomass-Activated Carbon Supported Platinum Nanoparticles as an Efficient and Durable Catalyst for Oxidation in Benzene

Carbon materials have been widely utilized as supports in different catalytic reactions; however, it has been rarely reported that carbon supports were used in the catalytic oxidation of volatile organic compounds because they have no catalytic activity and poor catalytic stability compared to metal supports. Herein, fabricating optimal carbon supports to facilitate the catalytic oxidation of benzene has become a great concern of research. A novel activated carbon (biomass–HCO) was prepared from different waste biomass via a three-stage route without the participation of harmful chemical reagents. The successful synthesis of C–O bonds and C═O bonds through this method could greatly increase oxygen-enriched functional groups and defects of the biomass–HCO surface, which could effectively promote the nucleation and growth of platinum. Benzene oxidation reactions were performed to evaluate the activity of catalysts. The results demonstrated that Pt/biomass–HCO catalyst made the reaction temperature sharply decrease to 160 °C at T₉₀. The 150 h on-stream reaction exhibited great thermal stability of Pt/biomass–HCO. The DFT calculations verified the strong interaction between Pt nanoparticles and carbon supports. Moreover, our demonstration of the superior benzene oxidation activity of Pt/biomass–HCO catalysts revealed that it is feasible to utilize oxygen-enriched biomass carbon as catalytic supports toward the oxidation of volatile organic compounds.

Solar-driven valorization of glycerol towards production of chemicals and hydrogen

Reverse microemulsion-based synthesis was successfully applied to the preparation of nanosized TiO2 particles in anatase and rutile crystalline phases. The resulted nano-oxides were found to have smaller average crystalline size, higher surface area and narrower band gap than commercial TiO2 samples, P25 and DT-51. All the TiO2 materials were used as supports for platinum nanoparticles prepared by incipient wetness impregnation and deposition-precipitation methods. The photo-catalytic activities of these materials were compared in the reaction of glycerol photo-reforming in aqueous media using simulated solar light. The results showed that different crystalline phases of titania have different effects on hydrogen production and selectivity of intermediate products. Anatase was found to be more selective towards glyceraldehyde, while the presence of rutile promoted a more selective reaction towards glycolaldehyde. Rutile also exhibited a higher productivity of hydrogen compared to anatase.

Cobalt ferrite supported platinum nanoparticles: Superb catalytic activity and outstanding reusability in hydrogen generation from the hydrolysis of ammonia borane

In this work, platinum(0) nanoparticles are deposited on the surface of magnetic cobalt ferrite forming magnetically separable Pt0/CoFe2O4 nanoparticles, which are efficient catalysts in H2 generation from the hydrolysis of ammonia borane. Catalytic activity of Pt0/CoFe2O4 nanoparticles decreases with the increasing platinum loading, parallel to the average particle size. Pt0/CoFe2O4 (0.23% wt. Pt) nanoparticles have an average diameter of 2.30 ± 0.47 nm and show an extraordinary turnover frequency of 3628 min−1 in releasing 3.0 equivalent H2 per mole of ammonia borane from the hydrolysis at 25.0 °C. Moreover, the magnetically separable Pt0/CoFe2O4 nanoparticles possess high reusability retaining 100% of their initial catalytic activity even after ten runs of hydrolysis. The superb catalytic activity and outstanding reusability make the Pt0/CoFe2O4 nanoparticles very attractive catalysts for the hydrogen generation systems in portable and stationary fuel cell applications.

Control of surface area and conductivity of niobium-added titanium oxides as durable supports for cathode of polymer electrolyte fuel cells

Niobium-added titanium oxide is a promising candidate as a substitute carbon support for cathodes of PEFCs. Nb-added TiO2 can act as a support for platinum nanoparticles to enhance the oxygen reduction reaction (ORR) activity and durability under acidic conditions. Nb-added TiO2 supports with the desired surface area (10–130 m2 g−1) and conductivity (10−7–10−2 S cm−1) were prepared by changing the amount of Nb and the heat treatment conditions. First, we conducted a systematic investigation with changes in the amount of niobium addition, heat-treatment temperature, and time under a pure hydrogen atmosphere to reveal the physicochemical factors that govern the surface area and conductivity. Finally, we successfully proposed a procedure to prepare highly durable Nb-added TiO2 supports with the desired surface area and conductivity by controlling the amount of niobium addition, heat-treatment temperature, and time under hydrogen. The charges of the double layer were almost unchanged after 5000 cycles of an accelerated durability test (ADT).

Carbon nanoparticle coated by silicon dioxide supported platinum nanoparticles towards oxygen reduction reaction

Herein, a SiO2 thin-layer is coated on the surface of carbon nanoparticles. Such a composite is further utilized as the support to load Pt nanoparticles (Pt/SiO2-C). This Pt/SiO2 -C catalyst features an improved interaction between Pt nanoparticles and the stable SiO2 thin-layer. In acid media, an optimal Pt/SiO2-C catalyst displays significantly improved ORR activity (e.g., a half-wave potential of 0.81 V vs. RHE and a limiting diffusion current of 5.55 mA cm−2) and enhanced ability towards CO andmethanol anti-poisoning. Such performance is superior to the commercial Pt/C catalysts, Pt/carbon nanoparticle based catalysts, and Pt catalysts deposited on other supports. As predicted by density functional theory calculations (DFT), such high ORR performance is mainly due to the reduced free energy barrier, derived from the hydrophilic of SiO2 thin-layer.

The Impact of Antimony on the Performance of Antimony Doped Tin Oxide Supported Platinum for the Oxygen Reduction Reaction

Antimony doped tin oxide (ATO) supported platinum nanoparticles are considered a more stable replacement for conventional carbon supported platinum materials for the oxygen reduction reaction. However, the interplay of antimony, tin and platinum and its impact on the catalytic activity and durability has only received minor attention. This is partly due to difficulties in the preparation of morphology- and surface-area-controlled antimony-doped tin oxide materials. The presented study sheds light onto catalyst–support interaction on a fundamental level, specifically between platinum as a catalyst and ATO as a support material. By using a previously described hard-templating method, a series of morphology controlled ATO support materials for platinum nanoparticles with different antimony doping concentrations were prepared. Compositional and morphological changes before and during accelerated stress tests are monitored, and underlying principles of deactivation, dissolution and catalytic performance are elaborated. We demonstrate that mobilized antimony species and strong metal support interactions lead to Pt/Sb alloy formation as well as partially blocking of active sites. This has adverse consequences on the accessible platinum surface area, and affects negatively the catalytic performance of platinum. Operando time-resolved dissolution experiments uncover the potential boundary conditions at which antimony dissolution can be effectively suppressed and how platinum influences the dissolution behavior of the support.

Fuel Cell Automotive Drive-Cycle Cathode Catalyst (Pt/C) Layer Durability: Dependence on Low Vs. High Carbon Supports and Ionomer-to-Carbon-Ratio

The typical urban automotive drive-cycle for proton exchange membrane fuel cells (PEMFC) consists of frequent idle-to-peak power cathode voltage transients, with extremes ranging from 1.2 V to 0.6 V, respectively. Understanding the platinum electrochemical surface area (ECSA) loss mechanisms dependence on material and operational conditions have been extensively investigated with the objective of minimizing performance losses over the lifetime of PEMFC powered automobiles. Commonly, automotive accelerated stress tests (AST) are performed ex-situ on thin catalyst films. The standard catalyst consists of carbon supported platinum nanoparticles (Pt/C). This study compares triangle waveform (TW) ASTs monitoring ECSA loss for ex-situ (thin film in 0.1 HClO4) and in-situ (catalyst layers bond with ionomeric electrolyte in a complete membrane electrode assembly (MEA)). The ionomer-to-carbon ratios (I/C) of the MEAs is varied from 0.6 to 1.5 on either low surface area carbon (LSAC) or high surface area carbon (HSAC) supports. The AST profiles included 25k cycles at 10 sec intervals, between the upper potential limit of either 0.9 V or 1.2 V and the lower potential limit of 0.6V, with intermediate ECSA evaluations from the H-desorption current (0.02 V → 0.4 V).The electrolyte environment alters, liquid vs. ionomer, the dominant AST decay mechanism, Figure 1A. The decay in the liquid electrolyte is most sever upon initiation of the AST and the rate of decay decrease after the first 2000 cycles. While the MEA decay is less initial, but maintains the same rate of initial decay over 5000 cycles resulting in a higher overall loss of ECSA. ECSA decay is exacerbated at temperatures of 70°C. Increasing the I/C increases the interfacial acidity at the surface of the Pt/C and results in exacerbated ECSA loss, Figure 1B. In accordance with the Pourbaix diagram for Pt, it is less stable in a more acidic environment. The relative rate of ECSA loss is reduced on HSAC supports. Figure 1

Selective oxidation of benzyl alcohol by reduced graphene oxide supported platinum nanoparticles

The Pt / rGO nanocatalyst was synthesized by the immobilization method by deposition of platinum nanoparticles on reduced graphene oxide (rGO) as a support material. The support (rGO) was prepared from the reduction of graphene oxide (GO) by the reducing agent sodium borohydride (NaBH4), while (GO) was prepared from the graphite oxidation using the modified Hummer method. Morphological, chemical and structural characteristics of synthesized samples were investigated by Scanning Electron Microscope (SEM), transmittance Scanning Microscope (TEM), Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), and X-ray and Raman Spectroscopy. The performance of the Pt/rGO catalysts were evaluated in the benzyl alcohol oxidation to produce benzaldehyde using an environmentally friendly oxidizing agent, hydrogen peroxide, under moderate conditions. The variables that were studied on oxidation of benzyl alcohol were temperature, catalyst mass and H2O2 concentration. The best results were achieved when the catalyst amount was 10 mg, 50% hydrogen peroxide concentration and 80 °C reaction temperature. The conditions under which the reaction was carried out are moderate reaction conditions, and the oxidizing agent (H2O2) is an environmentally friendly oxidizing agent.

Surface oxidation of Ti3C2Tx enhances the catalytic activity of supported platinum nanoparticles in ammonia borane hydrolysis

MXenes, first discovered in 2011, are two-dimensional transition metal carbides or nitrides. Because of their interesting electrical and optical properties, they are studied for applications in batteries, supercapacitors and electrocatalysis. However, MXenes are rarely used in heterogeneous catalysis and, to our knowledge, there are no reports on the use of oxidized MXenes in catalysis. Here we used Ti3C2Tx-derived materials as supports for platinum nanoparticles and studied their effectiveness for the hydrolysis of ammonia borane, which is a promising hydrogen carrier. Hydrogen can be released from ammonia borane through catalytic hydrolysis. Most heterogeneous catalysts reported for this purpose contain a noble metal supported on a metal oxide support. The interaction between the metal and the support is important in determining the catalytic performance. Our results show that the electronic environment of platinum can be modified by oxidising the surface of MXene, thus providing a new way of developing active catalysts. Oxidising agents such as water and ozone can be used for this purpose. This electronic modification enhances the catalytic activity of platinum for ammonia borane hydrolysis, which is relevant for other reactions related to energy production/storage.

DEMS and RAMAN study of the monatomic hydrogen adsorption during electro-reduction of NO3- and NO2- at Pt nanoparticles supported at W18O49-ZrO2-C nanocomposite

A multifunctional hybrid material composed of W18O49 nanobelts (NBs), zirconium oxide, and Vulcan carbon (W18O49-ZrO2-C) has been used as support for platinum nanoparticles (PtWZC). For comparison, platinum supported on Vulcan carbon (PtC) was also synthesized. These catalysts were evaluated in the NO3- and NO2- (NOx) reduction reactions. The addition of W18O49 and ZrO2 to the carbon improved the size and distribution of the platinum nanoparticles. The electrochemical results showed that enhanced electrocatalytic activity for the NOx reduction was obtained on the PtWZC catalyst compared to PtC synthesized by the same technique and PtEtek from a commercial source. Our findings suggest that the adsorbed monatomic hydrogen (Hads) over platinum inhibits the reduction of nitrates and nitrites. Therefore, these reactions need a material that removes Hads from the surface or modifies it for the NOx reduction. The WZC support adsorbed monatomic hydrogen from water to form active bronze species (Hx-W18O49) that interacted with the NO3- and NO2- ions enabling their reduction, in accord with the results from in-situ Raman spectroscopy and Tafel slopes. N2, NO, NH3, and N2H4 products were detected in nitrite ion reduction by the Differential electrochemical mass spectrometry (DEMS) technique on the PtWZC catalyst. The production of N2 dominated in the cathodic and anodic scan. Hence, the novel catalyst can follow the indirect pathway, where the reduction process involves adsorption of NHx and adsorption of NO. The higher electrocatalytic activity obtained by the PtWZC catalyst was attributed to the uniform distribution of platinum on the support, the increased electrical conductivity produced by the W18O49 nanobelts, and the modulation of Hads on the surface.