Preparation and Electrochemical Performance of a Graphene Cathode Catalyst Decorated With Pt by Prolysis

For fuel cells, to produce high-quality and low-platinum catalyst is a pressing technical problem. In this study, graphene cathode catalysts with controllable platinum content were decorated by pyrolyzing chloroplatinic acid under various process parameters to obtain a high catalytic activity and durability. The results show that platinum particles generated by pyrolyzing chloroplatinic acid are uniformly loaded on graphene without agglomeration. The average particle size of platinum particles is about 2.12 nm. The oxygen reduction reaction catalytic activity of catalyst samples first increases, then decreases with increasing platinum loading in cyclic voltammetry and LSV. Compared with the commercial Pt/C (20 wt% Pt) catalyst, the initial potential and the current density retention rate of the catalyst decorated with 8% platinum are 55 mV and 23.7% higher, respectively. From i-t curves, it was found that the stability of the catalyst prepared in this paper was improved compared with the commercial Pt/C catalyst. The catalysts prepared in the present research exhibits superior catalytic activity and stability.

Enhanced hydrogen generation by reverse spillover effects over bicomponent catalysts

The contribution of the reverse spillover effect to hydrogen generation reactions is still controversial. Herein, the promotion functions for reverse spillover in the ammonia borane hydrolysis reaction are proven by constructing a spatially separated NiO/Al2O3/Pt bicomponent catalyst via atomic layer deposition and performing in situ quick X-ray absorption near-edge structure (XANES) characterization. For the NiO/Al2O3/Pt catalyst, NiO and Pt nanoparticles are attached to the outer and inner surfaces of Al2O3 nanotubes, respectively. In situ XANES results reveal that for ammonia borane hydrolysis, the H species generated at NiO sites spill across the support to the Pt sites reversely. The reverse spillover effects account for enhanced H2 generation rates for NiO/Al2O3/Pt. For the CoOx/Al2O3/Pt and NiO/TiO2/Pt catalysts, reverse spillover effects are also confirmed. We believe that an in-depth understanding of the reverse effects will be helpful to clarify the catalytic mechanisms and provide a guide for designing highly efficient catalysts for hydrogen generation reactions.

Modulating catalytic oxygen activation over Pt-TiO2/SiO2 catalysts by defect engineering of a TiO2/SiO2 support

Binary TiO2/SiO2 oxides were synthesized via flame spray pyrolysis as supports for a Pt catalyst. The effect of the mole ratio of the silica and on the catalyst characteristics and...

A hydrogen generator coupled to a hydrogen heater for small scale portable applications

This study aims to build and test a small scale portable device able to couple a hydrogen generation system (based on a NaBH4 solution as liquid H2 carrier) to a hydrogen heater (based on the exothermic catalytic combustion of the released H2). The hydrogen generating system is based on the hydrolysis of stabilized solutions of NaBH4 (fuel solutions) which are pumped into the hydrolysis reactor. The generated H2 feeds the catalytic combustor. Two catalysts have been developed for the H2 generation and the combustion reactions able to operate at room temperature without need of additional energy supply. For the NaBH4 hydrolysis a Co-B catalyst was supported on a perforated and surface treated stainless steel (SS316) home-made monolith. For the flameless H2 catalytic combustion a Pt catalyst was prepared on a commercial SiC foam. The device was automatized and tested for the on-demand production of heat at temperatures up to 100ºC. In steady state conditions the NaBH4 solution flow is controlling the H2 flux and therefore the heater temperature. Once the steady-state is reached the system responds in a few minutes to up and down temperature demands from 80 to 100 ºC. The catalysts have shown no deactivation during the tests carried out in several days.

Understanding Catalytic Activity Trends of Electrochemical Ammonia Oxidation Reaction using Density Functional Theory Calculations and Microkinetic Modeling

Electrochemical ammonia oxidation reaction (AOR) is promising as an alternative anodic reaction to oxygen evolution in water electrolysis system. Herein, we develop a microkinetic model based on density functional theory (DFT) calculations for all possible reaction pathways considering both thermochemical and electrochemical N-N bond formation processes. From the microkinetic analysis, we discover that Faradaic bond formation contributes to AOR more significantly than non-Faradaic counterpart and we observe good agreements with the experimental results. We then construct a kinetic volcano plot using binding energies of two reaction intermediates as descriptors, which suggests a catalyst design strategy. Following this strategy, we enumerate numerous alloy combinations and identify a few promising candidates with higher catalytic activity than the most active monometallic Pt catalyst.

Technological Aspects of Highly Selective Synthesis of Allyloxyalcohols—New, Greener, Productive Methods

Allyl ethers bearing free hydroxyl groups of CH2=CH-CH-O-A-OH type (hydroxyalkyl allyl ethers, allyloxyalcohols) are valuable chemicals in many environmentally friendly industrial applications. The development of technologically attractive methods for their production is necessary. The two pathways (L-L PTC and non-catalytic solvent-free conditions) were optimized for the highly selective and yield synthesis of 4-allyloxybutan-1-ol. Improvements in the PTC method (50% NaOH(aq), the equimolar ratio of NaOH to diol, cyclohexane as solvent) with a new highly selective and effective PT catalyst, i.e., Me(n-Oct)3N+Br− (0.3 mol%), resulted in 88% yield and 98% selectivity of 4-allyloxybutan-1-ol with minimal formation of allyl chloride hydrolysis by-products (<1%). In turn, application of non-catalytic solvent-free conditions and the change in the key substrate with an excess of diol and use of solid NaOH solely led to a mono-O-allylation product with an excellent yield of 99% in a relatively short reaction time (3.5 h), with trace amounts of by-products (<0.1%). This sustainable method is perfectly suitable for the synthesis on a larger scale (3 moles of the key substrate) and for the full O-allylation process.

Evaluating the Response Time of an Optical Gas Sensor Based on Gasochromic Nanostructures

We propose a method for determining complex dielectric permittivity dynamics in the gasochromic oxides in the course of their interaction with a gas as well as for estimating the diffusion coefficient into a gasochromic oxide layer. The method is based on analysis of a time evolution of reflection spectra measured in the Kretschmann configuration. The method is demonstrated with a hydrogen-sensitive trilayer including an Au plasmonic film, WO3 gasochromic oxide layer, and Pt catalyst. Angular dependences of the reflectance as well as transmission spectra of the trilayer were measured in series at a constant flow of gas mixtures with hydrogen concentrations in a range of 0–0.36%, and a detection limit below 40 ppm (0.004%) of H2 was demonstrated. Response times to hydrogen were found in different ways. We show that the dielectric permittivity dynamics of WO3 must be retrieved in order to correctly evaluate the response time, whereas a direct evaluation from intensity changes for chosen wavelengths may have a high discrepancy. The proposed method gives insight into the optical properties dynamics for sensing elements based on gasochromic nanostructures.

Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode

Ionic liquid (IL) additives to both traditional and advanced oxygen reduction reaction (ORR) electrocatalysts have yielded remarkable improvements in catalyst performance and durability. However, incorporating ILs or IL-modified catalysts into the electrodes of a proton exchange membrane fuel cell (PEMFC) membrane electrode assembly (MEA) has proven to be challenging. Sulfonated poly(ionic liquid) block copolymers (S-PILBCP) present an opportunity to incorporate IL functionality directly into the ionomer, orthogonal to protonic conductivity. Here, we use a rotating disc electrode (RDE) to characterize the interface between a S-PILBCP and Pt catalyst in comparison to Nafion. Catalyst thin films prepared with S-PILBCP show an 80% improvement in the ORR activity over those containing Nafion. Thin films of S-PILBCP also show a significantly reduced degree of poisoning sulfonate adsorption on a Pt(111) surface in comparison to Nafion. These half-cell results provide useful insights that help to highlight the source of the impact of the S-PILBCP on PEMFC MEA performance.

Influence of Cathode Catalyst Layer with SiO2-Coated Pt/Ketjen Black Catalysts on Performance for Polymer Electrolyte Fuel Cells

In this study, we investigated the effect of silica (SiO2) layer included in a cathode catalyst layer (CL) on the performance for polymer electrolyte fuel cells (PEFCs). Porous carbons such as Ketjen black (KB) have been widely used as a support for Pt catalysts in PEFCs. Such KB-supported Pt catalyst (Pt/KB) was used as a cathode CL with low ionomer content (a condition of low proton conductivity). The Pt/KB was then coated with SiO2. In addition, the Pt/KB and SiO2-coated Pt/KB (SiO2-Pt/KB) were measured and analyzed under relative humidity (RH) conditions (100% and 20%). The catalyst ink of SiO2-Pt/KB showed higher stability and dispersion compared to Pt/KB, due to the hydrophilic surface characteristics of SiO2, which act as a binder-like ionomer. The performance of the SiO2-Pt/KB at 100% RH, was significantly lower than that of Pt/KB, whereas the performance of the Pt/KB at 20% RH, was significantly improved by SiO2 coating. This is due to an increase in the proton conductivity, which can be attributed to the hydrophilic properties of SiO2. Based on these results, the effect of SiO2 coating on performance, depending on carbon supports of SiO2-coated Pt/Carbon catalysts, could be evaluated.