Catalyst durability in electrocatalytic H2O2 production: key factors and challenges.

On-demand electrocatalytic hydrogen peroxide (H2O2) production is a significant technological advancement that offers a promising alternative to the traditional anthraquinone process. This approach leverages electrocatalysts for the selective reduction of oxygen through a two-electron transfer mechanism (ORR-2e-), holding great promise for delivering a sustainable and economically efficient means of H2O2 production. However, the harsh operating conditions during the electrochemical H2O2 production lead to the degradation of both structural integrity and catalytic efficacy in these materials. Here, we systematically examine the design strategies and materials typically utilized in the electroproduction of H2O2 in acidic environments. We delve into the prevalent reactor conditions and scrutinize the factors contributing to catalyst deactivation. Additionally, we propose standardised benchmarking protocols aimed at evaluating catalyst stability under such rigorous conditions. To this end, we advocate for the adoption of three distinct accelerated stress tests to comprehensively assess catalyst performance and durability.

Monitoring Photo-Fenton and Photo-Electro-Fenton process of contaminants emerging concern by a gas diffusion electrode using Ca10-xFex-yWy(PO4)6(OH)2 nanoparticles as heterogeneous catalyst.

The catalytic performance of modified hydroxyapatite nanoparticles, Ca10-xFex-yWy(PO4)6(OH)2, was applied for the degradation of methylene blue (MB), fast green FCF (FG) and norfloxacin (NOR). XPS analysis pointed to the successful partial replacement of Ca by Fe. Under photo-electro-Fenton process, the catalyst Ca4FeII1·92W0·08FeIII4(PO4)6(OH)2 was combined with UVC radiation and electrogenerated H2O2 in a Printex L6 carbon-based gas diffusion electrode. The application of only 10 mA cm-2 resulted in 100% discoloration of MB and FG dyes in 50 min of treatment at pH 2.5, 7.0 and 9.0. The proposed treatment mechanism yielded maximum TOC removal of ∼80% and high mineralization current efficiency of ∼64%. Complete degradation of NOR was obtained in 40 min, and high mineralization of ∼86% was recorded after 240 min of treatment. Responses obtained from LC-ESI-MS/MS are in line with the theoretical Fukui indices and the ECOSAR data. The study enabled us to predict the main degradation route and the acute and chronic toxicity of the by-products formed during the contaminants degradation.

Exploring the Potential of Heteroatom-Doped Graphene Nanoribbons as a Catalyst for Oxygen Reduction.

In this study, we created a series of N, S, and P-doped and co-doped carbon catalysts using a single graphene nanoribbon (GNR) matrix and thoroughly evaluated the impact of doping on ORR activity and selectivity in acidic, neutral, and alkaline conditions. The results obtained showed no significant changes in the GNR structure after the doping process, though changes were observed in the surface chemistry in view of the heteroatom insertion and oxygen depletion. Of all the dopants investigated, nitrogen (mainly in the form of pyrrolic-N and graphitic-N) was the most easily inserted and detected in the carbon matrix. The electrochemical analyses conducted showed that doping impacted the performance of the catalyst in ORR through changes in the chemical composition of the catalyst, as well as in the double-layer capacitance and electrochemically accessible surface area. In terms of selectivity, GNR doped with phosphorus and sulfur favored the 2e- ORR pathway, while nitrogen favored the 4e- ORR pathway. These findings can provide useful insights into the design of more efficient and versatile catalytic materials for ORR in different electrolyte solutions, based on functionalized carbon.

Highly porous seeding-free boron-doped ultrananocrystalline diamond used as high-performance anode for electrochemical removal of carbaryl from water.

Boron-doped diamond (BDD) electrodes are regarded as the most promising catalytic materials that are highly efficient and suitable for application in advanced electrochemical oxidation processes targeted at the removal of recalcitrant contaminants in different water matrices. Improving the synthesis of these electrodes through the enhancement of their morphology, structure and stability has become the goal of the material scientists. The present work reports the use of an ultranano-diamond electrode with a highly porous structure (B-UNCDWS/TDNT/Ti) for the treatment of water containing carbaryl. The application of the proposed electrode at current density of 75 mA cm-2 led to the complete removal of the pollutant (carbaryl) from the synthetic medium in 30 min of electrolysis with an electric energy per order of 4.01 kWh m-3 order-1. The results obtained from the time-course analysis of the carboxylic acids and nitrogen-based ions present in the solution showed that the concentrations of nitrogen-based ions were within the established maximum levels for human consumption. Under optimal operating conditions, the proposed electrode was successfully employed for the complete removal of carbaryl in real water. Thus, the findings of this study show that the unique, easy-to-prepare BDD-based electrode proposed in this study is a highly efficient tool which has excellent application potential for the removal of recalcitrant pollutants in water.

Using Palladium and Gold Palladium Nanoparticles Decorated with Molybdenum Oxide for Versatile Hydrogen Peroxide Electroproduction on Graphene Nanoribbons.

Electrocatalytic production of H2O2 via a two-electron oxygen reduction reaction (ORR-2e-) is regarded as a highly promising decentralized and environmentally friendly mechanism for the production of this important chemical commodity. However, the underlying challenges related to the development of catalytic materials that contain zero or low content of noble metals and that are relatively more active, selective, and resistant for long-term use have become a huge obstacle for the electroproduction of H2O2 on commercial and industrial scales. The present study reports the synthesis and characterization of low metal-loaded (≤6.4 wt %) catalysts and their efficiency in H2O2 electroproduction. The catalysts were constructed using gold palladium molybdenum oxide (AuPdMoOx) and palladium molybdenum oxide (PdMoOx) nanoparticles supported on graphene nanoribbons. Based on the application of a rotating ring-disk electrode, we conducted a thorough comparative analysis of the electrocatalytic performance of the catalysts in the ORR under acidic and alkaline media. The proposed catalysts exhibited high catalytic activity (ca. 0.08 mA gnoble metal-1 in an acidic medium and ca. 6.6 mA gnoble metal-1 in an alkaline medium), good selectivity (over 80%), and improved long-term stability toward ORR-2e-. The results obtained showed that the enhanced ORR activity presented by the catalysts, which occurred preferentially via the two-electron pathway, was promoted by a combination of factors including geometry, Pd content, interparticle distance, and site-blocking effects, while the electrochemical stability of the catalysts may have been enhanced by the presence of MoOx.

Electrochemical oxidation of ciprofloxacin in different aqueous matrices using synthesized boron-doped micro and nano-diamond anodes.

The present work investigates the electrocatalytic performance of two different morphologies of boron doped-diamond film electrode (microcrystalline diamond - MCD, and nanocrystalline diamond - NCD) used in electrochemical oxidation for the removal of the antibiotic ciprofloxacin (CIP). A thorough study was conducted regarding the formation of the MCD and NCD films through the adjustment of methane in CH4/H2 gas mixture, and the two films were compared in terms of crystalline structure, apparent doping level, and electrochemical properties. The physicochemical results showed that the NCD film had higher sp2 carbon content and greater doping level; this contributed to improvements in its surface roughness, as well as its specific capacitance and charge transfer, which consequently enhanced its electrocatalytic activity in comparison with the MCD. The results obtained from CIP removal and mineralization assays performed in sulfate medium also showed that the NCD was more efficient than the MCD under all the current densities investigated. The effects of CIP concentration and the evolution of the final by-products, including short-chain carboxylic acids and inorganic ions, were also investigated. The electrochemical performance of the NCD was evaluated in different aqueous matrices, including chloride medium, real wastewater and simulated urine. The application of the NCD led to complete or almost complete CIP degradation, regardless of the medium employed. The kinetic constant rates obtained under the different media investigated were as follows: synthetic urine (0.0416 min-1 - R2 = 0.991) < real wastewater (0.0923 min-1 R2 = 0.997) < synthetic matrix containing chloride (0.1992 min-1 - R2 = 0.995); this shows that the pollutant degradation was affected by the type of aqueous matrix and the oxidants that were electrogenerated in situ. The results obtained from the analysis of electrical energy per order (EE/O) showed that the treatment of simulated urine spkiked with required the highest energy consumption, followed by the real effluent and synthetic matrix containing chloride. The present study proves the viability of electrocatalytic nanostructured materials to the treatment of antibiotics in complex matrices.

Highly Electroactive Ni Pyrophosphate/Pt Catalyst toward Hydrogen Evolution Reaction.

Robust electrocatalysts toward the resourceful and sustainable generation of hydrogen by splitting of water via electrocatalytic hydrogen evolution reaction (HER) are a prerequisite to realize high-efficiency energy research. Highly electroactive catalysts for hydrogen production with ultralow loading of platinum (Pt) have been under exhaustive exploration to make them cutting-edge and cost-effectively reasonable for water splitting. Herein, we report the synthesis of hierarchically structured nickel pyrophosphate (ß-Ni2P2O7) by a precipitation method and nickel phosphate (Ni3(PO4)2) by two different synthetic routes, namely, simple cost-effective precipitation and solution combustion processes. Thereafter, Pt-decorated nickel pyrophosphate and nickel phosphate (ß-Ni2P2O7/Pt and Ni3(PO4)2/Pt) were prepared by using potassium hexachloroplatinate and ascorbic acid. The fabricated novel nickel pyrophosphate and nickel phosphate/Pt materials were utilized as potential and affordable electrocatalysts for HER by water splitting. The detailed electrochemical studies revealed that the ß-Ni2P2O7/Pt (1 µg·cm-2 Pt) electrocatalyst showed excellent electrocatalytic performances for HER in acidic solution with an overpotential of 28 mV at -10 mA·cm-2, a Tafel slope of 32 mV·dec, and an exchange current density ( j0) of -1.31 mA·cm-2, which were close to the values obtained using the Vulcan/Pt (8.0 µg·cm-2 Pt), commercial benchmarking electrocatalyst with eight times higher Pt amount. Furthermore, the ß-Ni2P2O7/Pt electrocatalyst maintains an excellent stability for over -0.1 V versus RHE for 12 days, keeping j0 equal after the stability test (-1.28 mA cm-2). Very well-distributed Pt NPs inside the "cages" on the ß-Ni2P2O7 structure with a crystalline pattern of 0.67 nm distance to the Ni2P2O7/Pt electrocatalyst, helping the Volmer-Tafel mechanism with the Tafel reaction as a major rate-limiting step, help to liberate very fast the Pt sites after HER. The high electrocatalytic performance and remarkable durability showed the ß-Ni2P2O7/Pt material to be a promising cost-effective electrocatalyst for hydrogen production.