MULTI-LAYER KESTERITE-BASED PHOTOCATHODES FOR NH3 PHOTOSYNTHESIS FROM N2 REDUCTION REACTION.

The necessity of new methods to substitute the Haber-Bosch process in the NH3 synthesis, generating fewer greenhouse gases, and dispensing less energy, drove the investigation of the photoelectrocatalytic approach in the N2 reduction reaction (N2RR). For that, this work presents the synthesis and characterization of the layered CZTSSe/CdS/TiO2 photocathode decorated with Pt nanoparticles for application in NH3 production using the photoelectrocatalysis technique. The CZTSSe/CdS/TiO2-Pt characterization showed a well-designed and stable photocatalyst synthesized layer by layer with an important contribution of the Pt nanoparticles for the catalyst performance, improving the photocurrent density and the charge transfer. The N2RR in a two-compartment photochemical cell with 0.1 mol L-1 Na2SO3 and 0.05 mol L-1 H2SO4 in the cathodic and anodic chamber, respectively, using CZTSSe/CdS/TiO2-Pt and under 1 sun of light incidence and applied potential of -0.4 VAg/AgCl reached 0.22 mmol L-1 cm-2 NH3, a value 28 folds higher than using the catalyst without Pt modification. The superiority of N2RR under the photoelectrocatalysis technique was demonstrated compared to photocatalytic and electrocatalytic techniques, together with the investigation of the supporting electrolyte influence in the cathodic compartment. Additionally, that is the first time a kesterite-based photocathode has been applied to NH3 photosynthesis, showing excellent photoconversion capability.

One-step preparation of Co2V2O7: synthesis and application as a Fenton-like catalyst in a gas diffusion electrode.

Bimetallic oxides and MOFs have been used as catalysts for the ORR via two-electron and Fenton-based processes. This work reports the development of a new green one-step route for obtaining Co2V2O7. The Co2V2O7 oxide was immobilized on Printex-L6 carbon and used as a catalyst for the oxygen reduction reaction (ORR) and in heterogeneous Fenton-based processes. The PL6C/2.5% Co2V2O7 sample exhibited the best performance in the ORR via a two-electron pathway, increasing the selectivity for H2O2 generation. Electrochemical impedance spectroscopy analysis showed a decrease in charge transfer resistance in the Co2V2O7/PL6C matrix. The application of a gas diffusion electrode (GDE) modified with 2.5% Co2V2O7 resulted in a 30% increase in H2O2 production compared to the unmodified GDE. The unmodified GDE promoted methyl-paraben (MeP) removal of ∼80% after 90 min treatment, whereas the modified GDE promoted ∼90% of MeP removal in 30 min. The results obtained point to the potential of Co2V2O7 in improving the efficiency of GDE when applied for the treatment of organic pollutants.

Synergic effect of silver nanoparticles and carbon nanotubes on the simultaneous voltammetric determination of hydroquinone, catechol, bisphenol A and phenol.

A glassy carbon electrode (GCE) was modified with multi-walled carbon nanotubes (MWCNT) and silver nanoparticles (AgNPs) and applied to the simultaneous determination of hydroquinone (HQ), catechol (CC), bisphenol A (BPA) and phenol by using square-wave voltammetry. The MWCNTs were deposited on the GCE and the AgNPs were then electrodeposited onto the MWCNT/GCE by the application of 10 potential sweep cycles using an AgNP colloidal suspension. The modified GCE was characterized by using SEM, which confirmed the presence of the AgNPs. The electrochemical behavior of the material was evaluated by using cyclic voltammetry, and by electrochemical impedance spectroscopy that employed hexacyanoferrate as an electrochemical probe. The results were compared to the performance of the unmodified GCE. The modified electrode has a lower charge-transfer resistance and yields an increased signal. The peaks for HQ (0.30 V), CC (0.40 V), BPA (0.74 V) and phenol (0.83 V; all versus Ag/AgCl) are well separated under optimized conditions, which facilitates their simultaneous determination. The oxidation current increases linearly with the concentrations of HQ, CC, BPA and phenol. Detection limits are in the order of 1 µM for all 4 species, and the sensor is highly stable and reproducible. The electrode was successfully employed with the simultaneous determination of HQ, CC, BPA and phenol in spiked tap water samples. Graphical abstract A glassy carbon electrode was modified with carbon nanotubes and silver nanoparticles and then successfully applied to the simultaneous determination of four phenolic compounds. The sensor showed high sensitivity in the detection of hydroquinone, catechol, bisphenol A and phenol in water samples.

Towards Highly Efficient Chalcopyrite Photocathodes for Water Splitting: The Use of Cocatalysts beyond Pt.

Solar radiation is a renewable and clean energy source used in photoelectrochemical cells (PEC) to produce hydrogen gas as a powerful alternative to carbon-based fuels. Semiconductors play a vital role in this approach, absorbing the incident solar photons and converting them into electrons and holes. The hydrogen evolution reaction (HER) occurs in the interface of the p-type semiconductor that works as a photocathode in the PEC. Cu-chalcopyrites such as Cu(In, Ga)(Se,S)2 (CIGS) and CuIn(Se,S)2 (CIS) present excellent semiconductor characteristics for this purpose, but drawbacks as charge recombination, deficient chemical stability, and slow charge transfer kinetics, demanding improvements like the use of n-type buffer layer, a protective layer, and a cocatalyst material. Concerning the last one, platinum (Pt) is the most efficient and stable material, but the high price due to its scarcity imposes the search for inexpensive and abundant alternative cocatalyst. The present Minireview highlighted the use of metal alloys, transition metal chalcogenides, and inorganic carbon-based nanostructures as efficient alternative cocatalysts for HER in PEC.

SiO2-Ag Composite as a Highly Virucidal Material: A Roadmap that Rapidly Eliminates SARS-CoV-2.

COVID-19, as the cause of a global pandemic, has resulted in lockdowns all over the world since early 2020. Both theoretical and experimental efforts are being made to find an effective treatment to suppress the virus, constituting the forefront of current global safety concerns and a significant burden on global economies. The development of innovative materials able to prevent the transmission, spread, and entry of COVID-19 pathogens into the human body is currently in the spotlight. The synthesis of these materials is, therefore, gaining momentum, as methods providing nontoxic and environmentally friendly procedures are in high demand. Here, a highly virucidal material constructed from SiO2-Ag composite immobilized in a polymeric matrix (ethyl vinyl acetate) is presented. The experimental results indicated that the as-fabricated samples exhibited high antibacterial activity towards Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as well as towards SARS-CoV-2. Based on the present results and radical scavenger experiments, we propose a possible mechanism to explain the enhancement of the biocidal activity. In the presence of O2 and H2O, the plasmon-assisted surface mechanism is the major reaction channel generating reactive oxygen species (ROS). We believe that the present strategy based on the plasmonic effect would be a significant contribution to the design and preparation of efficient biocidal materials. This fundamental research is a precedent for the design and application of adequate technology to the next-generation of antiviral surfaces to combat SARS-CoV-2.

Influence of the different carbon nanotubes on the development of electrochemical sensors for bisphenol A.

Different methods of functionalisation and the influence of the multi-walled carbon nanotube sizes were investigated on the bisphenol A electrochemical determination. Samples with diameters of 20 to 170 nmwere functionalized in HNO3 5.0 mol L(-1) and a concentrated sulphonitric solution. The morphological characterisations before and after acid treatment were carried out by scanning electron microscopy and cyclic voltammetry. The size and acid treatment affected the oxidation of bisphenol A. The multi-walled carbon nanotubes with a 20-40 nm diameter improved the method sensitivity and achieved a detection limit for determination of bisphenol A at 84.0 nmol L(-1).

Development of a versatile rotating ring-disc electrode for in situ pH measurements.

There are some electrocatalytic reactions in which the key parameter explaining their behavior is a local change in pH. Therefore, it is of utter importance to develop an electrode that could quantify this parameter in situ, but also be customizable to be used in different systems. The purpose of this work is to build a versatile rotating ring/disc electrode (RRDE) with IrOx deposited on a glass tube as a ring and any kind of material as disc. As the IrOx is sensitive to pH variation, the reactions promoted on the disc can trigger proportional pH shifts on the ring. In such assembly, the IrOx ring presents a fast response time even during the pH transients due to the small thickness of the ring (approximately 10 µm), which enables the detection of interfacial pH changes. The ring electrode was tested toward the interfacial pH shift observed during the electrolytic reduction of water on the disc and also characterized by acid-base titration to determine the response time. As the main conclusions, fast response and durable RRDE were obtained, and this assembly could be used to revisit many electrocatalytic reactions in order to test the importance of local pH on the process.