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In the evolving field of photocatalysis, heterojunction photocatalysts, especially Type II and S-scheme, the latter being also known as direct-Z scheme heterojunctions, are gaining increasing recognition for their pivotal role in enhancing photocatalytic efficiency. These heterojunctions, characterized by similar band alignments but distinct charge transfer mechanisms, play a crucial role in facilitating enhanced charge separation and transfer. This comprehensive review delves into the experimental methodologies essential for characterizing these heterojunctions, with a focus on understanding their unique charge transfer mechanisms. Key methods such as Electron Spin Resonance (ESR), radical trapping experiments, Photoluminescence (PL) probing, Nitro Blue Tetrazolium (NBT) transformation, Surface Photovoltage Spectroscopy (SPS), photodeposition of metals, and in-situ X-ray Photoelectron Spectroscopy (in-situ XPS) analysis are discussed in detail. Each technique is presented with necessary guidelines and accompanying information to ensure their appropriate and effective use in pinpointing the specifics of charge transfer processes. The review concludes that the right selection of experimental techniques is crucial in understanding the charge transfer mechanism in staggered type heterojunctions and achieving further advancements in the field of photocatalysis.

New ternary materials TiO2-Al2O3-GnPs (TAG) were prepared by using an innocuous sol-gel method with a slight modification for the addition of graphene nanoplatelets (GnPs), under room temperature and atmospheric pressure. The materials TiO2-Al2O3-GnPs were prepared with variations of concentration between 0.05 and 1 wt % of GnPs. In this study, we analyzed the physicochemical properties by X-ray diffraction (XRD) and UV-Vis spectroscopy, textural properties by N2 physisorption, morphology by scanning and transmission electron microscopy (SEM, TEM) and a chemical species analysis was carried out by X-ray photoelectron spectroscopic (XPS). The photocatalytic activity of each material was evaluated in the degradation of a model molecule, Diuron, a carcinogenic and cytotoxic herbicide used in farm fields. To determine reaction selectivity and mineralization degree, the photocatalytic reaction was monitored by using UV-Vis spectroscopy and total organic carbon (TOC). In samples with higher GnPs’ concentration, a good enough specific surface area of up to 379 m2/g was observed, and reduced band gap energy (2.8 eV) with respect to TiO2 and mixed oxide (3.2 and 3.1 eV respectively), was obtained. These resulting properties were the key indicator so that the materials could be applied as photocatalysts. In the photocatalytic activity determination, TAG-0.75 was the sample that showed the best results with respect to the mixed oxide; the highest photocatalytic conversion, the reduced average life time, and increased mineralization and reaction selectivity.

We studied the effect of urea on TiO2–CeO2 and paracetamol photodegradation. The contribution of TiO2, CeO2, and urea was analyzed by simplex-centroid mixture. Solid-state combustion at 500 °C was the method of synthesis. All samples were characterized by X-ray diffraction, nitrogen adsorption/desorption, Uv spectroscopy, and scanning electron spectroscopy (SEM). According to the results, urea influences particle morphology. Bandgap decreases due to interactions with residual urea carbon. The surface area depended on the crystallinity of the samples. The value of the kinetic constant increased as a function of the amount of urea. The selectivity to CO2 was the roll of cerium oxide.

Background: Amyotrophic lateral sclerosis (ALS) is a progressive disease characterized by degeneration of upper and lower motor neurons. Time from symptom onset to confirmed diagnosis has been reported from 8 to 15 months in ALS. Objectives: To describe the frequency of the split hand phenomenon and propose it as an early biomarker for ALS diagnosis. Methods: A retrospective, analytical, descriptive, and single-center observational study was performed. The split hand ratio was determined by dividing distal abductor pollicis brevis/abductor digit minimi compound muscle action potentials; a result < 0.6 was considered present. Results: Fifty-four patients with ALS diagnosis were included in the study. The split hand ratio was identified in 61.5% of patients with definite ALS, in 68.7% with probable ALS, 80% with possible ALS, and in 50% with suspected ALS. The split hand phenomenon was identified in 60% of patients within 12 months of symptom onset. Conclusion: We provide evidence for an additional neurophysiological tool that helps early diagnosis of ALS.

Abstract This paper studies Cu/Al2O3 catalysts, synthesized in two ways: copper deposit in the synthesis of alumina (sol gel) and incipient impregnation stabilized at 400 °C. The materials were characterized by X‐ray diffraction studies, nitrogen physisorption, temperature programmed reduction of H2, dehydration of isopropanol, scanning electronic microscopy, transmission electronic microscopy, which were evaluated in the liquid phase oxidation reaction of ethyl tert‐butyl ether and tert‐amyl methyl ether. The formation of CuAl2O4 and CuAlO2 in the samples synthesized by sol gel, led to a modification of the texture, thus resulting in an expansion of the specific area of the materials. CuAl2O4 and CuAlO2 have been identified by DRX from a content of 10 % Copper, the first showed the highest intensity with this technique. In the same way, these species favor the presence of Lewis acid sites; this is reflected in the materials with (Di‐isopropyl Ether) DIPE of 96.7 % and 91.1 % for the samples SAlCu5 and SAlCu15 respectively. The catalytic activity of the materials prepared by sol gel is in the function of the number of surface acid sites, the smaller particle size of the Cu and the surface of the contact, in the case of the ETBE meanwhile for TAME the activity was based mainly on the strength of the present acid sites. With impregnated materials, the activity is attributed to the smaller particle size of the Cu and the greater strength of the surface acid sites in the solid. The formation of spinel species inhibits the leaching phenomenon in the reaction milieu.

γ-Valerolactone (GVL) has been considered an alternative as biofuel in the production of carbon-based chemicals; however, the use of noble metals and corrosive solvents has been a problem. In this work, Ni supported nanocatalysts were prepared to produce γ-Valerolactone from levulinic acid using methanol as solvent at a temperature of 170 °C utilizing 4 MPa of H2. Supports were modified at pH 3 using acetic acid (CH3COOH) and pH 9 using ammonium hydroxide (NH4OH) with different tungsten (W) loadings (1%, 3%, and 5%) by the Sol-gel method. Ni was deposited by the suspension impregnation method. The catalysts were characterized by various techniques including XRD, N2 physisorption, UV-Vis, SEM, TEM, XPS, H2-TPR, and Pyridine FTIR. Based on the study of acidity and activity relation, Ni dispersion due to the Lewis acid sites contributed by W at pH 9, producing nanoparticles smaller than 10 nm of Ni, and could be responsible for the high esterification activity of levulinic acid (LA) to Methyl levulinate being more selective to catalytic hydrogenation. Products and by-products were analyzed by 1H NMR. Optimum catalytic activity was obtained with 5% W at pH 9, with 80% yield after 24 h of reaction. The higher catalytic activity was attributed to the particle size and the amount of Lewis acid sites generated by modifying the pH of synthesis and the amount of W in the support due to the spillover effect.

In this study, simplex centroid mixture design was employed to determine the effect of urea on ZnO-CeO. The heterojunction materials were synthesized using a solid-state combustion method, and the physicochemical properties were evaluated using X-ray diffraction, nitrogen adsorption/desorption, and UV–Vis spectroscopy. Photocatalytic activity was determined by a triclosan degradation reaction under UV irradiation. According to the results, the crystal size of zinc oxide decreases in the presence of urea, whereas a reverse effect was observed for cerium oxide. A similar trend was observed for ternary samples, i.e., the higher the proportion of urea, the larger the crystallite cerium size. In brief, urea facilitated the co-existence of crystallites of CeO and ZnO. On the other hand, UV spectra indicate that urea shifts the absorption edge to a longer wavelength. Studies of the photocatalytic activity of TCS degradation show that the increase in the proportion of urea favorably influenced the percentage of mineralization.

5-Hydroxymethylfurfural (5-HMF) has been described as one of the 12 key platform molecules derived from biomass by the US Department of Energy, and its hydrogenation reaction produces versatile liquid biofuels such as 2,5-dimethylfuran (2,5-DMF). Catalytic hydrogenation from 5-HMF to 2,5-DMF was thoroughly studied on the metal nickel catalysts supported on Al2O3-TiO2-ZrO2 (Ni/ATZ) mixed oxides using isopropanol and formic acid (FA) as hydrogen donors to find the best conditions of the reaction and hydrogen donor. The influence of metal content (wt%), Ni particle size (nm), Nickel Ni0, Ni0/NiO and NiO species, metal active sites and acid-based sites on the catalyst surface, and the effect of the hydrogen donor (isopropanol and formic acid) were systematically studied. The structural characteristics of the materials were studied using different physicochemical methods, including N2 physisorption, XRD, Raman, DRS UV-Vis, FT-IR, SEM, FT-IR Pyad, H2-TPD, CO2-TPD, H2-TPR, TEM and XPS. Second-generation 2,5-DMF biofuel and 5-HMF conversion by-products were analyzed and elucidated using 1H NMR. It was found that the Ni0NiO/ATZ3WI catalyst synthesized by the impregnation method (WI) generated a good synergistic effect between the species, showing the best catalytic hydrogenation of 5-HMF to 2,5-DMF using formic acid as a hydrogen donor for 24 h of reaction and temperature of 210 °C with 20 bar pressure of Argon (Ar).

Photocatalysis is an effective advanced oxidation process to mineralize recalcitrant contaminants in aqueous media. TiO2 is the most used photocatalyst in this type of process. To improve the deficiencies of this material, one of the most used strategies has been to dope TiO2 with metallic ions. Chemical reagents are often used as dopant precursors. However, due to the depletion of natural resources, in this work it was proposed to substitute chemical reagents and instead use a metallic residue (door key) as a doping precursor. The materials were synthesized using the sol–gel method and calcined at 400 °C to obtain the crystal structure of anatase. The characterization of the materials was carried out using X-ray diffraction (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), scanning electron microscopy–energy-dispersive X-ray analysis (SEM-EDX) methods X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma optical emission spectroscopy (ICP-OES). The results obtained indicate that Cu+/Cu2+ and Zn2+ ions coexist in the support, which modifies the physicochemical properties of TiO2 and improves its photocatalytic efficiency. The synergistic effect of the dopants in TiO2 allowed the mineralization of diclofenac in an aqueous medium when T-DK (1.0) was used as photocatalyst and simulated solar radiation as an activation source.

NiWAu trimetallic nanoparticles (NPs) on the surface of support Al2O3-CeO2-TiO2 were synthesized by a three-step synthetic method in which Au NPs were incorporated into presynthesized NiW/Al2O3-CeO2-TiO2. The recharge method, also known as the redox method, was used to add 2.5 wt% gold. The Al2O3-CeO2-TiO2 support was made by a sol–gel method with two different compositions, and then two metals were simultaneously loaded (5 wt% nickel and 2.5 wt% tungsten) by two different methods, incipient wet impregnation and ultrasound impregnation method. In this paper, we study the effect of Au addition using the recharge method on NiW nanomaterials supported on mixed oxides on the physicochemical properties of synthesized nanomaterials. The prepared nanomaterials were characterized by scanning electron microscopy, BET specific surface area, X-ray diffraction, diffuse reflectance spectroscopy in the UV–visible range and temperature-programmed desorption of hydrogen. The experimental results showed that after loading of gold, the dispersion was higher (46% and 50%) with the trimetallic nanomaterials synthesized by incipient wet impregnation plus recharge method than with impregnation plus ultrasound recharge method, indicating a greater number of active trimetallic (NiWAu) sites in these materials. Small-sized Au from NiWAu/ACTU1 trimetallic nanostructures was enlarged for NiWAu/ACT1. The strong metal NPs–support interaction shown for the formation of NiAl2O4, Ni-W-O and Ni-Au-O species simultaneously present in the surface of trimetallic nanomaterial probably plays an important role in the degree of dispersion of the gold active phase.

The isosteric enthalpy of adsorption (Δadsh˙) of CO2 in three different micro and mesoporous materials was evaluated in this work. These materials were a microporous material with functional groups of nitrogen and oxygen (CMFs, carbon microfibers), a mesoporous material with silanol groups (SBA-15, Santa Barbara Amorphous), and a mesoporous material with amine groups (SBA-15_APTES, SBA-15 amine-functionalized with (3-Aminopropyl)-triethoxysilane). The temperature interval explored was between 263 K and 303 K, with a separation of 5 K between each one, so a total of nine CO2 isotherms were obtained. Using the nine isotherms and the Clausius–Clapeyron equation, the reference value for Δadsh˙ was found. The reference value was compared with those Δadsh˙ obtained, considering some arrangement of three or five CO2 isotherms. Finally, it was found that at 298 K and 1 bar, the total amount of CO2 adsorbed is 2.32, 0.53, and 1.37 mmol g−1 for CMF, SBA-15, and SBA-15_APTES, respectively. However, at a coverage of 0.38 mmol g−1, Δadsh˙ is worth 38, 30, and 29 KJ mol−1 for SBA-15_APTES, CMFs, and SBA-15, respectively. So, physisorption predominates in the case of CMF and SBA-15 materials, and the Δadsh˙ values significantly coincide regardless of whether the isotherms arrangement used was three or five. Meanwhile, in SBA-15_APTES, chemisorption predominates as a consequence of the arrangements used to obtain Δadsh˙. This happens in such a way that the use of low temperatures (263–283 K) tends to produce higher Δadsh˙ values, while the use of high temperatures (283–303 K) decreases the Δadsh˙ values.

This work reports a new technique called “Suspension Impregnation Method” (SiM) as an alternative to the “Incipient Impregnation Method” (IiM) for the synthesis of noble metal (Au) nanoparticles. The SiM was used to synthesize gold nanoparticles supported by titanium oxide and compared with those of IiM. The reactor for the SiM technique was based on the principles of mixing, heat, and mass transfer of the suspension reactors and the metal particle synthesis was processed in situ under the oxidation reduction potentials. Three different conditions were established to observe the effect of pH on the size of the metal particles: acid (HCl), neutral (water) and alkaline (urea). The samples were characterized by nitrogen adsorption, X-Ray Diffraction (XRD), Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Thermogravimetric Analysis (TGA)/Differential Thermal Analysis (DTA), Transmission Electron Microscopy (TEM) and CO2 adsorption. The surface area was slightly modified, and the average pore diameter was reduced in all materials. The structure of the titanium oxide was not altered. A deposit of organic material was detected in samples synthesized in alkaline medium for both methods. The pH influenced the formation of conglomerates in IiM and resulted in large particle sizes (3–9 nm). In contrast, an in situ reduction in the species in SiM resulted in smaller particle sizes than IiM (2–3 nm).

Background: Bilateral third cranial nerve palsy has only been reported in a handful of conditions including some with inflammatory, tumoural and vascular causes. An urgent imaging study is mandatory to rule out vascular aetiology, mainly aneurysmal subarachnoid haemorrhage (aSAH). Case presentation: A 28-year-old Hispanic woman presented to the emergency department with a 21-day history of a sudden-onset and severe headache that on three occasions was accompanied by transient loss of awareness, the last episode occurring a week previously. The simple CT image showed minimal bleeding at the level of the perimesencephalic cisterns, with evidence of SAH. An angioCT revealed a 5×6 mm bilobed saccular aneurysm of the right posterior communicating artery and a 2×2 mm saccular aneurysm in the posterior left communicating artery. Conclusions: A mirror aneurysm is found in 2–25% of aSAH cases. To date there is no consensus about the optimal management of patients with these findings.

This study was conducted to identify the correlation between the CO chemisorption (linear interaction and gem dicarbonyl) and the specific size of rhodium particles, and further to determine the influence of this relationship on the catalytic oxidation reaction of methyl tert-butyl ether (MTBE). During the synthesis, first, TiO2 was developed by the sol-gel method under acidic conditions. Second, Rh was deposited (1 wt %) by the incipient wetness impregnation method. Later, with the aim of controlling the particle size, the Rh/TiO2 materials were crystallized at different reduction conditions during 3 h heat treatment. The results obtained by TEM micrographs indicated that the average particle size varies between 1.0 and 8.1 nm, depending on the conditions of heat treatment. From the histogram analysis of each TEM micrograph, two correlations were made: (i) the gem-dicarbonyl interaction was typical of Rh particles ≤ 1.5 nm, and (ii) a linear interaction, bridged interaction and dentate interaction were observed in particles ≥ 1.6 nm. The gem-dicarbonyl interaction (particle size ≤ 1.5 nm) was the most active in the oxidation reaction of MTBE.

Objective: To photodegrade Diuron with TiO2-Al2O3 nanomaterials supported on graphene nanoplatelets (GnPs) Design/methodology/approach: The synthesis of the materials was carried out by the sol-gel method under mild conditions. Subsequently, the obtained materials were subjected to thermal processing for structural stabilization and pulverized. Synthesized nanomaterials were then characterized by nitrogen adsorption/ desorption, X-ray diffraction, scanning electron microscopy, and Uv-Vis spectroscopy. Results: The adsorption/desorption results indicated that the ternary TiO2-Al2O3/GnPs nanomaterials were found to have complex porosity, which suggested that TiO2-Al2O3 was formed on agglomerated GnPs. X-ray diffraction data revealed that the anatase phase of TiO2 and the -Al2O3 phase coexist with the crystalline phase of graphene. The morphology of the materials indicates that the nanoplatelets were randomly dispersed in a continuous mixed oxide phase. About the UV analysis, the presence of GnPs at 1 wt % concentration reduces the band gap by 6%. Limitations on study/implications: The physical and chemical properties of GnPs make the material an excellent candidate for the degradation of pollutants by photocatalysis. Findings/conclusions: The addition of GnPs improved the Diuron degradation, probably by forming a nanostructured interface or heterojunction. [ABSTRACT FROM AUTHOR]

5-Hydroxymethylfurfural (5-HMF) has been described as one of the 12 key platform molecules derived from biomass by the US Department of Energy, and its hydrogenation reaction produces versatile liquid biofuels such as 2,5-dimethylfuran (2,5-DMF). Catalytic hydrogenation from 5-HMF to 2,5-DMF was thoroughly studied on the metal nickel catalysts supported on Al2O3-TiO2-ZrO2 (Ni/ATZ) mixed oxides using isopropanol and formic acid (FA) as hydrogen donors to find the best conditions of the reaction and hydrogen donor. The influence of metal content (wt%), Ni particle size (nm), Nickel Ni0, Ni0/NiO and NiO species, metal active sites and acid-based sites on the catalyst surface, and the effect of the hydrogen donor (isopropanol and formic acid) were systematically studied. The structural characteristics of the materials were studied using different physicochemical methods, including N2 physisorption, XRD, Raman, DRS UV-Vis, FT-IR, SEM, FT-IR Pyad, H2-TPD, CO2-TPD, H2-TPR, TEM and XPS. Second-generation 2,5-DMF biofuel and 5-HMF conversion by-products were analyzed and elucidated using 1H NMR. It was found that the Ni0NiO/ATZ3WI catalyst synthesized by the impregnation method (WI) generated a good synergistic effect between the species, showing the best catalytic hydrogenation of 5-HMF to 2,5-DMF using formic acid as a hydrogen donor for 24 h of reaction and temperature of 210 °C with 20 bar pressure of Argon (Ar). [ABSTRACT FROM AUTHOR]