Coffee-waste templated CeOx/TiO2 nanostructured materials for selective photocatalytic oxidations.

An environmentally friendly solvent-free approach was tested using spent coffee as a biomass sacrificial template for the preparation of TiO2 modified with CeOx. The use of coffee as a template pursues the preparation of a nanostructured heterojunction without the need for a solvent. Two variables were optimized in the synthesis process, i.e. calcination temperature and proportion of CeOx. Firstly, bare coffee-template titania was prepared to explore the effect of the calcination temperature, within 500-650 °C. The anatase phase was obtained up to 600 °C. Higher temperatures, i.e. 650 °C, led to the appearance of rutile (10%) and efficient removal of the sacrificial agent (0.6% residue). The maximum photocatalytic activity in terms of conversion, in the oxidation of benzyl alcohol, was achieved employing the bare coffee-template TiO2 at 650 °C, and it was found comparable to the benchmarked P25. The incorporation of ceria in the solvent-free approach considerably improved photocatalytic benzaldehyde production. No changes in the XRD pattern of TiO2 were appreciated in the presence of ceria due to the low amount added, within 1.5-6.0%, confirmed by XPS as superficial Ce3+/Ce4+. The UV-visible absorption spectra were considerably redshifted in the presence of Ce, reducing the bandgap values of bare titania. An optimum amount of ceria in the structure within 3-0% was found. In this case, the selectivity towards benzaldehyde was ca. 75%, 3 times higher than the selectivity value registered for the benchmarked P25 or the bare prepared TiO2.

Boosted Activity of g-C3N4/UiO-66-NH2 Heterostructures for the Photocatalytic Degradation of Contaminants in Water.

The combination of graphitic carbon nitride and the metal-organic framework UiO-66-NH2 has been developed with the aim to enhance the photocatalytic activity of pure semiconductors. Different proportions of g-C3N4 and UiO-66-NH2 were combined. Complete characterization analysis of the resulting photocatalytic materials was conducted, including N2 adsorption isotherms, XRD, FTIR, STEM-EDX microscopy, DRS-UV-visible, and photoluminescence. The photocatalytic activity was tested in an aqueous solution for the removal of acetaminophen as the target pollutant. From the obtained results, less than 50% of UiO-66-NH2 incorporated in the g-C3N4 structure enhanced the photocatalytic degradation rate of both bare semiconductors. Concretely, 75% of g-C3N4 in the final g-C3N4/UiO-66-NH2 heterostructure led to the best results, i.e., complete acetaminophen elimination initially at 5 mg·L-1 in 2 h with a pseudo-first order rate constant of ca. 2 h-1. The presence of UiO-66-NH2 in the g-C3N4 enhanced the optoelectronic properties, concretely, the separation of the photo-generated charges was improved according to photoluminescence characterization. The better photo-absorption uptake was also confirmed by the determination of the quantum efficiency values of the heterostructure if compared to either pure g-C3N4 or UiO-66-NH2. This photocatalyst with the best activity was further tested at different pH values, with the best degradation rate at a pH close to the pHpzc ~4.15 of the solid. Sequential recycling tests demonstrated that the heterostructure was stable after five cycles of use, i.e., 15 h. A high contribution of photo-generated holes in the process of the degradation of acetaminophen, followed marginally by superoxide radicals, was suggested by scavenger tests.

Metabolomics reveals synergy between Ag and g-C3N4 in Ag/g-C3N4 composite photocatalysts: a unique feature among Ag-doped biocidal materials.

INTRODUCTION: The silver/graphitic carbon nitride (Ag/g-C3N4) composite system exerts biocidal activity against the pathogenic bacterium Escherichia coli 1337-H that is stronger than that of well-known silver and titanium oxide (TiO2)-based composites. However, whether the Ag/g-C3N4 composite system has biocidal properties that the parent components do or do not have as separate chemical entities and whether they differ from those in Ag/TiO2 composite photocatalysts have not been clarified. OBJECTIVE: We investigated the chemical (cooperative charge handling and electronic properties) and biological (metabolic) effects exerted by the addition of Ag to g-C3N4 and to TiO2. METHODS: In this work, we undertook metabolome-wide analysis by liquid chromatography-electrospray ionization-quadrupole-time of flight-mass spectrometry to compare the metabolite profiles of untreated E. coli 1337-H cells or those subjected to disinfection with Ag, g-C3N4, 2Ag/g-C3N4, TiO2 and 2Ag/TiO2. RESULTS: While Ag or g-C3N4 moderately affected microbial metabolism according to the mean of the altered metabolites, multiple cell systems contributing to rapid cell death were immediately affected by the light-triggered radical species produced when Ag and g-C3N4 were as xAg/g-C3N4. The effects include drastically reduced production of small metabolites essential for detoxifying reactive oxygen species and those that regulate DNA replication fidelity, cell morphology and energy status. These biological consequences were different from those caused by Ag/TiO2-based biocides, demonstrating the uniqueness of the Ag/g-C3N4 system. CONCLUSIONS: Our results support the idea that the unique Ag/g-C3N4 biocidal properties are based on synergistic action and reveal new directions for designing future photocatalysts for use in disinfection and microbial control.

Nature-inspired hierarchical materials for sensing and energy storage applications.

Nature-inspired hierarchical architectures have recently drawn enormous interest in the materials science community, being considered as promising materials for the development of high-performance wearable electronic devices. Their highly dynamic interfacial interactions have opened new horizons towards the fabrication of sustainable sensing and energy storage materials with multifunctional properties. Nature-inspired assemblies can exhibit impressive properties including ultrahigh sensitivity, excellent energy density and coulombic efficiency behaviors as well as ultralong cycling stability and durability, which can be finely tuned and enhanced by controlling synergistic interfacial interactions between their individual components. This tutorial review article aims to address recent breakthroughs in the development of advanced Nature-inspired sensing and energy storage materials, with special emphasis on the influence of interfacial interactions over their improved properties.

Thermal and light irradiation effects on the electrocatalytic performance of hemoglobin modified Co3O4-g-C3N4 nanomaterials for the oxygen evolution reaction.

The oxygen evolution reaction (OER) plays a key role in the water splitting process and a high energy conversion efficiency is essential for the definitive advance of hydrogen-based technologies. Unfortunately, the green and sustainable development of electrocatalysts for water oxidation is nowadays a real challenge. Herein, a successful mechanochemical method is proposed for the synthesis of a novel hemoglobin (Hb) modified Co3O4/g-C3N4 composite nanomaterial. The controlled incorporation of cobalt entities as well as Hb functionalization, without affecting the g-C3N4 nanoarchitecture, was evaluated using different physicochemical techniques, such as X-ray diffraction, N2-physisorption, scanning electron microscopy, UV-visible spectroscopy and X-ray photoelectron spectroscopy. The beneficial effect of the resulting ternary bioconjugate together with the influence of the temperature and light irradiation was investigated by electrochemical analysis. At 60 °C and under light exposition, this electrocatalyst requires an overpotential of 370 mV to deliver a current density of 10 mA·cm-2, showing a Tafel slope of 66 mV·dec-1 and outstanding long-term stability for 600 OER cycles. This work paves a way for the controlled fabrication of multidimensional and multifunctional bio-electrocatalysts.

Improving Electrochemical Hydrogen Evolution of Ag@CN Nanocomposites by Synergistic Effects with α-Rich Proteins.

A graphitic carbon nitride nanostructure has been successfully functionalized by incorporation of different silver contents and subsequent modification with an α-rich protein, namely hemoglobin. Mechanochemistry has been employed, as an efficient and sustainable procedure, for the incorporation of the protein. A complete characterization analysis has been performed following a multitechnique approach. Particularly, XPS data exhibited considerable differences in the C 1s region for the Hb/xAg@CN, ensuring the successful protein anchorage on the surface of the graphitic carbon nitride-based materials. The as-synthesized nanomaterials delivered impressive performance toward hydrogen evolution reactions with an overpotential of 79 mV at a current density of 10 mA/cm2 for Hb/20Ag@CN nanohybrids, which is comparable with the most efficient HER electrocatalysts reported in the literature. The outstanding HER properties were associated with the unique synergistic interactions, quantitatively measured, between AgNPs, Hb tertiary architecture, and the graphitic carbon nitride networks.

Waste-derived Materials: Opportunities in Photocatalysis.

Waste-derived materials have been gaining increased attention in recent years due to their great potential and environmentally friendly nature. Several contributions in the literature have covered the advances achieved so far in this area. Nonetheless, to the best of our knowledge, no review has been dedicated specifically to waste-derived or templated photocatalytic materials. Both photocatalysis and (bio)waste-inspired design yield materials of a remarkably green nature. Therefore, the partnership between them may open promising possibilities for both waste valorization and photocatalytic processes, which in turn will lead to sustainable development globally, with the potential for full utilization of renewable energy sources such as biomass and sunlight. Several photocatalytic waste-derived materials, synthetic procedures, and applications will be described throughout this work, including waste-derived/templated TiO2, ZnO, and metal sulfide materials. Special attention will be given to biomass-inspired carbonaceous materials, including carbon quantum dots and graphitic carbon nitride (g-C3N4).

Characterization of Photo-catalysts: From Traditional to Advanced Approaches.

The article provides an overview of the most relevant characterization results of heterogeneous photo-catalytic materials available in the literature. First, we present a summary of the ex situ utilization of physico-chemical characterization techniques. In the majority of current works, pre and post-reaction samples are subjected to ex situ analysis using a multitechnique approach which attempts to render information about the morphological, structural, and electronic properties of relevance to interpret photoactivity. Details of the effects on physico-chemical observables of the nanostructure and the complex chemical nature (considering mono and multiphase materials with presence of several chemical elements) of typical photo-catalysts will be analyzed. Modern studies however emphasize the use of in situ tools in order to establish activity-structure links. To this end, the first point to pay attention to is to consider carefully the interaction between light and matter at the reaction cell where the characterization is carried out. Operando and spectro-kinetic methodologies will be reviewed as they would render valuable and trusting results and thus will pave the way for the future developments in photocatalysis.

Thermo-Photocatalysis: Environmental and Energy Applications.

Catalysis is an integral part of a majority of chemical operations focused on the generation of value-added chemicals or fuels. Similarly, the extensive use of fossil-derived fuels and chemicals has led to deterioration of the environment. Catalysis currently plays a key role in mitigating such effects. Thermal catalysis and photocatalysis are two well-known catalytic approaches that were applied in both energy and environmental fields. Thermo-photocatalysis can be understood as a synergistic effect of the two catalytic processes with key importance in the use of solar energy as thermal and light source. This Review provides an update on relevant contributions about thermo-photocatalytic systems for environmental and energy applications. The reported activity data are compared with the conventional photocatalytic approach and the base of the photothermal effect is analyzed. Some of the systems based on the positive aspects of thermo- and photocatalysis could be the answer to the energy and environmental crisis when taking into account the outstanding results with regard to chemical efficiency and energy saving.

Continuous Flow Synthesis of High Valuable N-Heterocycles via Catalytic Conversion of Levulinic Acid.

Graphitic carbon nitride (g-C3N4) was successfully functionalized with a low platinum loading to give rise to an effective and stable catalytic material. The synthesized g-C3N4/Pt was fully characterized by XRD, N2 physisorption, XPS, SEM-Mapping, and TEM techniques. Remarkably, XPS analysis revealed that Pt was in a dominant metallic state. In addition, XPS together with XRD and N2 physisorption measurements indicated that the g-C3N4 preserves its native structure after the platinum deposition process. g-C3N4/Pt was applied to the catalytic conversion of levulinic acid to N-heterocycles under continuous flow conditions. Reaction parameters (temperature, pressure, and concentration of levulinic acid) were studied using 3 levels for each parameter, and the best conditions were employed for the analysis of the catalyst's stability. The catalytic system displayed high selectivity to 1-ethyl-5-methylpyrrolidin-2-one and outstanding stability after 3 h of reaction.

Mimicking the bioelectrocatalytic function of recombinant CotA laccase through electrostatically self-assembled bioconjugates.

Unprecedented 3D nanobiosystems composed of recombinant CotA laccases and citrate-stabilised gold nanoparticles have been successfully achieved by an electrostatic self-assembly strategy. The bioelectrochemical reduction of O2 driven by CotA laccase at the spore coat was mimicked. Consequently key insights into its bioelectrocatalytic function were unravelled.

Braiding kinetics and spectroscopy in photo-catalysis: the spectro-kinetic approach.

The combination of kinetic and spectroscopic tools has become a key scientific methodology for the understanding of catalytic behavior but its application in photocatalysis has inherent difficulties due to the nature of the energy source of the reaction. This review article provides an overview of its use by, first, presenting mechanistically derived kinetic formulations and spectroscopic data handling methods including intrinsic expressions for light and, second, highlighting representative examples of application. To do it we consider universal catalytic systems, particularly (although not exclusively) titania-based materials, and the most frequent hole and/or electron triggered reaction schemes. This review also provides a general framework to pave the way for the future progress of the spectro-kinetic approach in the photocatalysis area.

Highly Active Catalytic Ruthenium/TiO2 Nanomaterials for Continuous Production of γ-Valerolactone.

Green energy production from renewable sources is an attractive, but challenging topic to face the likely energy crisis scenario in the future. In the current work, a series of versatile Ru/TiO2 catalysts were simply synthesized and employed in continuous-flow catalytic transfer hydrogenation of industrially derived methyl levulinate biowaste (from Avantium Chemicals B.V.) to form γ-valerolactone. Different analytical techniques were applied in the characterization of the as-synthesized catalysts, including XRD, SEM, energy-dispersion X-ray spectroscopy, TEM, and X-ray photoelectron spectroscopy. The effects of various reaction conditions (e.g., temperature, concentration, and flow rate) were investigated. Results suggested that optimum dispersion and distribution of Ru on the TiO2 surface could efficiently promote the production of γ-valerolactone; the 5 % Ru/TiO2 catalyst provided excellent catalytic performance and stability compared with commercial Ru catalysts.

Phase-Contact Engineering in Mono- and Bimetallic Cu-Ni Co-catalysts for Hydrogen Photocatalytic Materials.

Understanding how a photocatalyst modulates its oxidation state, size, and structure during a photocatalytic reaction under operando conditions is strongly limited by the mismatch between (catalyst) volume sampled by light and, to date, the physicochemical techniques and probes employed to study them. A synchrotron micro-beam X-ray absorption spectroscopy study together with the computational simulation and analysis (at the X-ray cell) of the light-matter interaction occurring in powdered TiO2 -based monometallic Cu, Ni and bimetallic CuNi catalysts for hydrogen production from renewables was carried out. The combined information unveils an unexpected key catalytic role involving the phase contact between the reduced and oxidized non-noble metal phases in all catalysts and, additionally, reveals the source of the synergistic Cu-Ni interaction in the bimetallic material. The experimental method is applicable to operando studies of a wide variety of photocatalytic materials.

Surface CuO, Bi2O3, and CeO2 Species Supported in TiO2-Anatase: Study of Interface Effects in Toluene Photodegradation Quantum Efficiency.

The enhancement of active triggered by surface deposition of Cu, Bi, and Ce containing oxidic species onto a high surface area anatase is analyzed through the calculation of the quantum efficiency for toluene photodegradation under UV and Sunlight-type illumination. To this end, series of Cu, Bi, and Ce containing oxides supported on anatase were synthesized having a growing content of the Cu, Bi, and Ce surface species and characterized with X-ray diffraction and photoelectron, UV-visible, and photoluminescence spectroscopies as well as transmission electron microscopy. Utilizing the surface concentration of Cu, Bi, and Ce species as a tool, we analyzed the influence of the system physicochemical properties affecting quantum efficiency in anatase-based materials. First, employing small surface concentrations of the Cu, Bi, and Ce species deposited onto (the unperturbed) anatase, we provided evidence that all steps of the photocatalytic event, including light absorption, charge recombination, as well as surface interaction with the pollutant and chemical output as to activity and selectivity have significance in the quantitative assessment of the enhancement of the efficiency parameter. Second, we analyzed samples rendering maximum quantum efficiency within all these series of materials. The study indicates that maximum enhancement over anatase displays a magnitude strongly dependent on the efficiency level of calculation and would thus require the use of the most accurate one, and that it occurs through a balance between optoelectronic and chemical properties of the composite materials. The (Cu, Bi, Ce) oxide-anatase interface plays a major role modulating the optoelectronic properties of the solids and thus the efficiency observable.

Interface Effects in Sunlight-Driven Ag/g-C3N4 Composite Catalysts: Study of the Toluene Photodegradation Quantum Efficiency.

Metallic silver (ranging from 1 to 10 wt %) was deposited onto a graphite-like carbon nitride photocatalyst through a microemultion method. Surface, morphological, and structural properties of the resulting materials were characterized using BET and porosity measurements, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and UV-vis and photoluminescence spectroscopy. The activity of the composite samples under sunlight-type and visible illumination was measured for toluene photodegradation and was analyzed by means of the reaction rate and the quantum efficiency parameter. To obtain the latter observable, the lamp emission properties as well as the radiation field interaction with the catalyst inside the reactor were modeled and numerically calculated. The stability of the samples under both illumination conditions was also studied. The results evidence that the composite samples containing 1-10 silver wt % outperform carbon nitride for sunlight-type and visible illumination, but the optimal use of the charge generated after light absorption is obtained for the sample with 1 wt % of silver acording to the quantum efficiency calculation. The study shows that the optimum silver-g-C3N4 contact is able to outperform TiO2 reference systems (nano-TiO2 and P25) under sunlight illumination and points out that this occurs as a direct consequence of the charge handling through the interface between catalyst components. This indicates that composite systems based on g-C3N4 can be competitive in sunlight-triggered photodegradation processes to eliminate tough polluctants such as toluene, rendering active and stable systems.