Improved mechanical stability of HKUST-1 in confined nanospace

One of the main concerns in the technological application of several metal–organic frameworks (MOFs) relates to their structural instability under pressure (after a conforming step). Here we report for the first time that mechanical instability can be highly improved via nucleation and growth of MOF nanocrystals in the confined nanospace of activated carbons.Financial support from MINECO projects MAT2013-45008-p and CONCERT Project-NASEMS (PCIN-2013-057) is gratefully acknowledged

Photocatalytic Oxidation of VOCs in Gas Phase Using Capillary Microreactors with Commercial TiO2 (P25) Fillings

The elimination of volatile organic compounds (VOCs) at low concentration is a subject of great interest because these compounds are very harmful for the environment and human health. In this work, we have developed an easy methodology to immobilize a benchmark photocatalyst (P25) inside a capillary microreactor (Fused silica capillary with UV transparent coating) without any previous treatment. For this purpose, a dispersion of the sample (P25) in EtOH was used obtaining a packed bed configuration. We have improved the immobilization of the benchmark photocatalyst (P25) inside the capillary incorporating a surfactant (F-127) to generate porosity inside the microreactor to avoid severe pressure drops (∆P < 0.5 bar). The resulting capillaries were characterized by Scanning Electron Microscopy (SEM). These microreactors show a good performance in the abatement of propene (VOC) under flow conditions per mol of active phase (P25) due to an improved mass transfer when the photocatalyst is inside the capillary. Moreover, the prepared microreactors present a higher CO2 production rate (mole CO2/(mole P25·s)) with respect to the same TiO2 operating in a conventional reactor. The microreactor with low pressure drop is very interesting for the abatement of the VOCs since it improves the photoactivity of P25 per mol of TiO2 operating at near atmospheric pressure.The authors thank MINECO (Project CTQ2015-66080-R, MINECO/FEDER) for financial support. JFC thanks MINECO for a researcher formation grant (BES-2016-078079)

Synthesis of TiO2/Nanozeolite Composites for Highly Efficient Photocatalytic Oxidation of Propene in the Gas Phase

In this work, we reported the preparation of composites based on titania (TiO2) and Zeolite Socony Mobil-5 (ZSM-5) nanozeolite, following two approaches (i.e., incorporating the presynthesized zeolite in the synthesis medium of TiO2 and incorporating presynthesized TiO2 in the synthesis medium of ZSM-5). The materials synthesized were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), nitrogen adsorption, X-ray photoelectron spectroscopy (XPS), ultraviolet–visible spectroscopy (UV–vis), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectrometry analysis, and their photocatalytic activities were assessed in the oxidation of propene in the gas phase. It was observed that the synthesis methodology affects the final properties of the composite, which ultimately affected their photocatalytic performance in the studied application. It was found that the Nano-ZSM5/TiO2 composite was the most active among the investigated samples, which was attributed to the intimate contact between the two components of the composite, the preserved properties of the photocatalytic active phase in the final material, and the positive contribution of the nanozeolite by increasing the local concentration of propene.The authors thank Ministerio de Ciencia Innovación y Universidades and FEDER (Project RTI2018-095291-B-I00) and the Generalitat Valenciana (PROMETEOII/2018/076) for financial support. J.F.-C. thanks MINECO for a researcher formation grant (BES-2016-078079). M.N.-G. gratefully acknowledges Generalitat Valenciana and Plan GenT (CDEIGENT/2018/027) for the postdoctoral grant

Shape-Controlled Synthesis of Cu3TeO6 Nanoparticles with Photocatalytic Features

Cu3TeO6 (CTO) has been synthesized by hydrothermal synthesis applying different pH values without any template or a calcination step to control the crystalline phase and the morphology of nanoparticles. The physicochemical properties characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, N2 adsorption, X-ray photoelectron spectroscopy, and diffuse reflectance ultraviolet–visible (DRUV–vis) spectroscopy techniques revealed that the pH values significantly influence the crystal growth. In acidic media (pH = 2), crystal growth has not been achieved. At pH = 4, the yield is low (10%), and the CTO presents irregular morphology. At pH = 6, the yield increases (up to 71%) obtaining an agglomeration of nanoparticles into spherical morphology. At basic conditions (pH = 8), the yield increases up to 90% and the morphology is the same as the sample obtained at pH = 6. At high basic conditions (pH = 10), the yield is similar (92%), although the morphology changes totally to dispersed nanoparticles. Importantly, the as-prepared CTO semiconductor presents photocatalytic activity for H2 production using triethanolamine as a sacrificial agent under visible light illumination. The results also revealed that the nanoparticles agglomerated in a spherical morphology with larger surface area presented almost double activities in H2 production compared to heterogeneously sized particles. These results highlight the suitable optoelectronic properties, including optical band gap, energy levels, and photoconductivity of CTO semiconductors for their use in photocatalytic H2 production.JFC thanks MARSALAS21-09 grant funded by MCIN/AEI/10.13039/501100011033 and European Union NextGeneration EU/PRTR. S.E. and M.D. thank the EPSRC grant EP/S030727/1 for financial support. Financial support from the ERC (European Research Council) Consolidator Grant CATCH (grant agreement no 101002219) is also acknowledged

g-C3N4-Based Direct Z-Scheme Photocatalysts for Environmental Applications

Photocatalysis represents a promising technology that might alleviate the current environmental crisis. One of the most representative photocatalysts is graphitic carbon nitride (g-C3N4) due to its stability, cost-effectiveness, facile synthesis procedure, and absorption properties in visible light. Nevertheless, pristine g-C3N4 still exhibits low photoactivity due to the rapid recombination of photo-induced electron-hole (e−-h+) pairs. To solve this drawback, Z-scheme photocatalysts based on g-C3N4 are superior alternatives since these systems present the same band configuration but follow a different charge carrier recombination mechanism. To contextualize the topic, the main drawbacks of using g-C3N4 as a photocatalyst in environmental applications are mentioned in this review. Then, the basic concepts of the Z-scheme and the synthesis and characterization of the Z-scheme based on g-C3N4 are addressed to obtain novel systems with suitable photocatalytic activity in environmental applications (pollutant abatement, H2 production, and CO2 reduction). Focusing on the applications of the Z-scheme based on g-C3N4, the most representative examples of these systems are referred to, analyzed, and commented on in the main text. To conclude this review, an outlook of the future challenges and prospects of g-C3N4-based Z-scheme photocatalysts is addressed.This research was funded by European Union-Next Generation EU, MINECO, and University of Alicante: MARSALAS21-09, Generalitat Valenciana: CDEIGENT/2018/027, University of Alicante: GRE20-19-A. PID2021-123079OB-I00 project funded by MCIN/AEI/10.13039/501100011033 and “ERDF A way of making Europe”, European Union’s Horizon 2020 research and innovation programme: Grant Agreement 101002219 and Generalitat Valenciana: Proyecto Prometeo CIPROM/2021/70

Waveguide bandstop filter based on irises and double corrugations for use in industrial microwave ovens

In this reported work it is shown that one of the most employed filtering systems for use in continuous-flow industrial microwave ovens, namely doubly corrugated filters, does not work properly for many values of the electric permittivity of the processed material when it is partially filled. Thus, a novel bandstop filter which solves these inconveniences, based on a combination of metallic irises and double corrugations, is designed by means of CST Microwave Studio® and experimentally validated.This work was supported in part by the Fundación Séneca under the fellowship 16381/FPI/10 and the project 11689/PI/09

Novelty without nobility: Outstanding Ni/Ti-SiO2 catalysts for propylene epoxidation

An efficient gas-phase production of propylene oxide (PO) with noble metal-free catalysts could modify the industrial output of this valuable compound. We present a novel catalyst based on well-dispersed Ni nanoparticles loaded on a Ti-SiO2 support for the propylene epoxidation reaction using H2/O2 mixtures. XPS, High Resolution Transmission Electron Microscopy (HRTEM), and UV–Vis corroborate both the small size of Ni particles and the excellent dispersion and incorporation of Ti as tetrahedral single site species into the silica framework. The catalytic results under steady-state conditions at low temperature (200 °C) show high PO selectivity (around 85%) with a substantial propylene conversion (over 6%) and excellent H2 efficiency (~37%) using only 0.5 wt% of Ni on Ti-SiO2 (Ti/Si = 0.01 M ratio). In this work, we have also carried out a preliminary DFT study to gain understanding of the characteristics that make this nickel catalyst active and selective for the propene epoxidation reaction.We thank the Spanish Ministry of Economy and Competitiveness (MINECO), Spanish Ministry of Science, Innovation and Universities, Generalitat Valenciana and FEDER (CTQ2015-66080-R, RTI2018-095291-B-I00, MAT2017-87579-R, and PROMETEO/2018/076) for financial support. JFC thanks MINECO for a researcher formation grant (BES-2016-078079)

HKUST-1@ACM hybrids for adsorption applications: A systematic study of the synthesis conditions

This work constitutes a guide towards the preparation of metal-organic framework materials (MOF) supported and/or confined in activated carbon monoliths (ACM). The resulting hybrid porous materials exhibit improved physico-chemical properties as compared with their parent constituents. The different hybrids were obtained exploring several experimental approaches, which were thoroughly discussed. All hybrids were characterized by N2 adsorption isotherms, SEM, TGA and XRD techniques. The characterization studies pointed out that the preparation conditions are of paramount importance in defining the nucleation and growth of HKUST-1, either outside of the carbon grains (surface coating), and/or in the internal pores (bulk confinement). While the surface coating was achieved by directly synthesizing the MOF in presence of the ACM (i.e. in-situ synthesis), bulk confinement is favored after applying an additional step that involves a pre-nucleation at low temperatures (5 °C). The hybrid material with the best performance, sample A5(1), shows enhanced mechanical properties compared to its parent counterparts, combined with high apparent surface area (up to 1300 m2/g), an improved crushing strength (about 8 times superior to ACM) and a geometrical density of around 0.45 cm3/g, which almost duplicates that of ACM. Last but not least, the adsorption behavior of the hybrid was tested for CO2 and CH4 adsorption. Application of IAST equation to the single component adsorption isotherms at room temperature gives rise to a CO2/CH4 selectivity factor of 5.5 in the hybrid material, larger than that on ACM (S = 3.5).This work was supported by MINECO projects: MAT2013-45008-p. MEC wants to thank the Spanish Government for the fellowship FPU AP2010-4920

Synthesis of TiO2 with Hierarchical Porosity for the Photooxidation of Propene

The elimination of volatile organic compounds (VOCs) at low concentration is a subject of great interest because these compounds are very harmful for the environment and human health. In this work, we have developed a synthesis methodology of TiO2 that allows obtaining meso-macroporous materials with hierarchical porosity and with high thermal stability for their application as photocatalysts in the removal of VOCs, specifically propene. The materials synthesized in this work were characterized by Scanning electron microscope (SEM), Transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Thermogravimetric Analysis (TG), and nitrogen adsorption. It is observed that the samples calcined at 250 °C and 500 °C present a high photoactivity for the photooxidation of propene, which is similar to the benchmark material P25 (commercial TiO2). Moreover, the textural properties are better than those for P25, indicating that the samples are interesting for the preparation of photocatalysts with different conformations, such as in the form of coatings and fillings in different size scales.The authors thank MINECO (CTQ2015-66080-R, MINECO/FEDER, BES-2016-078079) and Generalitat Valenciana (PROMETEOII/2014/010) for financial support

Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption

Synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N2 with a total BET surface area of around 380 m2 g−1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I) structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to induce the breathing. The presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.J. S. A. and C. C. C. acknowledge financial support from the University of Alicante (ACIE16-04) to cover all the expenses for the INS measurements at ORNL. J. S. A. gratefully acknowledges financial support from MINECO (MAT2016-80285-p), European Union H2020 (MSCA-RISE-2016/NanoMed Project) and Generalitat Valenciana (PROMETEOII/2014/004), Spanish ALBA synchrotron for beam time availability (Project ID: 2016021724) and Oak Ridge beam time availability (Project ID: IPTS-16291.1)