Solar Gas-Phase CO2 Hydrogenation by Multifunctional UiO-66 Photocatalysts.

Solar-assisted CO2 conversion into fuels and chemical products involves a range of technologies aimed at driving industrial decarbonization methods. In this work, we report on the development of a series of multifunctional metal-organic frameworks (MOFs) based on nitro- or amino-functionalized UiO-66(M) (M: Zr or Zr/Ti) supported RuOx NPs as photocatalysts, having different energy band level diagrams, for CO2 hydrogenation under simulated concentrated sunlight irradiation. RuOx(1 wt %; 2.2 ± 0.9 nm)@UiO-66(Zr/Ti)-NO2 was found to be a reusable photocatalyst, to be selective for CO2 methanation (5.03 mmol g-1 after 22 h;, apparent quantum yield at 350, 400, and 600 nm of 1.67, 0.25, and 0.01%, respectively), and to show about 3-6 times activity compared with previous investigations. The photocatalysts were characterized by advanced spectroscopic techniques like femto- and nanosecond transient absorption, spin electron resonance, and photoluminescence spectroscopies together with (photo)electrochemical measurements. The photocatalytic CO2 methanation mechanism was assessed by operando FTIR spectroscopy. The results indicate that the most active photocatalyst operates under a dual photochemical and photothermal mechanism. This investigation shows the potential of multifunctional MOFs as photocatalysts for solar-driven CO2 recycling.

Valorization of Field-Spent Granular Activated Carbon as Heterogeneous Ozonation Catalyst for Water Treatment.

Developing sustainable cost-effective strategies for valorization of field-spent granular activated carbon (s-GAC) from industrial water treatment has gained much interest. Here, we report a cost-effective strategy for the regeneration of s-GAC as an adsorbent in a large-scale drinking water treatment plant and used as an efficient and durable ozonation catalyst in water. To achieve this, a series of samples is prepared by subjecting s-GAC to thermally controlled combustion treatments with and without pyrolysis. The catalytic performance of the optimized sample is evaluated for oxalic acid degradation as the model pollutant under batch (>15 h) and continuous flow operations (>200 h). The partially deactivated catalyst upon reuse is restored by thermal treatment. Electron paramagnetic resonance and selective quenching experiments show the formation of singlet oxygen (1O2) during catalytic ozonation. The GAC-ozonation catalyst is efficient to minimize the formation of chlorinated disinfection by-products like trihalomethanes and haloacetic acids in an urban wastewater effluent.

Enhanced Visible Light-Driven Photocatalytic Water-Splitting Reaction of Titanate Nanotubes Sensitised with Ru(II) Bipyridyl Complex.

The ion exchange of Na+ cations was used to photosensitise titanates nanotubes (Ti-NTs) with tris(2,2'-bipyridine)ruthenium(II) cations (Ru(bpy)32+); this yielded a light-sensitised Ti-NTs composite denoted as (Ru(bpy)3)Ti-NTs, exhibiting the characteristic absorption of Ru(bpy)32+ in visible light. Incident photon-to-current efficiency (IPCE) measurements and the photocatalytic reduction of methyl viologen reaction confirmed that in the photosensitisation of the (Ru(bpy)3)Ti-NTs composite, charge transfer and charge separation occur upon excitation by ultraviolet and visible light irradiation. The photocatalytic potential of titanate nanotubes was tested in the water-splitting reaction and the H2 evolution reaction using a sacrificial agent and showed photocatalytic activity under various light sources, including xenon-mercury lamp, simulated sunlight, and visible light. Notably, in the conditions of the H2 evolution reaction when (Ru(bpy)3)Ti-NTs were submitted to simulated sunlight, they exceeded the photocatalytic activity of pristine Ti-NTs and TiO2 by a factor of 3 and 3.5 times, respectively. Also, (Ru(bpy)3)Ti-NTs achieved the photocatalytic water-splitting reaction under simulated sunlight and visible light, producing, after 4 h, 199 and 282 µmol×H2×gcat-1. These results confirm the effective electron transfer of Ru(bpy)3 to titanate nanotubes. The stability of the photocatalyst was evaluated by a reuse test of four cycles of 24 h reactions without considerable loss of catalytic activity and crystallinity.

Porphyrin-Based MOF Thin Film on Transparent Conducting Oxide: Investigation of Growth, Porosity and Photoelectrochemical Properties.

Synthesizing metal-organic frameworks (MOFs) composites with a controlled morphology is an important requirement to access materials of desired patterning and composition. Since the last decade, MOF growth from sacrificial metal oxide layer is increasingly developed as it represents an efficient pathway to functionalize a large number of substrates. In this study, porphyrin-based Al-PMOF thin films were grown on conductive transparent oxide substrates from sacrificial layers of ALD-deposited alumina oxide. The control of the solvent composition and the number of atomic layer deposition (ALD) cycles allow us to tune the crystallinity, morphology and thickness of the produced thin films. Photophysical studies evidence that Al-PMOF thin films present light absorption and emission properties governed by the porphyrinic linker, without any quenching upon increasing the film thickness. Al-PMOF thin films obtained through this methodology present a remarkably high optical quality both in terms of transparency and coverage. The porosity of the samples is demonstrated by ellipsometry and used for Zn(II) insertion inside the MOF thin film. The multifunctional transparent, porous and luminescent thin film grown on fluorine-doped tin oxide (FTO) is used as an electrode capable of photoinduced charge separation upon simulated sunlight irradiation.

Room temperature design of Ce(iv)-MOFs: from photocatalytic HER and OER to overall water splitting under simulated sunlight irradiation.

The development of MOF-based efficient and reusable catalysts for hydrogen production under simulated sunlight irradiation, especially through overall water splitting, remains challenging. This is mainly due to either the inappropriate optical features or poor chemical stability of the given MOFs. Room temperature synthesis (RTS) of tetravalent MOFs is a promising strategy to design robust MOFs and their related (nano)composites. By employing these mild conditions, herein, we report for the first time that RTS leads to the efficient formation of highly redox active Ce(iv)-MOFs that are inaccessible at elevated temperatures. Consequently, not only highly crystalline Ce-UiO-66-NH2 is synthesized, but also many other derivatives and topologies (8 and 6-connected phases) without compromise in space-time yield. Their photocatalytic HER and OER activities under simulated sunlight irradiation are in good agreement with their energy level band diagrams: Ce-UiO-66-NH2 and Ce-UiO-66-NO2 are the most active photocatalysts for the HER and OER, respectively, with a higher activity than other metal-based UiO-type MOFs. Combining Ce-UiO-66-NH2 with supported Pt NPs results finally in one of the most active and reusable photocatalysts for overall water splitting into H2 and O2 under simulated sunlight irradiation, due to its efficient photoinduced charge separation evidenced by laser flash photolysis and photoluminescence spectroscopies.

Photocatalytic Hydrogen Production from Glycerol Aqueous Solutions as Sustainable Feedstocks Using Zr-Based UiO-66 Materials under Simulated Sunlight Irradiation.

There is an increasing interest in developing cost-effective technologies to produce hydrogen from sustainable resources. Herein we show a comprehensive study on the use of metal-organic frameworks (MOFs) as heterogeneous photocatalysts for H2 generation from photoreforming of glycerol aqueous solutions under simulated sunlight irradiation. The list of materials employed in this study include some of the benchmark Zr-MOFs such as UiO-66(Zr)-X (X: H, NO2, NH2) as well as MIL-125(Ti)-NH2 as the reference Ti-MOF. Among these solids, UiO-66(Zr)-NH2 exhibits the highest photocatalytic H2 production, and this observation is attributed to its adequate energy level. The photocatalytic activity of UiO-66(Zr)-NH2 can be increased by deposition of small Pt NPs as the reference noble metal co-catalyst within the MOF network. This photocatalyst is effectively used for H2 generation at least for 70 h without loss of activity. The crystallinity of MOF and Pt particle size were maintained as revealed by powder X-ray diffraction and transmission electron microscopy measurements, respectively. Evidence in support of the occurrence of photoinduced charge separation with Pt@UiO-66(Zr)-NH2 is provided from transient absorption and photoluminescence spectroscopies together with photocurrent measurements. This study exemplifies the possibility of using MOFs as photocatalysts for the solar-driven H2 generation using sustainable feedstocks.

Photocatalytic Water Splitting Promoted by 2D and 3D Porphyrin Covalent Organic Polymers Synthesized by Suzuki-Miyaura Carbon-Carbon Coupling.

This work deals with the synthesis of metal-free and porphyrin-based covalent organic polymers (COPs) by the Suzuki-Miyaura coupling carbon-carbon bond forming reaction to study the photocatalytic overall water splitting performance. Apart from using 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin, we have chosen different cross-linker monomers to induce 2-dimensional (2D) or 3-dimensional (3D) and different rigidity in their resulting polymeric molecular structure. The synthesised COPs were extensively characterised to reveal that the dimensionality and flexibility of the molecular structure play an intense role in the physical, photochemical, and electronic properties of the polymers. Photoinduced excited state of the COPs was evaluated by nanosecond time-resolved laser transient absorption spectroscopy (TAS) by analysing excited state kinetics and quenching experiments, photocurrent density measurements and photocatalytic deposition of Ru3+ to RuO2, and photocatalysis. In summary, TAS experiments demonstrated that the transient excited state of these polymers has two decay kinetics and exhibit strong interaction with water molecules. Moreover, photocurrent and photocatalytic deposition experiments proved that charges are photoinduced and are found across the COP molecular network, but more important charges can migrate from the surface of the COP to the medium. Among the various COPs tested, COP-3 that has a flexible and 3D molecular structure reached the best photocatalytic performances, achieving a photocatalytic yield of 0.4 mmol H2 × gCOP-3-1 after 3 h irradiation.

SARS-CoV-2 detection in bioaerosols using a liquid impinger collector and ddPCR.

The airborne route is the dominant form of COVID-19 transmission, and therefore, the development of methodologies to quantify SARS-CoV-2 in bioaerosols is needed. We aimed to identify SARS-CoV-2 in bioaerosols by using a highly efficient sampler for the collection of 1-3 µm particles, followed by a highly sensitive detection method. 65 bioaerosol samples were collected in hospital rooms in the presence of a COVID-19 patient using a liquid impinger sampler. The SARS-CoV-2 genome was detected by ddPCR using different primer/probe sets. 44.6% of the samples resulted positive for SARS-CoV-2 following this protocol. By increasing the sampled air volume from 339 to 650 L, the percentage of positive samples went from 41% to 50%. We detected five times less positives with a commercial one-step RT-PCR assay. However, the selection of primer/probe sets might be one of the most determining factor for bioaerosol SARS-CoV-2 detection since with the ORF1ab set more than 40% of the samples were positive, compared to <10% with other sets. In conclusion, the use of a liquid impinger collector and ddPCR is an adequate strategy to detect SARS-CoV-2 in bioaerosols. However, there are still some methodological aspects that must be adjusted to optimize and standardize a definitive protocol.

Optimization of α-Fe2O3 Nanopillars Diameters for Photoelectrochemical Enhancement of α-Fe2O3-TiO2 Heterojunction.

Global warming is pushing the world to seek to green energy sources and hydrogen is a good candidate to substitute fossil fuels in the short term. In future, it is expected that production of hydrogen will be carried out through photo-electrocatalysis. In this way, suitable electrodes that acts as photoanode absorbing the incident light are needed to catalyse water splitting reaction. Hematite (α-Fe2O3) is one of the most attractive semiconductors for this purpose since it is a low-cost material and it has a suitable band gap of 2.1 eV, which allows the absorption of the visible region. Although, hematite has drawbacks such as low carrier mobility and short holes diffusion lengths, that here it has been tried to overcome by nanoengineering the material, and by using a semiconductor as a scaffold that enhances charge carrier separation processes in the electrode. In this work, we fabricate ultrathin quasi transparent electrodes composed by highly ordered and self-standing hematite nanopillars of a few tens of nanometers length on FTO and TiO2 supports. Photoanodes were fabricated utilizing electron beam evaporation technique and anodized aluminum oxide templates with well-defined pores diameters. Thus, the activity of the compact layer hematite photoanode is compared with the photoanodes fabricated with nanopillars of controllable diameters (i.e., 90, 260 and 400 nm) to study their influence on charge separation processes. Results indicated that optimal α-Fe2O3 photoanodes performance are obtained when nanopillars reach hundreds of nanometers in diameter, achieving for photoanodes with 400 nm nanopillars onto TiO2 supports the highest photocurrent density values.

Study of the Photothermal Catalytic Mechanism of CO2 Reduction to CH4 by Ruthenium Nanoparticles Supported on Titanate Nanotubes.

The Sabatier reaction could be a key tool for the future of the renewable energy field due to the potential of this reaction to produce either fuels or to stabilize H2 in the form of stable chemicals. For this purpose, a new composite made of ruthenium oxide nanoparticles (NPs) deposited on titanate nanotubes (TiNTs) was tested. Titanate nanotubes are a robust semiconductor with a one-dimensional (1D) morphology that results in a high contact area making this material suitable for photocatalysis. Small ruthenium nanoparticles (1.5 nm) were deposited on TiNTs at different ratios by Na+-to-Ru3+ ion exchanges followed by calcination. These samples were tested varying light power and temperature conditions to study the reaction mechanism during catalysis. Methanation of CO2 catalyzed by Ru/TiNT composite exhibit photonic and thermic contributions, and their ratios vary with temperature and light intensity. The synthesized composite achieved a production rate of 12.4 mmol CH4·gcat-1·h-1 equivalent to 110.7 mmol of CH4·gRu-1·h-1 under 150 mW/cm2 simulated sunlight irradiation at 210 °C. It was found that photo-response derives either from Ru nanoparticle excitation in the visible (VIS) and near-infrared (NIR) region (photothermal and plasmon excitation mechanism) or from TiNT excitation in the ultraviolet (UV) region leading to electron-hole separation and photoinduced electron transfer.

Plasma production of nanomaterials for energy storage: continuous gas-phase synthesis of metal oxide CNT materials via a microwave plasma.

In this work we show for the first time that a continuous plasma process can synthesize materials from bulk industrial powders to produce hierarchical structures for energy storage applications. The plasma production process's unique advantages are that it is fast, inexpensive, and scalable due to its high energy density that enables low-cost precursors. The synthesized hierarchical material is comprised of iron oxide and aluminum oxide aggregate particles and carbon nanotubes grown in situ from the iron particles. New aerosol-based methods were used for the first time on a battery material to characterize aggregate and primary particle morphologies, while showing good agreement with observations from TEM measurements. As an anode for lithium ion batteries, a reversible capacity of 870 mA h g-1 based on metal oxide mass was observed and the material showed good recovery from high rate cycling. The high rate of material synthesis (∼10 s residence time) enables this plasma hierarchical material synthesis platform to be optimized as a means for energetic material production for the global energy storage material supply chain.

Gas-Phase Photochemical Overall H2 S Splitting by UV Light Irradiation.

Splitting of hydrogen sulfide is achieved to produce value-added chemicals. Upon irradiation at 254 nm in the gas phase and in the absence of catalysts or photocatalysts at near room temperature, H2 S splits into stoichiometric amounts of H2 and S with a quantum efficiency close to 50 %. No influence of the presence of CH4 and CO2 (typical components in natural gas and biogas in which H2 S is an unwanted component) on the efficiency of overall H2 S splitting was observed. A mechanism for the H2 and S formation is proposed.

Phthalocyanine-Gold Nanoparticle Hybrids: Modulating Quenching with a Silica Matrix Shell.

An asymmetrically substituted zinc phthalocyanine (ZnPc) with a terminal dithiolane group is anchored to Au nanoparticles (NPs) directly or through an interposed silica matrix. Transient absorption spectroscopy shows that the quenching of the ZnPc excited state by AuNPs occurs through a photoinduced electron transfer, the efficiency of which is modulated by the presence of the insulating silica matrix.

Photoinduced Charge Separation on the Microsecond Timescale in Graphene Oxide and Reduced Graphene Oxide Suspensions.

Transient absorption spectroscopy of graphene oxide (GO) and reduced graphene oxide (rGO) suspensions provides evidence for the photochemical generation of a charge-separated state on the microsecond timescale upon laser excitation. The lifetime and quantum yield of charge separation in suspended rGO were found to be higher than for GO. This could be advantageous for optoelectronic and photocatalytic applications, where graphene-based materials act as charge (electron) carriers. The electron-transfer quenching of the rGO charge-separated state by different amines is more efficient when the amine is a better electron donor and more easily oxidized.

Perylenetetracarboxylic anhydride as a precursor of fluorescent carbon nanoonion rings.

Thermal annealing at 400 °C of perylenetetracarboxylic anhydride in low molecular mass PEG gives rise to the formation of well defined nanoobjects of 2.5 nm height and size distribution from 10 to 65 nm (average 40 nm) after purification of the raw mixture with silicagel chromatography. TEM reveals that the flat nanoobjects are constituted of concentric graphenic rings (0.34 nm interlayer distance). The morphology of the nanoparticles resembles onion rings of nanometric dimensions (nanoonion rings C-NOR). C-NOR particles have an excitation dependent emission with λem from 430 to 570 nm and a maximum emission quantum yield of 0.49. C-NOR particles can be internalized into Hep3B human hepatoma cells as determined by confocal fluorescence microscopy and are remarkably biocompatible affecting slightly cell viability according to the MTT test.

Visible-light photoresponse of gold nanoparticles supported on TiO2 : a combined photocatalytic, photoelectrochemical, and transient spectroscopy study.

In the context of gaining understanding on the origin of the visible-light photoresponse of TiO2 containing gold nanoparticles, the photocurrent spectra and photocatalytic H2 evolution of titania (P25) and Au-P25 were compared. Whereas no photocurrent was detected upon visible-light irradiation for either of the two photocatalysts, Au-P25 exhibited photocatalytic H2 evolution for wavelengths between 400 and 575 nm. This contradictory behavior under visible-light irradiation of Au-P25 was rationalized by transient absorption spectroscopy. It was suggested that photocatalytic H2 generation results from methanol quenching of the charge-separation state in each semiconductor nanoparticle, but the lack of photocurrent is due to the short lifetime of the charge separation, which makes interparticle charge migration for micrometric distances unlikely.

Highly fluorescent C-dots obtained by pyrolysis of quaternary ammonium ions trapped in all-silica ITQ-29 zeolite.

C-dots obtained in the homogeneous phase may exhibit a broad particle size distribution. The formation of C-dots within nanometric reaction cavities could be a methodology to gain control on their size distribution. Among the various possibilities, in the present work, the cavities of small pore size zeolites have been used to confine C-dots generated by the pyrolysis of the organic structure directing agent present in the synthesis of these crystalline aluminosilicates. To explore this methodology, ITQ-29 zeolite having a Linde type A (LTA) structure was prepared as pure silica with 4-methyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]quinolinium as the organic structure directing agent. Pyrolysis under an inert atmosphere at 550 °C of a pure-silica ITQ-29 sample (cubic particles of 4 µm edge) renders a highly fluorescent zeolite containing about 15 wt% of the carbonised residue. While another small pore zeolite, ITQ-12 (ITW), also renders photoluminescent C-dots under similar conditions, medium or large pore zeolites, such as silicalite (MFI) or pure silica Beta (BEA), failed to produce fluorescent powders under analogous thermal treatment and only decomposition and complete removal of the corresponding quaternary ammonium ion templates was observed for these zeolites. The dissolution of the pyrolysed ITQ-29 zeolite framework and the extraction of the carbon residue with ethyl acetate have allowed the characterisation of C-dots with particle sizes between 5 and 12 nm and a photoluminescence quantum yield of 0.4 upon excitation at 350 nm that is among the highest reported for non-surface functionalized C-dots. Photoluminescence varies with the excitation wavelength and is quenched by oxygen. Pyrolysed ITQ-29 powders can act as fluorescent oxygen sensors.