Electrochemical reduction of CO2: a review of cobalt based catalysts for carbon dioxide conversion to fuels

Electrochemical CO2 reduction reaction (CO2RR) provides a promising approach to curbing harmful emissions contributing to global warming. However, several challenges hinder the commercialization of this technology, including high overpotentials, electrode instability, and low Faradic efficiencies of desirable products. Several materials have been developed to overcome these challenges. This mini-review discusses the recent performance of various cobalt (Co) electrocatalysts, including Co-single atom, Co-multi metals, Co-complexes, Co-based metal–organic frameworks (MOFs), Co-based covalent organic frameworks (COFs), Co-nitrides, and Co-oxides. These materials are reviewed with respect to their stability of facilitating CO2 conversion to valuable products, and a summary of the current literature is highlighted, along with future perspectives for the development of efficient CO2RR

Fluorescein Hydrazide-Appended Metal–Organic Framework as a Chromogenic and Fluorogenic Chemosensor for Mercury Ions

In this work, we prepared a fluorescein hydrazide-appended Ni(MOF) (Metal–Organic Framework) [Ni3(BTC)2(H2O)3]·(DMF)3(H2O)3 composite, FH@Ni(MOF). This composite was well-characterized by PXRD (powder X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), N2 adsorption isotherm, TGA (thermogravimetric analysis), XPS (X-ray photoelectron spectroscopy), and FESEM (field emission scanning electron microscopy). This composite was then tested with different heavy metals and was found to act as a highly selective and sensitive optical sensor for the Hg2+ ion. It was found that the aqueous emulsion of this composite produces a new peak in absorption at 583 nm, with a chromogenic change to a pink color visible to the naked eye upon binding with Hg2+ ions. In emission, it enhances fluorescence with a fluorogenic change to green fluorescence upon complexation with the Hg2+ ion. The binding constant was found to be 9.4 × 105 M−1, with a detection limit of 0.02 μM or 5 ppb. This sensor was also found to be reversible and could be used for seven consecutive cycles. It was also tested for Hg2+ ion detection in practical water samples from ground water, tap water, and drinking water

Bimetallic Metal-Organic Framework Derived Nanocatalyst for CO₂ Fixation through Benzimidazole Formation and Methanation of CO₂

In this paper, a bimetallic Metal-Organic Framework (MOF) CoNiBTC was employed as a precursor for the fabrication of bimetallic nanoalloys CoNi@C evenly disseminated in carbon shells. These functional nanomaterials are characterized by powdered X-ray diffraction (PXRD), Fourier Transform Infra-Red spectroscopy (FTIR), surface area porosity analyzer, X-ray photoelectron spectroscopy (XPS), Field emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Hydrogen Temperature-Programmed Reduction (H2 TPR), CO2 Temperature-Programmed Desorption (CO2-TPD), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). This nanocatalyst was utilized in the synthesis of benzimidazole from o-phenylenediamine in the presence of CO2 and H2 in a good yield of 81%. The catalyst was also efficient in the manufacture of several substituted benzimidazoles with high yield. Due to the existence of a bimetallic nanoalloy of Co and Ni, this catalyst was also employed in the methanation of CO2 with high selectivity (99.7%)

UV-Protected Polyurethane/f-Oil Fly Ash-CeO2 Coating: Effect of Pre-Mixing f-Oil Fly Ash-CeO2 with Monomers

A series of UV-protected coatings were prepared using cerium-oxide-functionalized oil fly ash (f-OFA-CeO2) in waterborne polyurethane (WBPU) dispersions. Three monomers, namely, poly(tetramethyleneoxide glycol) (PTMG), polydimethylsiloxane-hydroxy terminated (PDMS) and 4,4-dicyclohexylmethane diisocyanate (H12MDI), were used to pre-mix with f-OFA-CeO2 separately, followed by the synthesis of WBPU/f-OFA-CeO2 dispersions. The f-OFA-CeO2 distribution and enrichment into any part (top/bottom/bulk) of the coating was strongly affected by the pre-mixing of f-OFA-CeO2. The f-OFA-CeO2 was densely distributed in the top, bottom and bulk when the f-OFA-CeO2 was pre-mixed with PDMS, H12MDI and PTMG, respectively. Only an f-OFA-CeO2-enriched top surface showed excellent UV protection. The lowest UV-degraded exposed coating was found when the top surface of the coating was f-OFA-CeO2-enriched

Schiff Base Ligand Coated Gold Nanoparticles for the Chemical Sensing of Fe(III) Ions

New Schiff base-coated gold nanoparticles (AuNPs) of type AuNP@L (where L: thiolated Schiff base ligand) have been synthesized and characterized using various spectroscopic techniques. The AuNPs and AuNP@L were imaged by transmission electron microscopy (TEM) and were confirmed to be well-dispersed, uniformly distributed, spherical nanoparticles with an average diameter of 8–10 nm. Their potential applications for chemosensing were investigated in UV-Vis and fluorescence spectroscopic studies. The AuNP@L exhibited selectivity for Fe3+ in an ethanol/water mixture (ratio 9 : 1 v/v). The absorption and emission spectral studies revealed a 1 : 1 binding mode for Fe3+, with binding constants of 8.5×105 and 2.9×105 M−1, respectively

Controlled Covalent Functionalization of ZIF-90 for Selective CO₂ Capture & Separation

Mixed Matrix Membranes (MMM) with enhanced selectivity and permeability are preferred for gas separations. The porous metal-organic frameworks (MOFs) materials incorporated in them play a crucial part in improving the performance of MMM. In this study, Zeolitic imidazolate frameworks (ZIF-90) are selected to fabricate Polyetherimide (PEI) MMMs owing to their lucrative structural and chemical properties. This work reports new controlled post-synthetic modifications of ZIF-90 (50-PSM-ZIF-90) with ethanolamine to control the diffusion and uptake of CO2. Physical and chemical properties of ZIF-90, such as stability and presence of aldehyde functionality in the imidazolate linker, allow for easy modulation of the ZIF-90 pores and window size to tune the gas transport properties across ZIF-90-based membranes. Effects of these materials were investigated on the performance of MMMs and compared with pure PEI membranes. Performance of the MMMs was evaluated in terms of permeability of different gases and selective separation of CO2 and H2 gas. Results presented that the permeability of all membranes was in the following order, i.e., P(H2) > P(CO2) > P(O2) > P(CH4) > P(C2H6) > P(C3H8) > P(N2), demonstrating that kinetic gas diffusion is the predominant gas transport mode in these membranes. Among all the membranes, permeability of pure PEI membrane was highest for all gases due to the uniform porous morphology. The pure PEI membrane showed highest permeability of H2, which is 486.5 Barrer, followed by 49 Barrer for O2, 29 Barrer for N2, 142 Barrer for CO2, 41 Barrer for CH4, 40 Barrer for C2H6 and 39.6 Barrer for C3H8. Results also confirm the superiority of controlled PSM-ZIF-90-PEI membrane over the pure PEI and ZIF-90-PEI membranes in CO2 and H2 separation performance. The 50-PSM-ZIF-90 PEI membrane exhibited a 20% increase in CO2 separation from methane and a 26% increase over nitrogen compared to the ZIF-90-PEI membrane. The 50-PSM-ZIF-90 PEI membrane showed 15% more H2/O2 separation and 9% more H2/CH4 separation than ZIF-90 PEI membrane. Overall, this study represents the role of controlled PSM in enhancing the property of new materials like ZIF and its application in MMMs fabrication to develop a promising approach for the CO2 capture and separation

Propene Adsorption-Chemisorption Behaviors on H-SAPO-34 Zeolite Catalysts at Different Temperatures

Propene is an important synthetic industrial product predominantly formed by a methanol-to-olefins (MTO) catalytic process. Propene is known to form oligomers on zeolite catalysts, and paramters to separate it from mixtures and its diffusion properties are difficult to measure. Herein, we explored the adsorption–chemisorption behavior of propene by choosing SAPO-34 zeolites with three different degrees of acidity at various adsorption temperatures in an ultra-high-vacuum adsorption system. H-SAPO-34 zeolites were prepared by a hydrothermal method, and their structural, morphological, and acidic properties were investigated by XRD, SEM, EDX, and temperature-programmed desorption of ammonia (NH3-TPD) analysis techniques. The XRD analysis revealed the highly crystalline structure which posses cubic morphology as confirmed by SEM images. The analysis of adsorption of propene on SAPO-34 revealed that a chemical reaction (chemisorption) was observed between zeolite and propene at room temperature (RT) when the concentration of acidic sites was high (0.158 mmol/g). The reaction was negligible when the concentration of the acidic sites was low (0.1 mmol/g) at RT. However, the propene showed no reactivity with the highly acidic SAPO-34 at low temperatures, i.e., −56 °C (using octane + dry ice), −20 °C (using NaCl + ice), and 0 °C (using ice + water). In general, low-temperature conditions were found to be helpful in inhibiting the chemisorption of propene on the highly acidic H-SAPO-34 catalysts, which can facilitate propene separation and allow for reliable monitoring of kinetic parameters