Uncovering the reaction mechanism behind CoO as active phase for CO2 hydrogenation

Transforming carbon dioxide into valuable chemicals and fuels, is a promising tool for environmental and industrial purposes. Here, we present catalysts comprising of cobalt (oxide) nanoparticles stabilized on various support oxides for hydrocarbon production from carbon dioxide. We demonstrate that the activity and selectivity can be tuned by selection of the support oxide and cobalt oxidation state. Modulated excitation (ME) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that cobalt oxide catalysts follows the hydrogen-assisted pathway, whereas metallic cobalt catalysts mainly follows the direct dissociation pathway. Contrary to the commonly considered metallic active phase of cobalt-based catalysts, cobalt oxide on titania support is the most active catalyst in this study and produces 11% C2+ hydrocarbons. The C2+ selectivity increases to 39% (yielding 104 mmol h−1 gcat−1 C2+ hydrocarbons) upon co-feeding CO and CO2 at a ratio of 1:2 at 250 °C and 20 bar, thus outperforming the majority of typical cobalt-based catalysts.

The Role of Different Lanthanoid and Transition Metals in Perovskite Gas Sensors

Beginning with LaFeO3, a prominent perovskite-structured material used in the field of gas sensing, various perovskite-structured materials were prepared using sol–gel technique. The composition was systematically modified by replacing La with Sm and Gd, or Fe with Cr, Mn, Co, and Ni. The materials synthesized are comparable in grain size and morphology. DC resistance measurements performed on gas sensors reveal Fe-based compounds solely demonstrated effective sensing performance of acetylene and ethylene. Operando diffuse reflectance infrared Fourier transform spectroscopy shows the sensing mechanism is dependent on semiconductor properties of such materials, and that surface reactivity plays a key role in the sensing response. The replacement of A-site with various lanthanoid elements conserves surface reactivity of AFeO3, while changes at the B-site of LaBO3 lead to alterations in sensor surface chemistry.

Insight into Composition and Intermediate Evolutions of Copper-Based Catalysts during Gas-Phase CO2 Electroreduction to Multicarbon Oxygenates

Conversion of CO2 to valuable chemicals driven by renewable electricity via electrocatalytic reduction processes is of great significance for achieving carbon neutrality. Copper-based materials distinguish themselves from other electrocatalysts for their unique capability to produce multicarbon compounds in CO2 electroreduction. However, the intrinsic active composition and C–C coupling mechanism of copper-based catalysts are still ambiguous. This is largely due to the absence of appropriate in situ approaches to monitor the complicated processes of CO2 electroreduction. Here, we adopted operando spectroscopy techniques, including Raman and infrared, to investigate the evolution of compositions and intermediates during gas-phase CO2 electroreduction on Cu foam, Cu2O nanowire and CuO nanowire catalysts. Although all the three copper-based catalysts possessed the activity of electroreducing gas-phase CO2 to multicarbon oxygenates, Cu2O nanowires showed the much superior performance with a 71.9% Faradaic efficiency of acetaldehyde. Operando Raman spectra manifested that the cuprous oxide remained stable during the whole gas-phase CO2 electroreduction, and operando diffuse reflectance infrared Fourier transform spectroscopy (DRFITS) results provide direct evidences of key intermediates and their evolutions for producing multicarbon oxygenates, in consistence with the density functional theory calculations.

Potential of Mechanochemically Activated Sulfidic Mining Waste Rock for Alkali Activation

Sulfidic mining waste rock is a side stream from the mining industry with a potential environmental burden. Alkali activation is a promising method for transforming mining waste into construction materials. However, the low reactivity of minerals can be a sizeable challenge in alkali activation. In the present study, the reactivity of waste rock was enhanced by mechanochemical treatment with a LiCl-containing grinding aid. X-ray diffraction (XRD) and diffuse reflectance infrared Fourier transform (DRIFT) analysis were utilized to display the structural alteration of individual minerals. A schematic implication of the grinding mechanism of mica was provided according to the results of transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The alkaline solubility displayed the enhanced chemical reactivity of the waste rock, in which Si and Al solubility increased by roughly 10 times and 40 times, respectively. The amorphization of aluminosilicate is achieved through chemical assisted mechanochemical activation. Sulfidic waste rock, as the sole precursor in alkali activation, achieved a 28-day compressive strength exceeding 10 MPa under ambient curing conditions. The simulation of the upscaled grinding process was conducted via the HSC Chemistry® software with a life-cycle assessment. The results showed that mining waste rock can be a promising candidate for geopolymer production with a lower carbon footprint, compared to traditional Portland cement. Graphical Abstract

In Situ DRIFTS-MS Methanol Adsorption Study onto Supported NiSn Nanoparticles: Mechanistic Implications in Methanol Steam Reforming

Methanol adsorption over both supported NiSn Nps and analogous NiSn catalyst prepared by impregnation was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to gain insights into the basis of hydrogen production from methanol steam reforming. Different intermediate species such as methoxides with different geometry (bridge and monodentate) and formate species were identified after methanol adsorption and thermal desorption. It is proposed that these species are the most involved in the methanol steam reforming reaction and the major presence of metal-support interface sites in supported NiSn Nps leads to higher production of hydrogen. On the basis of these results, a plausible reaction mechanism was elucidated through the correlation between the thermal stability of these species and the evolution of the effluent gas released. In addition, it was demonstrated that DME is a secondary product generated by condensation of methoxides over the acid sites of alumina support in an acid-catalyzed reaction.

One-Pot Synthesis of Ni0.05Ce0.95O2−δ Catalysts with Nanocubes and Nanorods Morphology for CO2 Methanation Reaction and in Operando DRIFT Analysis of Intermediate Species

The valorization of CO2 via renewable energy sources allows one to obtain carbon-neutral fuels through its hydrogenation, like methane. In this study, Ni0.05Ce0.95O2−δ catalysts were prepared using a simple one-pot hydrothermal method yielding nanorod and nanocube particles to be used for the methanation reaction. Samples were characterized by XRD, BET, TEM, H2-TPR, and H2-TPD experiments. The catalytic activity tests revealed that the best performing catalyst was Ni0.05Ce0.95O2−δ, with nanorod morphology, which gave a CO2 conversion of 40% with a selectivity of CH4 as high as 93%, operating at 325 °C and a GHSV of 240,000 cm3 h−1 g−1. However, the lower activation energy was found for Ni0.05Ce0.95O2−δ catalysts with nanocube morphology. Furthermore, an in operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis was performed flowing CO2:H2 or CO:H2 mixture, showing that the main reaction pathway, for the CO2 methanation, is the direct hydrogenation of formate intermediate.

Comparative Study of SO2 and SO2/SO3 Poisoning and Regeneration of Cu/BEA and Cu/SSZ-13 for NH3 SCR

Two copper-exchanged zeolites, Cu/SSZ-13 and Cu/BEA, were studied as catalysts for the selective reduction of NOx by NH3 (NH3-SCR). Their activities for standard SCR (NOx = NO) and fast SCR (NOx = 50% NO + 50% NO2) were measured before and after sulfur poisoning at 250 °C. The effect of 30 ppm SO2 and a mixture of 24 ppm SO3 + 6 ppm SO2 was evaluated. The repetition of subsequent activity measurements served as regeneration method in SCR conditions. SO2 deactivated Cu/SSZ-13 whereas Cu/BEA was only moderately affected. SO3 led to stronger deactivation of both catalysts than SO2. However, also for this case, the Cu/BEA was significantly less affected than Cu/SSZ-13, even though Cu/BEA contained larger amount of stored sulfur. One possible reason for this could be the large pores of Cu/BEA, where the sulfur species possibly resulted in less sterical hindrance than in the small pore SSZ-13 structure. NH3 temperature-programmed desorption (NH3-TPD) showed no loss of storage sites upon sulfur treatment and subsequent regeneration. Partial activity recovery was observed after a period in SCR conditions at 400 °C and 500 °C. Temperature at 300 °C was insufficient to regenerate the catalysts. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of NO adsorption suggested that SO2 interacts with the ZCuOH sites on Cu/SSZ-13, causing the strong poisoning.

Pretreatment of Automotive Shredder Residues, Their Chemical Characterisation, and Pyrolysis Kinetics

Automotive Shredder Residue (ASR), a waste when metals are mostly removed from end-of-life vehicles, has constituents similar to municipal solid waste (MSW) consisting of plastics, rubber, textiles, and some metals. The processing of ASR is a challenge due to its heterogeneous nature, making feeding to a reactor difficult. In this work, a new procedure of ASR pretreatment is proposed to bring particulate nature in the sample for easier feeding during pyrolysis. The thermal breakdown characteristics of the pretreated ASR solids under slow pyrolysis conditions were assessed in a thermogravimetric analyser following the International Confederation for Thermal Analysis and Calorimetry (ICTAC) kinetics committee recommendations. The effect of particle sizes and heating rates were studied at temperatures up to 800 °C at different heating rates of 2, 5, and 10 °C/min for three particle sizes, 38–63 µm, 63–90 µm, and 90–106 µm, and the kinetic data were derived. The volatiles emitted during pyrolysis were characterized by Diffuse Reflectance Infrared Spectroscopy (DRIFTS). We also developed an algorithm for the selection of heating rate during the pyrolysis of the pretreated ASR. The DRIFTS results, kinetic data, and heating rate for the selected particle sizes are useful for the development of a pyrolysis process for pretreated ASR.