Temperature-programmed Desorption Research Articles

Highly Efficient PtSn/Al2O3 and PtSnZnCa/Al2O3 Catalysts for Ethane Dehydrogenation: Influence of Catalyst Pretreatment Atmosphere

Increased demand for ethylene has motivated direct ethane dehydrogenation over Pt-based catalysts. PtSn/γ-Al2O3 and PtSnZnCa/γ-Al2O3 catalysts were investigated with the aim of understanding the effect of the pretreatment environment on the state of dispersed Pt for ethane dehydrogenation. The catalysts were prepared by the impregnation method and pretreated in different environments like static air (SA), flowing air (FA), and nitrogen (N2) atmospheres. A comprehensive characterization of the catalysts was performed using Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR), NH3 Temperature-Programmed Desorption (NH3-TPD), X-ray photoelectron spectroscopy (XPS), and Transmission Electron Microscopy (TEM) techniques. The results reveal that the PtSn on Al2O3 catalyst pretreated in the static air environment (PtSn-SA) exhibits 21% ethylene yield with 95% selectivity at 625 °C. XPS analysis found more platinum and tin on the catalyst surface after static air treatment. The overall acidity of the catalysts decreased after thermal treatment in static air. Elemental mapping demonstrated that Pt agglomeration was pronounced in catalysts calcined under flowing air and nitrogen. These factors are responsible for the enhanced activity of the PtSn-SA catalyst compared to the other catalysts. The addition of Zn and Ca to the PtSn catalysts increases the yield of the catalyst calcined in static air (PtSnZnCa-SA). The PtSnZnCa-SA catalyst showed the highest ethylene yield of 27% with 99% selectivity and highly stable activity at 625 °C for 10 h.

Electron-induced deposition using Fe(CO)4MA and Fe(CO)5 – effect of MA ligand and process conditions

The electron-induced decomposition of Fe(CO)4MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)4MA and Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)4MA and Fe(CO)5 were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)4MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)4MA and Fe(CO)5 on an Fe seed layer prepared by EBID was compared. While Fe(CO)5 sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)4MA. The heteroleptic precursor Fe(CO)4MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes.

Effect of Bystander Hydrogen Atoms on Hydrogen Desorption on Single-Atom Alloy Surfaces: Insights from Simulated Temperature-Programmed Desorption Spectra.

Single-atom alloy (SAA) catalysts exhibit unique and excellent catalytic properties in heterogeneous hydrogenation/dehydrogenation reactions. A thorough understanding of the microscopic surface processes is essential to improve the catalytic performance. Here, from a new perspective of the temperature-programmed desorption (TPD) spectra of hydrogen (H) on two common SAA surfaces, Pt@Cu(111) and Pd@Cu(111), we reveal and confirm the key influence of H atoms attached to Pt/Pd dopants, i.e., the H atom bystander, on the desorption process of surface H atoms. It is found that only after considering the effect of the H atom bystander can the simulated TPD spectra well reproduce the experimentally observed higher desorption temperature on Pt@Cu(111) than on Pd@Cu(111) and the leftward shift of the TPD peak with increasing H atom coverage; otherwise, the features are inconsistent with experiments. Our work provides direct evidence for the effect of bystander H atoms from a simulation perspective.

Characterization of carbon dioxide on Ganymede and Europa supported by experiments: Effects of temperature, porosity, and mixing with water

The surfaces of icy moons are primarily composed of water ice that can be mixed with other compounds, such as carbon dioxide. The carbon dioxide (CO$_2)$ stretching fundamental band observed on Europa and Ganymede appears to be a combination of several bands that are shifting location from one moon to another. We investigate the cause of the observed shift in the CO$_2$ stretching absorption band experimentally. We also explore the spectral behaviour of CO$_2$ ice by varying the temperature and concentration. We analyzed pure CO$_2$ ice and ice mixtures deposited at 10 K under ultra-high vacuum conditions using Fourier-transform infrared (FTIR) spectroscopy and temperature programmed desorption (TPD) experiments. Laboratory ice spectra were compared to JWST observation of Europa's and Ganymede's leading hemispheres. The simulated IR spectra were calculated using density functional theory (DFT) methods, exploring the effect of porosity in CO$_2$ ice. Pure CO$_2$ and CO$_2$-water ice show distinct spectral changes and desorption behaviours at different temperatures, revealing intricate CO$_2$ and H$_2$O interactions. The number of discernible peaks increases from two in pure CO$_2$ to three in CO$_2$-water mixtures. The different CO$_2$ bands were assigned to $ nu $ (2351 cm$^ $, 4.25 mu m) caused by CO$_2$ dangling bonds (CO$_2$ found in pores or cracks) and $ nu $ (2345 cm$^ $, 4.26 mu m) due to CO$_2$ segregated in water ice, whereas $ nu $ (2341 cm$^ $, 4.27 mu m) is due to CO$_2$ molecules embedded in water ice. The JWST NIRSpec CO$_2$ spectra for Ganymede and for Europa can be fitted with two Gaussians attributed to $ nu $ and $ nu $. For Europa, $ nu $ is located at lower wavelengths due to a lower temperature. The Ganymede data reveal latitudinal variations in CO$_2$ bands, with $ nu $ dominating in the pole and $ nu $ prevalent in other regions. This shows that CO$_2$ is embedded in water ice at the poles and it is present in pores or cracks in other regions. Ganymede longitudinal spectra reveal an increase of the CO$_2$ $ nu $ band throughout the day, possibly due to ice cracks or pores caused by large temperature fluctuations.

Designing alkali-exchanged ZSM-5 catalysts for the dehydration of lactic acid to acrylic acid

This report shows that complete control of the degree of alkali exchange is possible by controlling the pH strength, and that is possible to distinguish the selectivity of the cations themselves in the lactic acid (LA) dehydration reaction by excluding undesired active sites arising from excess salts. We discovered that strong base conditions induced by alkali hydroxides (e.g., KOH) increase the degree of alkali ion exchange, and that in the absence of additional salts−such as halogen anions, oxides−the KOH-ZSM-5 catalyst exhibited high acrylic acid (AA) selectivity (~70%) and durability (100h). Characterization via temperature-programmed desorption (TPD) and pyridine-infrared (Py-IR) analysis revealed a full exchange of the protons bound to the Si–O–Al sites with potassium in commercial ZSM-5. In addition, structural pore expansion due to the desilication by KOH leads to significant enhancement in the selectivity for AA. The mechanistic impact of KOH treatment on lactic acid dehydration is also systematically verified by in situ IR spectroscopy.

Performance of sulfided NiMo catalyst supported on pillared bentonite Al and Ti under hydrodeoxygenation reaction of guaiacol

Bio-crude oil is known to be sustainable, eco-environmentally, and an alternative energy source produced by biomass pyrolysis. However, its quality remains relatively low due to a higher oxygen concentration compared to liquid fuels from fossils. Therefore, an upgrading process is necessary through the catalytic hydrodeoxygenation (HDO) process. This work synthesized pillared bentonite using Al and Ti metals as the pillaring agent to produce Al-PILC and Ti-PILC as catalyst support for sulfided NiMo. Their catalytic activity in HDO reaction using guaiacol as a model compound of bio-crude oil were also evaluated. Characterization of the bentonite-pillared materials, including Al-PILC, Mo/Al-PILC, NiMo/Al-PILC, Ti-PILC, Mo/Ti-PILC, and NiMo/Ti-PILC, was performed using Surface Area Analyzer, X-ray Diffractometer (XRD), Temperature-Programmed Desorption of ammonia (NH3-TPD), X-Ray Fluorescence (XRF), and Scanning Electron Microscope (SEM) techniques. The characterization results confirm the pillarization process of bentonite using Al and Ti metals as the pillaring agent, and the preparation of the NiMo catalyst using the stepwise impregnation method was successfully prepared. The NiMo/Ti-PILC catalyst performs a superior conversion value on the HDO guaiacol reaction than other catalysts. A well dispersion of Mo and Ni metals on the surface support (NiMo/Ti-PILC), thus creating numerous active sites of the catalyst after the sulfidation. Variations in time and temperature during the HDO guaiacol reaction significantly affected the conversion.

In situ Ni2P catalyst for the selective processing of terephthalic acid into BTX fraction

In situ obtained Ni2P-based catalysts were proposed for the selective conversion of terephthalic acid into the benzene-toluene-xylene fraction. The catalysts were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and NH3 temperature-programmed desorption. The influence of reaction time, temperature and H2 pressure on the conversion of terephthalic acid and benzene-toluene-xylene selectivity was studied. Direct deoxygenation and decarboxylation were found to be the main reaction pathways using in situ Ni2P catalysts. Selectivity for the benzene-toluene-xylene fraction reached up to 100% (at full terephthalic acid conversion) under moderate reaction conditions. The reusability of the in situ Ni2P catalyst before and after regeneration was demonstrated.

Multi-methodological analysis of hydrogen desorption from graphene

Chemisorption of hydrogen on graphene has been extensively investigated in last decades, but the reported values of over several eV, depending on different factors, such as the local structural environment, substrates or previously bound hydrogen.In this work, we combine Temperature-Programmed Desorption experiments with simulations using empirical reactive force fields and Density Functional Theory calculations. We observe that desorption occurs through processes with different activation energies, which we are able to identify by analyzing simulation data and post-processing experimental ones through a procedure based on Arrhenius fit with feedback. The result is the assignment of experimentally observed desorption peaks to different desorption processes, namely desorption from isolated sp3 H, or couples of H in conformation cis or trans, or edge sp3 or sp2 H.The protocol we outline is generally applicable and might be particularly useful in more complex cases with larger multiplicity of desorption peaks.

Synthesize and Characterization of Pt-supported Co-ZIF for Catalytic Hydrocracking and Hydroisomerization of n-Hexadecane

Zeolitic Imidazole Frameworks (ZIFs) are prospective porous materials as catalyst support due to their relatively large surface area, and tunability in size, structure, and porosity. Recent studies have also shown that ZIF is the best candidate for various catalytic redox reactions such as the oxidation of benzyl aromatic hydrocarbons. In this study, the synthesized Pt catalyst supported on Co-ZIF was varied by the organic ligands: imidazole, benzimidazole, and 1-(3-aminopropyl) imidazole, then followed by impregnation of Pt precursor. The catalysts were characterized its physical and chemicals properties such as Fourier Transform Infrared (FTIR), X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Brunauer Emmet Teller (BET), Temperature-Programmed Desorption (NH3-TPD and CO2-TPD). The prepared catalysts were evaluated for catalytic hydrocracking and hydroisomerization of n-hexadecane in a 100 ml-batch reactor. GC-MS analysis presented that the Pt/ZIF catalyst with imidazole ligands has better performance than others. Hence, the optimization of n-Hexadecane conversion was carried out by the Pt/ZIF-imidazole catalyst varying the amount of metal loading, time and temperature reaction. The results showed that the reaction temperature of 350 ºC using 20 bar H2 for 4 h and the addition of 15 wt% Pt successfully achieved 90.77% conversion and produced the highest yield of isomers and alkanes, 4.04% and 35.75%, respectively. Copyright © 2024 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Polyurethane-based thin-film composites with carbon micro- to nanoscale fillers and their microwave properties

Polyurethane-based thin-film composites (PUR-based TFCs) with different carbon fillers, namely, carbon flocs formed by carbon dots (CDs) containing O, N, and F heteroatoms and carbon nanotubes (CNTs), were prepared by hot pressing. The morphology and composition of the carbon fillers were investigated by SEM/EDX. Temperature-programmed desorption mass spectrometry and thermogravimetric analysis revealed that the CNTs have the highest thermostability among the fillers. Microwave studies in the X-band showed that the PUR-based TFCs with the CNTs were characterized by higher reflection losses and lower transmission losses than the PUR-based TFCs with the flocs formed by the studied CDs.

Hydrogen Storage Capacity of Cobalt Cluster Ions.

The adsorption of H2 on gas-phase Con± (n = 5-12) clusters at 300 K and the desorption of H2 from ConHm± upon heating were studied experimentally by combining thermal desorption spectrometry and mass spectrometry to elucidate the hydrogen storage property of the Co clusters. Hydrogen atoms adsorbed well on Con+ (n = 5, 10-12) and Con- (n = 5-12) at 300 K to form ConHm±. The atomic ratios, m/n, for ConHm- (0.9-1.4) were higher than those for ConHm+ (0.2-1.1). According to density functional theory (DFT) calculations, the first few H2 molecules had a tendency to dissociatively adsorb onto the Co clusters. Further, the bonding nature of the H atoms was ionic, similar to the H atoms in the metallic hydrides. In contrast, H2, adsorbed molecularly, was explained in terms of σ complex formation. H2 molecules were desorbed from the clusters upon heating. The temperature dependences showed that ConHm- released H2 at a higher temperature (700-800 K) than ConHm+ (600-700 K), suggesting that Con- should have a higher affinity to hydrogen than Con+. The desorption temperatures were lower than those of VnHm+, which was consistent with the fact that the adsorption energies of H2 were lower for the Co clusters than those for the V clusters. The low adsorption energies were ascribed to their large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps in the Co clusters.

Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd.

The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. We examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al2O3. Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt-CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt-CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal-C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd-CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.

Sublimation of volatiles from H2O:CO2 bulk ices in the context of comet 67P/Churyumov–Gerasimenko. II. Noble gases

The ROSINA instrument on board the Rosetta spacecraft measured, among others, the outgassing of noble gases from comet 67P/Churyumov–Gerasimenko. The interpretation of this dataset and unravelling underlying desorption mechanisms requires detailed laboratory studies. We aim to improve our understanding of the desorption patterns, trapping, and fractionation of noble gases released from the H$_ $O:CO$_ $-dominated ice of comet 67P. In the laboratory, ice films of neon, argon, krypton, or xenon (Ne, Ar, Kr, and Xe) mixed in CO$_ $:H$_ $O were prepared at 15 K. Temperature-programmed desorption mass spectrometry is employed to analyse the desorption behaviour of the noble gases. Mass spectrometric ROSINA data of 67P were analysed to determine the fraction of argon associated with CO$_ $ and H$_ $O, respectively. CO$_ $ has a significant effect on noble gas desorption behaviour, resulting in the co-release of noble gases with CO$_ $, decreasing the amount of noble gas trapped within water, shifting the pure phase noble gas peak desorption temperature to lower temperatures, and prolonging the trapping of neon. These effects are linked to competition for binding sites in the water ice and the formation of crystalline CO$_ $. Desorption energies of the pure phase noble gas release were determined and found to be higher than those previously reported in the literature. Enhancement of the Ar/Kr and Ar/Xe ratios are at best 40<!PCT!> and not significantly influenced by the addition of CO$_ $. Analysis of ROSINA mass spectrometric data shows that the fraction of argon associated with H$_ $O is 0.53 pm 0.30, which cannot be explained by our laboratory results. Multicomponent ice mixtures affect the desorption behaviour of volatiles compared to simple binary mixtures and experiments on realistic cometary ice analogues are vital to understanding comet outgassing.

Optimization of syngas production via methane bi-reforming using CeO2 promoted Cu/MnO2 catalyst

Currently, syngas plays an important role in renewable and sustainable energy production. The idea of manufacturing syngas via bi-reforming methane, which involves the combination of methane (CH4), carbon dioxide (CO2), and steam, appears very promising. As a result, the goal of this research is to improve syngas output by improving process parameters in methane bi-reforming using a 3%Ce-15%Cu/MnO2 catalyst. Optimization analysis was performed using response surface methodology (RSM). The ultrasonic impregnation (UI) method was employed to synthesize the catalysts used in this study. Following that, the catalyst was characterized using several techniques such as Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption (TPD), and temperature programmed oxidation (TPO). The findings of the characterization show that the presence of CeO2 promoters has a dual effect on the size of CuO crystallites. Firstly, it reduces the size from 19.07 nm to 13.66 nm because to the dilutive effect generated by the inclusion of CeO2. Second, the presence of CeO2 promoter accelerates the transition from CuO to Cu0 metallic phase. Furthermore, the addition of CeO2 boosts the CH4 and CO2 conversion rates by 23.65% and 24.93%, respectively. As a result, the H2 yield increases significantly when compared to the unpromoted catalyst. The study investigates the influence of process parameters, specifically the reaction temperature (700–900℃), CO2 ratio (0.2–1), and gas hourly space velocity (GHSV) (16–36 L g cat−1 hr−1), on the conversion of CH4 and CO2, as well as the H2/CO ratio. The optimization study finds that the highest conversion rates for CH4 and CO2 are 78.32% and 72.45%, respectively, when the reaction temperature is 800 °C, the CO2 ratio is 0.6, and the gas hourly space velocity (GHSV) is 26 L g cat−1 hr−1. The optimum conditions result in the highest syngas ratio of 1.77. The results of the optimization are then assessed using the mean errors. The H2/CO ratio, as well as the average errors for CH4 and CO2 conversions, are discovered to be 0.15%, 0.95%, and 0%, respectively.

Fine-tuned MOF-74 type variants with open metal sites for high volumetric hydrogen storage at near-ambient temperature

Adsorbent-based hydrogen storage systems offer a potential solution to current challenges in hydrogen storage, particularly those requiring high pressures or cryogenic temperatures. Specifically, the use of metal–organic frameworks (MOFs) featuring open metal sites that strongly adsorb hydrogen represents a promising strategy for near-ambient-temperature hydrogen storage. This study investigates the hydrogen storage properties of M2(dondc) (M = Mg2+, Co2+, and Ni2+), an extended version of MOF-74. Among this series, Ni2(dondc) exhibits the second-highest volumetric hydrogen capacity of 10.74 g L−1 at 298 K under pressure swing adsorption conditions (100 to 5 bar) at ambient temperatures. The superior hydrogen storage performance of Ni2(dondc) is attributed to its highly polarizable Ni open metal sites and a significant heat of adsorption of 12.2 kJ mol−1. These findings are corroborated by temperature-programmed desorption spectroscopy and van der Waals-corrected density functional theory calculations. In addition to its exceptional hydrogen capacity, Ni2(dondc) exhibits robust structural stability and long-term durability, positioning it as a promising candidate for near-ambient-temperature hydrogen storage applications.

Simple Fabrication of Hydrophobicity-Controlled Fe-ZSM-5 for Aqueous-Phase Partial Oxidation of Methane with Hydrogen Peroxide

Surface hydrophobicity is an important factor in controlling the catalytic activity of heterogeneous catalysts in various reactions, particularly liquid-phase reactions using water as the (co)solvent. In this study, the surface hydrophobicity of Fe-ZSM-5 was successfully controlled using a simple coating method in which furfuryl alcohol was used as the carbon precursor. Various techniques, such as N2 physisorption, temperature-programmed desorption of ammonia, and contact angle measurements of water droplets, were used to characterize the catalysts. Fe-ZSM-5 catalysts with different degrees of hydrophobicity were used for the aqueous-phase selective oxidation of methane with H2O2. The positive effect of the surface carbon coating on the catalytic performance was confirmed when the carbon content was not sufficiently high to block the pores.

Fabrication of 3-(trihydroxysilyl)-1-propanesulfonic acid membranes with superior affinity and selectivity for NH3 permeation over H2 and N2 at 50–300 °C

Ammonia (NH3) produced by Haber-Bosch process is separated through the condensation process, which needs a large amount of energy consumption. Membrane separation technology is compelling for achieving energy-saving and efficient NH3 separation. Therefore, 3-(trihydroxysilyl)-1-propanesulfonic acid (TPS) was applied, for the first time, to fabricate sulfonic silica-based membranes and evaluated for NH3 selective permeation. The amorphous siloxane network can be formed by simple condensation of silanol (Si–OH) under sulfonic acid (-SO3H) self-catalysis, as confirmed by the results of Fourier transform infrared spectroscopy and X-Ray diffractometry. Moreover, TPS xerogel powders dried from TPS sols showed excellent thermal stability and dense structure via thermogravimetric and N2 adsorption analyses. Importantly, an intensive NH3 adsorption amount of ∼3.0 mmol g−1 for TPS xerogels from NH3 adsorption and temperature-programmed desorption was twice higher than the reported oxidized (3-mercaptopropyl)trimethoxysilane xerogels (∼1.41 mmol g−1), which was ascribed to the inherently stronger proton-acidic -SO3H groups in TPS. Finally, TPS membranes prepared using TPS solutions diluted with ethanol expressed superior NH3-selective permeation based on favorable molecular sieving and NH3 adsorption-diffusion via single and binary gas permeation, especially remarkable NH3 permeance of ∼2.6 × 10−7 mol m−2 s−1 Pa−1 and excellent NH3/N2 selectivity of 266 at 300 °C.

Hydrogen isotope permeation and retention behavior in the RAFM steel manufactured by laser powder bed fusion

Laser powder bed fusion (LPBF) has emerged as a promising additive manufacturing technique for producing complex components across various industries. This method is particularly instrumental in fabricating reduced activation ferritic/martensitic (RAFM) steel, a candidate structural material for the tritium breeding blanket. Hydrogen transport behaviors in the conventional RAFM steel have been largely investigated; however, they are not well understood in the LPBF-RAFM steel. In this work, we studied the hydrogen isotope permeation and retention behavior in the RAFM steel fabricated by LPBF, utilizing the deuterium gas driven permeation and thermal desorption spectroscopy experiments. The results show that the hydrogen isotope permeability of the LPBF-RAFM steel is close to the conventionally fabricated RAFM steel, but the diffusion coefficient is greatly lower and the retention is markedly higher in the LPBF-RAFM steel compared to the conventional RAFM steel. The large number density of microvoids and TiC precipitates in the LPBF-RAFM steel could be the predominant factors that result in the decrease in hydrogen isotope diffusion coefficient and the increase in the total amount of deuterium retention.

Performance of NiO doped on alkaline sludge from waste photovoltaic industries for catalytic dry reforming of methane.

Alkali sludge (AS) is waste abundantly generated from solar photovoltaic (PV) solar cell industries. Since this potential basic material is still underutilized, a combination with NiO catalyst might greatly influence coke resentence, especially in high-temperature thermochemical reactions (Arora and Prasad, RSC Adv. 6:108,668-108688, 2016). This paper investigated alkaline sludge containing 3CaO-2SiO2 doped with well-known NiO to enhance the dry reforming of methane (DRM) reaction. The wet-impregnation method was used to prepare the xNiO/AS (x = 5-15%) catalysts. Subsequently, all catalysts were tested by using X-ray diffraction (XRD), nitrogen adsorption/desorption (BET), temperature-programmed reduction of hydrogen (H2-TPR), temperature-programmed desorption of carbon dioxide (TPD-CO2), field emission scanning electron microscopy (FESEM-EDX), and X-ray photoelectron spectroscopy (XPS). The spent catalysts were analyzed by thermogravimetric analysis (TGA/DTG), transmission electron microscopy (TEM), and temperature-programmed oxidation (TPO). The catalytic performance of xNiO/AS catalysts was investigated in a fixed bed reactor connected with gas chromatography thermal conductivity detector (GC-TCD) at a CH4:CO2 flow rate of 30 mL-1 during a 10-h reaction by following (Shamsuddin et al., Int. J. Energy Res. 45:15,463-15,480, 2021d). For optimization parameters, the effects of NiO concentration (5, 10, and 15%), reaction temperature (700, 750, 800, 850, and 900 °C), catalyst loading (0.1, 0.2, 0.3, 0.4, and 0.5 g), and gas hourly space velocity (GHSV) range from 3000, 6000, 9000, 12,000, and 15,000 h-1 were evaluated. The results showed that physical characteristics such as BET surface area and porosity do not significantly impact NiO percentages of dispersion, whereas chemical characteristics like reducibility are crucial for the catalysts' efficient catalytic activity. Due to the active sites on the catalyst surface being more accessible, increased NiO dispersion resulted in higher reactant conversion. The catalytic performance on various parameters that showed 15%NiO/AS exhibited high reactant conversion up to 98% and 40-60% product selectivity in 700 °C, 0.2 g catalyst loading, and 12,000 h-1 GHSV. According to spent catalyst analyses, the catalyst was stable even after the DRM reaction. Meanwhile, increased reducibility resulted in more and better active site formation on the catalyst. Synergetic effect of efficient NiO as active metal and medium basic sites from AS enhanced DRM catalytic activity and stability with low coke formation.

Polymorphism and Its Influence on Catalytic Activities of Lanthanide-Glutamate-Oxalate Coordination Polymers.

To study the relationship between polymorphism and catalytic activities of lanthanide coordination polymers in the cycloaddition reactions of CO2 with epoxides, the monoclinic and triclinic polymorphs of [LnIII(NH3-Glu)(ox)]·2H2O, where LnIII = LaIII (I), PrIII (II), NdIII (III), SmIII (IV), EuIII (V), GdIII (VI), TbIII (VII), and DyIII (VIII), NH3-Glu- = NH3+ containing glutamate, and ox2- = oxalate, were synthesized and characterized. Factors determining polymorphic preference, the discrepancy between the two polymorphic framework structures, potential acidic and basic sites, thermal and chemical stabilities, active surface areas, void volumes, CO2 sorption/desorption isotherms, and temperature-programmed desorption of NH3 and CO2 are comparatively presented. Based on the cycloaddition of CO2 with epichlorohydrin in the presence of tetrabutylammonium bromide under solvent-free conditions and ambient pressure, catalytic activities of the two polymorphs were evaluated, and the relationship between polymorphism and catalytic performances has been established. Better performances of the monoclinic catalysts have been revealed and rationalized. In addition, the scope of monosubstituted epoxides was experimented and the outstanding performance of the monoclinic catalyst in the cycloaddition reaction of CO2 with allyl glycidyl ether under ambient pressure has been disclosed.