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We explore here, through reactive force field (ReaxFF) molecular dynamics simulations, oleic acid upgrading on beta zeolite (BEA) regulated with nine silica-to-aluminium ratios (SARs) to investigate their acid-catalyzed deoxygenation and coking susceptibility. The selected computational descriptors involved conversion, hydrodeoxygenation, and decarboxylation/decarbonylation selectivity, biofuels yield, and coke deposition characteristics. Simulations were validated by 20.3 SAR available experimental data and used for the systematic study. High deoxygenation selectivity was found to be related to the structural sensitivity of BEA(100) on the upgrading mechanism. ReaxFF simulations revealed that altering the Al-substitution could greatly promote biofuel formation. Specifically, SARs towards the mid-region (SAR 47) favored gasoline production, while 31 SAR exploited diesel-like hydrocarbons. An optimum ratio of 37.4 SAR achieved maximum oleic acid conversion (69.8%), with high yields of gasoline and diesel fuels (15.6 and 20.4 wt%, respectively) and moderate coking (8.6 wt%). Density functional theory screening of metallic dopants allowed investigating of their deoxygenation and coke susceptibility, obtaining that Cu-BEA structure favored the optimal carbon and O moiety adsorption (-3.89 and -1.8 eV, respectively). Furthermore, the economic and environmental analysis showed that Cu-dopped BEA displayed the lowest market price and global warming potential (71 USD/kg and 2.8 kg CO2-eq/kg).

Abstract This study presents a single‐site microkinetic model for methanol synthesis by CO2 hydrogenation over intermetallic Pd2Ga/SiO2. A reaction path analysis (RPA) combining theoretical results and realistic catalyst surface reaction data is established to elucidate the reaction mechanism and kinetic models of CO2 hydrogenation to methanol and CO. The RPA leads to the derivation of rate expressions for both reactions without presumptions about the most abundant reactive intermediate (MARI) and rate‐determining step (rds). The formation of H2COOH* is found to be the rds (step 19) for methanol synthesis via the formate pathway, with CO2 and H‐atoms adsorbed on intermetallic sites as the MARIs. The derived kinetic model is corroborated with experimental data acquired under different reaction conditions, using a lab‐scale fixed‐bed reactor and Pd2Ga/SiO2 nanoparticles prepared by incipient wetness impregnation. The excellent agreement between the experimental data and the kinetic model (R2 = 0.99) substantiates the proposed mechanism with an activation energy of 61.52 kJ mol‐1 for methanol synthesis. The reported catalyst exhibits high selectivity to methanol (96%) at 1 bar, 150 °C, and H2/CO2 ratio of 3:1. These findings provide critical insights to optimize catalysts and processes targeting CO2 hydrogenation at atmospheric pressure and low temperatures for on‐demand energy production.

Catalysis has optimized and improved production rates in many industrial processes. Conventional catalysis plays a key role in the mass-production of otherwise difficult to obtain substances. Plasma catalysis, plasma incorporation to appropriate catalysts, has been shown in literature to further outperform the typical conventional methods, and has shown potential to become a key production method in deep space exploration and survival. However, it faces a few more challenges that hinder it from being used industrially. In this review, we discuss known mechanisms in literature and the instrumentation and diagnostics that were utilized to be able to determine and explain these mechanisms in detail, and thus have led to the development of plasma catalysts with up to 80 % conversion rates for CO2 conversion processes. We also discuss diagnostics that may be employed in the near future to reveal the last few unconventional mechanisms that must be explained in order to address the current instability and short life of catalysts due to the harsh conditions of plasma. In successful implementations of diagnostics in literature, they have proven to be the key to unlocking the knowledge required to develop appropriate catalysts optimized for converting CO2 in a plasma environment.

Abstract The ordered porous frameworks like MOFs and COFs are generally constructed using the monomers through distinctive metal-coordinated and covalent linkages. Meanwhile, the inter-structural transition between each class of these porous materials is an under-explored research area. However, such altered frameworks are expected to have exciting features compared to their pristine versions. Herein, we have demonstrated a chemical-induction phase-engineering strategy to transform a two-dimensional conjugated Cu-based SA-MOF (Cu-Tp) into 2D-COFs (Cu-TpCOFs). The structural phase transition offered in-situ pore size engineering from 1.1 nm to 1.5–2.0 nm. Moreover, the Cu-TpCOFs showed uniform and low percentage-doped (~ 1–1.5%) metal distribution and improved crystallinity, porosity, and stability compared to the parent Cu-Tp MOF. The construction of a framework from another framework with new linkages opens interesting opportunities for phase-engineering.

Abstract This work presents a hydrothermal-based facile method for synthesizing ZnFe2O4, whose size can be controlled with the concentration of sodium acetate used as a fuel and its physical changes at nanoscales when exposed to two different gases. The structural, morphological, compositional, and electronic properties of the synthesized samples are also presented in this paper. The crystal structure of the synthesized samples was determined using an X-ray Diffractometer (XRD). The results revealed fluctuations in the size, lattice parameter, and strain in the nanoparticles with increasing the concentration of sodium acetate. Field-Emission Scanning Electron Microscopy (FESEM) was used to determine synthesized materials’ morphology and particle size. It revealed that the particles possessed approximately spherical morphology whose size decreased significantly with the increasing amount of sodium acetate. Transmission Electron Microscopy (TEM) was utilized to determine the structure, morphology, and elemental distributions in particles at the nanoscale, and it confirmed the findings of XRD and FESEM analyses. The high-resolution TEM (HRTEM) imaging analysis of the nanoparticles in our studied samples revealed that the particles predominantly possessed (001) type facets. X-ray photoelectron spectroscopy (XPS) and core-loss electron energy loss spectroscopy (EELS) showed an increasing fraction of Fe2+ with the decreasing size of the particles in samples. The Brunauer, Emmett, and Tellers (BET) analysis of samples revealed a higher surface area as the particle size decreases. In addition, the determined surface area and pore size values are compared with the literature, and it was found that the synthesized materials are promising for gas-sensing applications. The ab initio calculations of the Density of States (DOS) and Band structure of (001) surface terminating ZnFe2O4 were carried out using Quantum Espresso software to determine the bandgap of the synthesized samples. They were compared to their corresponding experimentally determined bandgap values and showed close agreement. Finally, in-situ TEM measurement was carried out on one of the four studied samples with robust properties using Ar and CO2 as reference and target gases, respectively. It is concluded from the presented study that the size reduction of the ZnFe2O4 nanoparticles (NPs) tunes the bandgap and provides more active sites due to a higher concentration of oxygen vacancies. The in-situ TEM showed us a nanoscale observation of the change in one of the crystal structure parameters. The d spacing of ZnFe2O4 NPs showed a noticeable fluctuation, reaching more than 5% upon exposure to CO2 and Ar gases.

Abstract Color blindness or color vision deficiency (CVD) is a congenital ocular deficiency that hampers patients’ daily life activities. CVD patients rely mostly on using wearable visual aids that enhance color distinction by blocking problematic wavelengths of light. Contributing to that, this study examines the fabrication of 3D‐printed colored contact lens for color blindness management. A vat photopolymerization based 3D printing technology is utilized to fabricate the contact lenses for CVD patients. An in‐house prepared resin is mixed with a low‐cost colored ink to attain the desired blocking range (520–580 nm). The fabricated lens blocks more than 50% of light at the problematic wavelengths, along with exhibiting minimal leakage when stored and examined in water and contact lens storage solution. Average contact angle and water content values are 48° and 56%, respectively. Mechanical properties demonstrate the physical adequacy of the contact lens. The CVD filtering efficacy of the tinted contact lens and its potential as a CVD wearable is evaluated by comparing its optical performance with that of commercial products. Finally, cytotoxicity analysis of the lens to dermal fibroblast cells reveals the biocompatibility of the lens as the cell viability remains greater than 75% after 24 h.

The premature creep rupture of cast reformer tubes made of HP-Nb steel due to short-term overheating, was investigated. Investigation was performed on specimens from ruptured, cracked, and uncracked tubes and included metallography, mechanical testing, and SEM/EDX analysis. It was found that accidental short-term overheating, after 5 years of normal operation, caused rapid tertiary creep, manifested by the formation of dense cavities and cracking, which eventually led to the premature creep rupture of several tubes of the reformer. Creep cavities formed preferentially at M7C3 carbides but also at M23C6 and MC carbides while crack propagation took place along the interdendritic carbide network. It appears that the radial direction of the columnar grains from the inside to outside diameter orients the grain boundaries perpendicular to the hoop stress, a situation which degrades creep rupture resistance. An analysis based on the Larson–Miller parameter confirmed the premature creep rupture of the tubes due to overheating.

Replacing the conventionally used steam reforming of methane (SRM) with a process that has a smaller carbon footprint, such as dry reforming of methane (DRM), has been found to greatly improve the industry’s utilization of greenhouse gases (GHGs). In this study, we numerically modeled a DRM process in lab-scale packed and fluidized beds using the Eulerian–Lagrangian approach. The simulation results agree well with the available experimental data. Based on these validated models, we investigated the effects of temperature, inlet composition, and contact spatial time on DRM in packed beds. The impacts of the side effects on the DRM process were also examined, particularly the role the methane decomposition reaction plays in coke formation at high temperatures. It was found that the coking amount reached thermodynamic equilibrium after 900 K. Additionally, the conversion rate in the fluidized bed was found to be slightly greater than that in the packed bed under the initial fluidization regime, and less coking was observed in the fluidized bed. The simulation results show that the adopted CFD approach was reliable for modeling complex flow and reaction phenomena at different scales and regimes.

Structural and morphological control of crystalline nanoparticles is crucial in heterogeneous catalysis. Applying DFT-assisted solid-state NMR spectroscopy, we determine the surface crystal and electronic structure of Ni2P nanoparticles, unveiling NMR nanocrystallography as an emerging tool in facet-engineered nanocatalysts.

In this study, we examine the effect of integrating different carbon nanostructures (carbon nanotubes, CNTs, graphene nanoplatelets, GNPs) into Ni- and Ni-W-based bi-functional catalysts for hydrocracking of heptane performed at 400 °C. The effect of varying the SiO2/Al2O3 ratio of the zeolite Y support (between 5 and 30) on the heptane conversion is also studied. The results show that the activity, in terms of heptane conversion, followed the order CNT/Ni-ZY5 (92%) > GNP/Ni-ZY5 (89%) > CNT/Ni-W-ZY30 (86%) > GNP/Ni-W-ZY30 (85%) > CNT/Ni-ZY30 (84%) > GNP/Ni-ZY30 (83%). Thus, the CNT-based catalysts exhibited slightly higher heptane conversion as compared to the GNP-based ones. Furthermore, bimetallic (Ni-W) catalysts possessed higher BET surface areas (725 m2/g for CNT/Ni-W-ZY30 and 612 m2/g for CNT/Ni-ZY30) and exhibited enhanced hydrocracking activity as compared to the monometallic (Ni) catalyst with the same zeolite support and type of carbon structure. It was also shown that CNT-based catalysts possessed higher regeneration capability than their GNP-based counterparts due to the slightly higher thermal stability of the CVD-grown CNTs.

The dry reforming of methane (DRM) reaction is among the most popular catalytic reactions for the production of syngas (H2/CO) with a H2:CO ratio favorable for the Fischer–Tropsch reaction; this makes the DRM reaction important from an industrial perspective, as unlimited possibilities for production of valuable products are presented by the FT process. At the same time, simultaneously tackling two major contributors to the greenhouse effect (CH4 and CO2) is an additional contribution of the DRM reaction. The main players in the DRM arena—Ni-supported catalysts—suffer from both coking and sintering, while the activation of the two reactants (CO2 and CH4) through different approaches merits further exploration, opening new pathways for innovation. In this review, different families of materials are explored and discussed, ranging from metal-supported catalysts, to layered materials, to organic frameworks. DRM catalyst design criteria—such as support basicity and surface area, bimetallic active sites and promoters, and metal–support interaction—are all discussed. To evaluate the reactivity of the surface and understand the energetics of the process, density-functional theory calculations are used as a unique tool.

This review presents the structural elements and discusses the great potential of high entropy oxides (HEO) as promising catalysts. A critical comparison is provided with the medium and low entropy metal oxides in terms of the important functionality of HEO to exhibit higher oxygen mobility and withhold high population of oxygen vacancies as well as leading to high metal dispersion. This review study critically compares the performance of the thermal, electro- and photo- high entropy oxides catalysts with the conventional metal oxides and demonstrates their superiority over them while discussing the governing characteristics of HEO. The HEO complex structure is highlighted using ab initio calculations on understanding and tuning their electronic/structural properties. Catalysts’ design criteria and direction in the studies of the HEO as catalysts for energy and sustainability are proposed.

Hydrodeoxygenation (HDO) reaction is a route with much to offer in the conversion and upgrading of bio-oils into fuels; the latter can potentially replace fossil fuels. The catalyst’s design and the feedstock play a critical role in the process metrics (activity, selectivity). Among the different classes of catalysts for the HDO reaction, the transition metal phosphides (TMP), e.g., binary (Ni2P, CoP, WP, MoP) and ternary Fe-Co-P, Fe-Ru-P, are chosen to be discussed in the present review article due to their chameleon type of structural and electronic features giving them superiority compared to the pure metals, apart from their cost advantage. Their active catalytic sites for the HDO reaction are discussed, while particular aspects of their structural, morphological, electronic, and bonding features are presented along with the corresponding characterization technique/tool. The HDO reaction is critically discussed for representative compounds on the TMP surfaces; model compounds from the lignin-derivatives, cellulose derivatives, and fatty acids, such as phenols and furans, are presented, and their reaction mechanisms are explained in terms of TMPs structure, stoichiometry, and reaction conditions. The deactivation of the TMP’s catalysts under HDO conditions is discussed. Insights of the HDO reaction from computational aspects over the TMPs are also presented. Future challenges and directions are proposed to understand the TMP-probe molecule interaction under HDO process conditions and advance the process to a mature level.

We report herein the synthesis of siloxane-functionalized CBP molecules (4,4′-bis(carbazole)-1,1′-biphenyl) for liquid optoelectronic applications. The room-temperature liquid state is obtained through a convenient functionalization of the molecules with heptamethyltrisiloxane chains via hydrosilylation of alkenyl spacers. The synthesis comprises screening of metal-catalyzed methodologies to introduce alkenyl linkers into carbazoles (Stille and Suzuki Miyaura cross-couplings), incorporate the alkenylcarbazoles to dihalobiphenyls (Ullmann coupling), and finally introduce the siloxane chains. The used conditions allowed the synthesis of the target compounds, despite the high reactivity of the alkenyl moieties bound to π-conjugated systems toward undesired side reactions such as polymerization, isomerization, and hydrogenation. The features of these solvent-free liquid CBP derivatives make them potentially interesting for fluidic optoelectronic applications.

Highly active metal-free mesoporous phosphated silica was synthesized by a two-step process and used as a SO2 hydrogenation catalyst. With the assistance of a microwave, MCM-41 was obtained within a 10 min heating process at 180 °C, then a low ratio of P precursor was incorporated into the mesoporous silica matrix by a phosphorization step, which was accomplished in oleylamine with trioctylphosphine at 350 °C for 2 h. For benchmarking, the SiO2 sample without P precursor insertion and the sample with P precursor insertion into the calcined SiO2 were also prepared. From the microstructural analysis, it was found that the presence of CTAB surfactant was important for the incorporation of active P species, thus forming a highly dispersed, ultrafine (uf) phosphate silica, (Si-P) catalyst. The above approach led to the promising catalytic performance of uf-P@meso-SiO2 in the selective hydrogenation of SO2 to H2S; the latter reaction is very important in sulfur-containing gas purification. In particular, uf-P@meso-SiO2 exhibited activity at the temperature range between 150 and 280 °C, especially SO2 conversion of 94% and H2S selectivity of 52% at 220 °C. The importance of the CTAB surfactant can be found in stabilizing the high dispersion of ultrafine P-related species (phosphates). Intrinsic characteristics of the materials were studied using XRD, FTIR, EDX, N2 adsorption/desorption, TEM, and XPS to reveal the structure of the above catalysts.

The rapid increase in anthropogenic greenhouse gas concentrations in the last several decades means that the effects of climate change are fast becoming the familiar horsemen of a planetary apocalypse. Catalysis, one of the pillars of the chemical and petrochemical industries, will play a critical role in the effort to reduce the flow of greenhouse gases into the atmosphere. This Special Issue is timely, as it provides a collection of high-quality manuscripts in a diverse range of topics, which include the production of green hydrogen via water electrolysis, the steam reforming of ethanol, propane or glycerol, the dry reforming of methane, and the autothermal reforming of diesel surrogate fuel. The topic of the transformation of biomass waste to chemicals is also well represented as is the tackling of CO2 emissions via novel utilization technologies. The Editors are grateful to all authors for their valuable contributions and confident that this Special Issue will prove valuable to scholars, university professors and students alike.

Significant improvement of the catalytic activity of palladium-based catalysts toward carbon monoxide (CO) oxidation reaction has been achieved through alloying and using different support materials. This work demonstrates the promoting effects of the nanointerface and the morphological features of the support on the CO oxidation reaction using a Pd-Cu/TiO2 catalyst. Pd-Cu catalysts supported on TiO2 were synthesized with wet chemical approaches and their catalytic activities for CO oxidation reaction were evaluated. The physicochemical properties of the prepared catalysts were studied using standard characterization tools including SEM, EDX, XRD, XPS, and Raman. The effects of the nanointerface between Pd and Cu and the morphology of the TiO2 support were investigated using three different-shaped TiO2 nanoparticles, namely spheres, nanotubes, and nanowires. The Pd catalysts that are modified through nanointerfacing with Cu and supported on TiO2 nanowires demonstrated the highest CO oxidation rates, reaching 100% CO conversion at temperature regime down to near-ambient temperatures of ~45 °C, compared to 70 °C and 150 °C in the case of pure Pd and pure Cu counterpart catalysts on the same support, respectively. The optimized Pd-Cu/TiO2 nanowires nanostructured system could serve as efficient and durable catalyst for CO oxidation at near-ambient temperature.

This work reports the preparation and detailed characterization of stannum indium sulfide (SnIn4S8) semiconductor photocatalyst for degradation of ethiofencarb (toxic insecticide) under visible-light irradiation. The as-prepared SnIn4S8 showed catalytic efficiency of 98% in 24 h under optimal operating conditions (pH = 3, catalyst dosage of 0.5 g L−1). The photodegradation reaction followed pseudo-first-order kinetics. The major intermediates have been identified using gas chromatography/mass spectrometry. •O2− and •OH radicals appeared to be the primary active species in the degradation process as revealed by scavenger and electronic spin resonance studies, while photogenerated holes had a secondary role in this process. A plausible mechanism involving two routes was proposed for ethiofencarb degradation by SnIn4S8 after identifying the major intermediate species: oxidative cleavage of the CH2-S and the amide bonds of the carbamate moiety. Lastly, SnIn4S8 was found to be efficient, stable, and reusable in treating real water samples in three successive photodegradation experiments. This study demonstrates the prospect of SnIn4S8 photocatalysis in treatment of natural and contaminated water from extremely toxic organic carbamates as ethiofencarb.

“Bottom-up” additive manufacturing (AM) is the technology whereby a digitally designed structure is built layer-by-layer, i.e., differently than by traditional manufacturing techniques based on subtractive manufacturing. AM, as exemplified by 3D printing, has gained significant importance for scientists, among others, in the fields of catalysis and separation. Undoubtedly, it constitutes an enabling pathway by which new complex, promising and innovative structures can be built. According to recent studies, 3D printing technologies have been utilized in enhancing the heat, mass transfer, adsorption capacity and surface area in CO2 adsorption and separation applications and catalytic reactions. However, intense work is needed in the field to address further challenges in dealing with the materials and metrological features of the structures involved. Although few studies have been performed, the promise is there for future research to decrease carbon emissions and footprint. This review provides an overview on how AM is linked to the chemistry of catalysis and separation with particular emphasis on reforming reactions and carbon adsorption and how efficient it could be in enhancing their performance.

A promising route for the energetic valorisation of the main by-product of the biodiesel industry is the steam reforming of glycerol, as it can theoretically produce seven moles of H2 for every mole of C3H8O3. In the work presented herein, CeO2–Al2O3 was used as supporting material for Ir, Pd and Pt catalysts, which were prepared using the incipient wetness impregnation technique and characterized by employing N2 adsorption–desorption, X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR), Temperature Programmed Desorption (TPD), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The catalytic experiments aimed at identifying the effect of temperature on the total conversion of glycerol, on the conversion of glycerol to gaseous products, the selectivity towards the gaseous products (H2, CO2, CO, CH4) and the determination of the H2/CO and CO/CO2 molar ratios. The main liquid effluents produced during the reaction were quantified. The results revealed that the Pt/CeAl catalyst was more selective towards H2, which can be related to its increased number of Brønsted acid sites, which improved the hydrogenolysis and dehydrogenation–dehydration of condensable intermediates. The time-on-stream experiments, undertaken at low Water Glycerol Feed Ratios (WGFR), showed gradual deactivation for all catalysts. This is likely due to the dehydration reaction, which leads to the formation of unsaturated hydrocarbon species and eventually to carbon deposition. The weak metal–support interaction shown for the Ir/CeAl catalyst also led to pronounced sintering of the metallic particles.

This paper examines the effect of incorporating graphene nanoplatelets (GNPs) in an Ni-based/Zeolite-Y catalyst on the hydrocracking of heptane fuel at two temperatures, 350 and 400 °C. Specifically, reduced GNP/NiO-ZY and NiO-ZY catalysts, each with a 5 wt. % Ni loading, were compared in this study. The results show that the reduced GNP/NiO-ZY enhanced the conversion percentage by 31% at 350 °C and by 6% at 400 °C as compared with the reduced NiO-ZY, and the GNP/NiO-ZY also showed superior stability, reporting a less than 2% drop in conversion over 20 h of time-on-stream. The enhancement in performance is linked to the surface and texture characteristics of both catalysts. Although the calcined GNP/NiO-ZY possessed a lower Brunauer–Emmett–Teller (BET) surface area of 458 m2/g compared with 536 m2/g for the calcined NiO-ZY, it showed a more hydrophobic nature, as deduced from the water adsorption profiles, which corroborates the hypothesis that the increased affinity between the catalyst surface and heptane molecules during the reaction leads to an improved catalytic activity.

Boron chemistry has evolved to become one of the most diverse and applied fields in organic synthesis and catalysis. Various valuable reactions such as hydroborylations and Suzuki−Miyaura cross-couplings (SMCs) are now considered as indispensable methods in the synthetic toolbox of researchers in academia and industry. The development of novel sterically- and electronically-demanding C(sp3)−Boron reagents and their subsequent metal-catalyzed cross-couplings attracts strong attention and serves in turn to expedite the wheel of innovative applications of otherwise challenging organic adducts in different fields. This review describes the significant progress in the utilization of classical and novel C(sp3)−B reagents (9-BBN and 9-MeO-9-BBN, trifluoroboronates, alkylboranes, alkylboronic acids, MIDA, etc.) as coupling partners in challenging metal-catalyzed C(sp3)−C(sp2) cross-coupling reactions, such as B-alkyl SMCs after 2001.

The time-on-stream catalytic performance and stability of 8 wt. % Ni catalyst supported on two commercially available catalytic supports, ZrO2 and 15 wt.% WO3-ZrO2, was investigated under the biogas dry reforming reaction for syngas production, at 750°C and a biogas quality equal to CH4/CO2 = 1.5, that represents a common concentration of real biogas. A number of analytical techniques such as N2 adsorption/desorption (BET method), XRD, H2-TPR, NH3- and CO2-TPD, SEM, ICP, thermal analysis (TGA/DTG) and Raman spectroscopy were used in order to determine textural, structural and other physicochemical properties of the catalytic materials, and the type of carbon deposited on the catalytic surface of spent samples. These techniques were used in an attempt to understand better the effects of WO3-induced modifications on the catalyst morphology, physicochemical properties and catalytic performance. Although Ni dispersion and reducibility characteristics were found superior on the modified Ni/WZr sample than that on Ni/Zr, its dry reforming of methane (DRM) performance was inferior; a result attributed to the enhanced acidity and complete loss of the basicity recorded on this catalyst, an effect that competes and finally overshadows the benefits of the other superior properties. Raman studies revealed that the degree of graphitization decreases with the insertion of WO3 in the crystalline structure of the ZrO2 support, as the ID/IG peak intensity ratio is 1.03 for the Ni/Zr and 1.29 for the Ni/WZr catalyst.

The tackling of carbon deposition during the dry reforming of biogas (BDR) necessitates research of the surface of spent catalysts in an effort to obtain a better understanding of the effect that different carbon allotropes have on the deactivation mechanism and correlation of their formation with catalytic properties. The work presented herein provides a comparative assessment of catalytic stability in relation to carbon deposition and metal particle sintering on un-promoted Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts for different reaction temperatures. The spent catalysts were examined using thermogravimetric analysis (TGA), Raman spectroscopy, high angle annular dark field scanning transmission electron microscopy (STEM-HAADF) and X-ray photoelectron spectroscopy (XPS). The results show that the formation and nature of carbonaceous deposits on catalytic surfaces (and thus catalytic stability) depend on the interplay of a number of crucial parameters such as metal support interaction, acidity/basicity characteristics, O2− lability and active phase particle size. When a catalytic system possesses only some of these beneficial characteristics, then competition with adverse effects may overshadow any potential benefits.

Multifunctional materials for energy conversion and storage could act as a key solution for growing energy needs. In this study, we synthesized nanoflower-shaped iron-nickel sulfide (FeNiS) over a nickel foam (NF) substrate using a facile hydrothermal method. The FeNiS electrode showed a high catalytic performance with a low overpotential value of 246 mV for the oxygen evolution reaction (OER) to achieve a current density of 10 mA/cm2, while it required 208 mV at 10 mA/cm2 for the hydrogen evolution reaction (HER). The synthesized electrode exhibited a durable performance of up to 2000 cycles in stability and bending tests. The electrolyzer showed a lower cell potential requirement for a FeNiS-Pt/C system (1.54 V) compared to a standard benchmark IrO2-Pt/C system (1.56 V) to achieve a current density of 10 mA/cm2. Furthermore, the FeNiS electrode demonstrated promising charge storage capabilities with a high areal capacitance of 13.2 F/cm2. Our results suggest that FeNiS could be used for multifunctional energy applications such as energy generation (OER and HER) and storage (supercapacitor).

Attapulgite (ATP, a natural clay) was used as carrier to produce a nickel-based catalyst (Ni/ATP) for the work that is presented herein. Its catalytic performance was comparatively assessed with a standard Ni/Al2O3 sample for the glycerol steam reforming (GSR) reaction. It was shown that the ATP support led to lower mean Ni crystallite size, i.e., it increased the dispersion of the active phase, to the easier reduction of NiO and also increased the basicity of the catalytic material. It was also shown that it had a significant effect on the distribution of the gaseous products. Specifically, for the Ni/ATP catalyst, the production of liquid effluents was minimal and subsequently, conversion of glycerol into gaseous products was higher. Importantly, the Ni/ATP favored the conversion into H2 and CO2 to the detriment of CO and CH4. The stability experiments, which were undertaken at a low WGFR, showed that the activity of both catalysts was affected with time as a result of carbon deposition and/or metal particle sintering. An examination of the spent catalysts revealed that the coke deposits consisted of filamentous carbon, a type that is known to encapsulate the active phase with fatal consequences.

The gas compressibility factor, also known as the deviation or Z-factor, is one of the most important parameters in the petroleum and chemical industries involving natural gas, as it is directly related to the density of a gas stream, hence its flow rate and isothermal compressibility. Obtaining accurate values of the Z-factor for gas mixtures of hydrocarbons is challenging due to the fact that natural gas is a multicomponent, non-ideal system. Traditionally, the process of estimating the Z-factor involved simple empirical correlations, which often yielded weak results either due to their limited accuracy or due to calculation convergence difficulties. The purpose of this study is to apply a hybrid modeling technique that combines the kernel ridge regression method, in the form of the recently developed Truncated Regularized Kernel Ridge Regression (TR-KRR) algorithm, in conjunction with a simple linear-quadratic interpolation scheme to estimate the Z-factor. The model is developed using a dataset consisting of 5616 data points taken directly from the Standing−Katz chart and validated using the ten-fold cross-validation technique. Results demonstrate an average absolute relative prediction error of 0.04%, whereas the maximum absolute and relative error at near critical conditions are less than 0.01 and 2%, respectively. Most importantly, the obtained results indicate smooth, physically sound predictions of gas compressibility. The developed model can be utilized for the direct calculation of the Z-factor of any hydrocarbon mixture, even in the presence of impurities, such as N 2 , CO 2 , and H 2 S, at a pressure and temperature range that fully covers all upstream operations and most of the downstream ones. The model accuracy combined with the guaranteed continuity of the Z-factor derivatives with respect to pressure and temperature renders it as the perfect tool to predict gas density in all petroleum engineering applications. Such applications include, but are not limited to, hydrocarbon reserves estimation, oil and gas reservoir modeling, fluid flow in the wellbore, the pipeline system, and the surface processing equipment.

In this study, a critical comparison between two low metal (Ni) loading catalysts is presented, namely Ni/Al2O3 and Ni/AlCeO3 for the glycerol steam reforming (GSR) reaction. The surface and bulk properties of the catalysts were evaluated using a plethora of techniques, such as N2 adsorption/desorption, Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP−AES), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy / Energy Dispersive X-Ray Spectroscopy (SEM/EDX, Transmission Electron Microscopy (TEM), CO2 and NH3− Temperature Programmed Desorption (TPD), and Temperature Programmed Reduction (H2−TPR). Carbon deposited on the catalyst’s surfaces was probed using Temperature Programmed Oxidation (TPO), SEM, and TEM. It is demonstrated that Ce-modification of Al2O3 induces an increase of the surface basicity and Ni dispersion. These features lead to a higher conversion of glycerol to gaseous products (60% to 80%), particularly H2 and CO2, enhancement of WGS reaction, and a higher resistance to coke deposition. Allyl alcohol was found to be the main liquid product for the Ni/AlCeO3 catalyst, the production of which ceases over 700 °C. It is also highly significant that the Ni/AlCeO3 catalyst demonstrated stable values for H2 yield (2.9−2.3) and selectivity (89−81%), in addition to CO2 (75−67%) and CO (23−29%) selectivity during a (20 h) long time-on-stream study. Following the reaction, SEM/EDX and TEM analysis showed heavy coke deposition over the Ni/Al2O3 catalyst, whereas for the Ni/AlCeO3 catalyst TPO studies showed the formation of more defective coke, the latter being more easily oxidized.

To contribute to solving global energy problems, a multifunctional CoFe2O4 spinel was synthesized and used as a catalyst for overall water splitting and as an electrode material for supercapacitors. The ultra-fast one-step electrodeposition of CoFe2O4 over conducting substrates provides an economic pathway to high-performance energy devices. Electrodeposited CoFe2O4 on Ni-foam showed a low overpotential of 270 mV and a Tafel slope of 31 mV/dec. The results indicated a higher conductivity for electrodeposited compared with dip-coated CoFe2O4 with enhanced device performance. Moreover, bending and chronoamperometry studies suggest excellent durability of the catalytic electrode for long-term use. The energy storage behavior of CoFe2O4 showed high specific capacitance of 768 F/g at a current density of 0.5 A/g and maintained about 80% retention after 10,000 cycles. These results demonstrate the competitiveness and multifunctional applicability of the CoFe2O4 spinel to be used for energy generation and storage devices.

In the present study, Ni/Ce-Sm-xCu (x = 5, 7, 10 at.%) catalysts were prepared using microwave radiation coupled with sol-gel and followed by wetness impregnation method for the Ni incorporation. Highly dispersed nanocrystallites of CuO and NiO on the Ce-Sm-Cu support were found. Increase of Cu content seems to facilitate the reducibility of the catalyst according to the H2 temperature-programmed reduction (H2-TPR). All the catalysts had a variety of weak, medium and strong acid/basic sites that regulate the reaction products. All the catalysts had very high XC3H8O3 for the entire temperature (400–750 °C) range; from ≈84% at 400 °C to ≈94% at 750 °C. Ni/Ce-Sm-10Cu catalyst showed the lowest XC3H8O3-gas implying the Cu content has a detrimental effect on performance, especially between 450–650 °C. In terms of H2 selectivity (SH2) and H2 yield (YH2), both appeared to vary in the following order: Ni/Ce-Sm-10Cu > Ni/Ce-Sm-7Cu > Ni/Ce-Sm-5Cu, demonstrating the high impact of Cu content. Following stability tests, all the catalysts accumulated high amounts of carbon, following the order Ni/Ce-Sm-5Cu < Ni/Ce-Sm-7Cu < Ni/Ce-Sm-10Cu (52, 65 and 79 wt.%, respectively) based on the thermogravimetric analysis (TGA) studies. Raman studies showed that the incorporation of Cu in the support matrix controls the extent of carbon graphitization deposited during the reaction at hand.

Stress-oriented hydrogen-induced cracking (SOHIC) of an amine absorber column made of a Hydrogen Induced Cracking (HIC) resistant steel and operating under wet H2S service was investigated. SOHIC was not related to welds in the column and evolved in two steps: initiation of HIC cracks in the rolling plane and through-thickness linking of the HIC cracks. Both the original HIC cracks as well as the linking cracks propagated with a cleavage mechanism. The key factors identified were periods with high hydrogen charging conditions, manifested by high H2S/amine ratio, and stress triaxiality, imposed by the relatively large thickness of the plate. In addition, the mechanical properties of the steel away from cracked regions were unaffected, indicating the localized nature of SOHIC.

In this study, the effect of reduction on the electrical conductivity of Graphene Oxide (GO) is investigated. The aim of this fabrication was to render electromagnetic interference (EMI) shielding to thin polymer films using GO as fillers. The electrical conductivity was determined using the four-probe method and shielding effectiveness was theoretically determined using the experimentally obtained conductivity values. The initial oxidation of graphite was performed using Hummers’ method and the oxidized GO was dispersed in water for further exfoliation by ultrasonication. Thin films of sonicated GO dispersions were solution casted and dried in a convection oven at 50 °C overnight. The dried films were treated with 48% hydrobromic acid (HBr), 95% hydrochloric acid (HCl) or 66% hydroiodic acid (HI) for 2 h, 24 h or 48 h. A partial factorial design of experiments based on Taguchi method was used to identify the best reducing agent to obtain maximum electrical conductivity in the partially reduced GO films. The experimental analysis indicates that the electrical resistivity of GO is highly dependent on the type of acid treatment and the samples treated with HI acid exhibited lowest resistivity of ~0.003 Ω·cm. The drop in resistivity value after chemical reduction was of the order of 10,000 times, and range obtained in this work is among the lowest reported so far. The theoretical EMI shielding of the reduced GO film provided a shielding effectiveness of 5.06 dB at 12 GHz.