Renovated FeCoP-NC nanospheres wrapped by CoP-NC nanopetals: As a tremendously effectual and robust MOF-assisted electrocatalyst for hydrogen energy production.

The future of energy technology is significantly influenced by hydrogen (H2) energy. However, hydrogen energy production through water-splitting entirely depends on the catalyst's performance. Modifying the morphological structure and increasing the number of active sites by changing the metal composition are pivotal factors in enhancing the catalytic activity for the hydrogen evolution reaction (HER). In this context, we introduce the impact of metal-organic framework (MOF) strategies for decorating CoP petals onto α-Fe2O3 and FeCoP-NC (NC-nitrogen-doped carbon) nanoflowers. This method results in an excellent electrocatalyst for HER. The study demonstrated the influence of different MOF precursors, the impact of calcination temperatures, and the importance of composition percentages in Fe1-xCoxP-NC. As a result, FeCoP-NC shows excellent electrochemical performance potential (η) of 57 mV, a rapid kinetic Tafel value of 61 mV/dec, and remarkable electrochemical stability of around 2000 cycles and 20 h in stand potential. Additionally, the composite has numerous active surfaces at 4.7 mF/cm2 during the electrochemical reactions. This work concludes that MOF-assisted FeCoP-NC nanoflowers are an ideal electrocatalyst for HER in an alkaline medium.

Photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction to methane with simultaneous H2 production.

This study assessed the photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction. The TNA photocatalysts were fabricated by titanium anodization and submitted to an annealing treatment for crystallization and/or cathodic reduction to introduce Ti3+ and oxygen vacancies into the TiO2 structure. The cathodic reduction demonstrated a significant effect on the generated photocurrent. The photoactivity of the four TNA catalysts in CO2 reduction with water vapor was evaluated under UV irradiation for 3 h, where CH4 and H2 were detected as products. The annealed sample exhibited the best performance towards methane with a production rate of 78 µmol gcat-1 h-1, followed by the amorphous film, which also exhibited an impressive formation rate of 64 µmol gcat-1 h-1. The amorphous and reduced-amorphous films exhibited outstanding photoactivity regarding H2 production (142 and 144 µmol gcat-1 h-1, respectively). The annealed catalyst also revealed a good performance for H2 production (132 µmol gcat-1 h-1) and high stability up to five reaction cycles. Molecular dynamic simulations demonstrated the changes in the band structure by introducing oxygen vacancies. The topics covered in this study contribute to the Sustainable Development Goals (SDG), involving affordable and clean energy (SDG#7) and industry, innovation, and infrastructure (SDG#9).

Controlling the Fe2O3-SiO2 interaction: The effect on the H2S selective catalytic oxidation and catalyst deactivation.

Biogas utilization is one of the most promising options for reducing the consumption of fossil fuels for energy production, but the presence of H2S represents a serious industrial and environmental problem. In this work, two different synthesis methods (sol-gel and incipient wetness impregnation) were used to synthesize iron oxide supported on silica catalysts (Fe2O3/SiO2) with metal loadings ranging from 0.5 to 10 %wt. The catalysts were tested for the selective oxidation of H2S, changing the operating conditions like O2/H2S (0.5-2.5), temperature (170-250°C), and water content (0-50%). The optimum condition was O2/H2S = 0.5 and no water at 230 °C with the conversion of approximately 100%, the selectivity of 97%, and the deactivation of 0.6%. A detailed characterization of the fresh and spent catalysts' surface revealed the presence of four deactivation mechanisms: metal surface reduction, oxygen vacancy loss, pore plugging, and sintering. Among the observed deactivation mechanisms, the sintering showed the highest impact on catalytic activity and deactivation. The sol-gel catalysts (SG) showed the highest metal-oxide/support interaction, which reduced the metal-oxide nanoparticles sintering compared with the incipient wetness impregnation method (IWI), reporting a lower sintering, higher activity, and selectivity, lower deactivation rates and lower sensitivity to the operating conditions. A catalytic cycle representing the possible surface intermediate states of the catalyst is proposed based on the performance and characterization results obtained.

Synthesis and Characteristics of CaO/MgO Mixed Oxides for the Double Bond Isomerization of 1-Butene.

The MgO catalysts containing only weak/medium basic sites were doped with a strong basic oxide CaO by co-precipitation method with 0.19-3.64 wt% CaO. While the amount of strong basic sites linearly increased with wt.% CaO, the activity for isomerization of 1-butene to 2-butenes of the CaO-doped MgO catalysts was maximized at 1.77 wt% CaO. Addition of a small amount of CaO-dopant altered the MgO structure (i.e., the formation of step, edge, and corner sites), resulting in different OH- adsorption abilities and enhanced catalytic activities.

Liquid-phase hydrogenation of phenylacetylene over the nano-sized Pd/TiO2 catalysts.

Understanding the mechanisms of metal-support interaction and/or adhesion and growth of the metal particles is important not only in the field of catalysis but also the design of advanced nanostructure materials. In the present work, the strong metal-support interaction (SMSI) effect occurred on the Pd/TiO2 catalysts synthesized by the sonochemical method when reduced at 500 degrees C whereas the ones prepared by the conventional impregnation resulted in sintering of Pd0 particles instead. The presence of SMSI was correlated to the amount of oxygen vacancies or Ti3+ defective sites. Smaller Pd0 particles with more uniform size distribution on the sonochemical-derived catalysts may promote hydrogen spillover from Pd0 surface to TiO2 support so that the reduction of Ti4+ to Ti3+ occurred, resulting in the SMSI. As a consequence, the catalysts exhibited improved catalytic performances in the liquid-phase selective hydrogenation of phenylacetylene to styrene.

Desorption of water from distinct step types on a curved silver crystal.

We have investigated the adsorption of H2O onto the A and B type steps on an Ag single crystal by temperature programmed desorption. For this study, we have used a curved crystal exposing a continuous range of surface structures ranging from [5(111) × (100)] via (111) to [5(111) × (110)]. LEED and STM studies verify that the curvature of our sample results predominantly from monoatomic steps. The sample thus provides a continuous array of step densities for both step types. Desorption probed by spatially-resolved TPD of multilayers of H2O shows no dependence on the exact substrate structure and thus confirms the absence of thermal gradients during temperature ramps. In the submonolayer regime, we observe a small and linear dependence of the desorption temperature on the A and B step density. We argue that such small differences are only observable by means of a single curved crystal, which thus establishes new experimental benchmarks for theoretical calculation of chemically accurate binding energies. We propose an origin of the observed behavior based on a "two state" desorption model.

A single-site platinum CO oxidation catalyst in zeolite KLTL: microscopic and spectroscopic determination of the locations of the platinum atoms.

A stable site-isolated mononuclear platinum catalyst with a well-defined structure is presented. Platinum complexes supported in zeolite KLTL were synthesized from [Pt(NH3)4](NO3)2, oxidized at 633 K, and used to catalyze CO oxidation. IR and X-ray absorption spectra and electron micrographs determine the structures and locations of the platinum complexes in the zeolite pores, demonstrate the platinum-support bonding, and show that the platinum remained site isolated after oxidation and catalysis.

Value-added bioproducts by bioethanol dehydrogenation to acetaldehyde through Cu and Zn modified biochar catalysts.

In this study, the efficiency of a series of biochar-supported Cu catalysts, biochar-supported Zn catalysts, and biochar-supported Cu-Zn catalysts was determined through bioethanol dehydrogenation to the high-value chemical, acetaldehyde. Each metal, with weight percentages of 10, 20, and 30, and the combination of Cu-Zn, including 10 wt% of Cu and Zn, 15 wt% of Cu - 5 wt% of Zn, and 15 wt% of Cu and Zn, were fully loaded onto biochar using an incipient wetness impregnation technique. Subsequently, all biocatalysts were subjected to bioethanol dehydrogenation reactions in a temperature range of 200-400 °C. The optimum metal loading for the catalyst was found to be the combination of 15 wt% Cu and 15 wt% Zn. This catalyst resulted in a reasonable acetaldehyde yield of 56.2%, an initial bioethanol conversion of 57.3%, and a very high acetaldehyde selectivity of 98.1% at a mild reaction temperature of 300 °C and ambient pressure. These results were attributed to the optimal concentration of weak-medium acid and medium base sites. Active acid and base sites were identified through temperature-programmed desorption of ammonia (NH3-TPD) and temperature-programmed desorption of carbon dioxide (CO2-TPD), respectively. Furthermore, the reaction stability test of the best biocatalyst (15Cu-15Zn/BB) was proven by maintaining this reaction at the same temperature (300 °C) for 10 h. However, the catalytic performance slightly decreased due to the coke formation of Cu species.

Pd-loaded hierarchical titanosilicalite-1 catalysts on CO2 cycloaddition with epoxides: Experimental and DFT investigations.

This work presents the synthesis of Pd-loaded microporous titanosilicalite-1 (Pd/TS-1) and Pd-loaded hierarchical titanosilicalite-1 (Pd/HTS-1) with abundant mesopores (2-30 nm) inside the framework via hydrothermal method using polydiallydimethyl ammonium chloride as the non-surfactant mesopore template. XRD, N2 sorption, FT-IR, FESEM-EDX, TEM, XPS, and DR-UV techniques were used to characterize the morphological and physicochemical properties of the synthesized materials. These materials were tested as heterogeneous catalysts, along with tetrapropylammonium bromide as co-catalyst, for cycloaddition reactions of CO2 with epoxides to produce cyclic carbonates. It was found that the epoxide conversions were influenced by acidity and pore accessibility of the catalysts. Using Pd/HTS-1 facilitated bulky substrates to access active sites, resulting in higher conversions than Pd/TS-1. Over 85 % conversions were achieved for at least five consecutive cycles without significant loss in catalytic activity. The interaction between the Pd active surfaces and epichlorohydrin (ECH) was further studied by DFT calculations. The existence of Pd(200) was more influential on adsorbing epichlorohydrin (ECH) and subsequent formation of dissociated ECH (DECH) intermediate than Pd(111) surface. However, Pd(111) was dominant in enhancing the activity of DECH species for capturing CO2. Therefore, the co-existence of Pd(200) and Pd(111) surfaces was needed for cycloaddition of CO2 with ECH.

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiOx Catalysts.

Recently, interest in converting bio-derived fatty acid methyl esters (FAMEs) into added-value products has significantly increased. The selectivity of ketonization reaction in the conversion of the FAMEs has significantly hampered the efficiency of this process. Herein, this work reports the preparation of catalysts with different levels of oxygen vacancies while the crystal phase remained unchanged. The catalyst with the highest level of oxygen vacancy exhibited the maximum selectivity. The density functional theory (DFT) simulation showed an increase in interatomic distances leading to the formation of frustrated Lewis pairs (FLPs) upon the creation of oxygen vacancies. The surface measurements, type and density of acid sites of the catalysts, showed that the Lewis acid sites enhanced the selectivity for ketone production; while Bronsted acid sites increased the formation of by-products. Moreover, the ketone formation rate was directly proportional to acid density. The findings of this research provide a different approach for catalyst design, based on defects engineering and their effect on the surface activity, which could be used for enhancing the catalytic performance of novel metal oxides.

Experimental and first-principles investigation on how support morphology determines the performance of the Ziegler-Natta catalyst during ethylene polymerization.

One class of the Ziegler-Natta catalysts (ZNC) - the TiCl4/MgCl2 having triethyl aluminum (AlEt3), has been widely utilized during ethylene polymerization. Although the Ti species plays the role of a major active site, an increase of Ti species does not always improve the activity of ZNC. Herein, investigations of experiments and density functional theory (DFT) elucidate this inverse effect of the increased amount of TiCl4 deposition in ZNC because of the pretreatment process. However, the activity of ZNC on pretreated MgCl2 dropped to 60% of the unpretreated one. The DFT demonstrates that the pretreatment strengthened the interaction between TiCl4 and ZNC, especially on the (104) surface, forming the TiCl4-TiCl4 cluster. The existence of this TiCl4-TiCl4 cluster found on the ZNC (104) surface weakens the adsorption of the first AlEt3 molecule and obstructs further alkylation process, making another Ti site of the alkylated TiCl4-TiCl4 cluster inactive. However, the difficult formation of the TiCl4-TiCl4 cluster found on the ZNC (110) is an important key point that enables the activation of all adsorbed TiCl4 on this surface by facilitating the alkylation process. Moreover, the existence of the MgCl2 (110) surface prevents the formation of the TiCl4-TiCl4 cluster significantly. Hence, it is suggested that the existence of the (110) plane on ZNC plays a key role in controlling the performance of the ZNC, especially the stability via the prevention of deactivation caused by the clustering of TiCl4.

3D Hierarchical MOF-Derived Defect-Rich NiFe Spinel Ferrite as a Highly Efficient Electrocatalyst for Oxygen Redox Reactions in Zinc-Air Batteries.

The strategy of defect engineering is increasingly recognized for its pivotal role in modulating the electronic structure, thereby significantly improving the electrocatalytic performance of materials. In this study, we present defect-enriched nickel and iron oxides as highly active and cost-effective electrocatalysts, denoted as Ni0.6Fe2.4O4@NC, derived from NiFe-based metal-organic frameworks (MOFs) for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). XANES and EXAFS confirm that the crystals have a distorted structure and metal vacancies. The cation defect-rich Ni0.6Fe2.4O4@NC electrocatalyst exhibits exceptional ORR and OER activities (ΔE = 0.68 V). Mechanistic pathways of electrochemical reactions are studied by DFT calculations. Furthermore, a rechargeable zinc-air battery (RZAB) using the Ni0.6Fe2.4O4@NC catalyst demonstrates a peak power density of 187 mW cm-2 and remarkable long-term cycling stability. The flexible solid-state ZAB using the Ni0.6Fe2.4O4@NC catalyst exhibits a power density of 66 mW cm-2. The proposed structural design strategy allows for the rational design of electronic delocalization of cation defect-rich NiFe spinel ferrite attached to ultrathin N-doped graphitic carbon sheets in order to enhance active site availability and facilitate mass and electron transport.

Effect of Strontium Modification in Mg-Al Mixed Oxide Catalysts on Product Distribution toward Catalytic Reaction of Ethanol.

The aim of this research was to examine the effect of strontium content in the MgAlO catalyst for the catalytic ethanol reaction on the product distribution. The structure of the catalysts and the actual amount of strontium on the catalysts were verified using XRD and ICP techniques, respectively. The acid and basic strength characteristics of catalysts were examined using NH3-TPD and CO2-TPD techniques, respectively. The strontium content was found to influence the textural properties and the acidic and basic characteristics of the catalysts, leading to differences in product selectivity and ethanol conversion. The MgAlO catalyst with 1.9 wt % strontium provided the maximum ethylene and butanol selectivity, probably due to the presence of appropriate medium acidic and strong basic sites. All catalysts can efficiently produce ethylene by a dehydration reaction and acetaldehyde by a dehydrogenation reaction. Acetaldehyde selectivity was dominant with increased strontium loading.

Evaluation of the hydrogenation reaction on the electrocatalytic nitrobenzene degradation over (FeCoNiCuZn)xOy high entropy oxides (HEOs).

Environmental pollution is one of the main challenges currently faced by mankind; especially industrial waste-waters treatment and remediation using energy-efficient methodologies. This research focused on the electrochemical degradation of the hazardous nitrobenzene (NB) in aqueous solutions, using novel high-entropy oxide (HEO) electrodes to elucidate the influence of the electrochemical reduction step on the degradation process. The effect of solution pH, dissolved oxygen concentration, anodic applied potential, and cell configurations on NB hydrogenation reaction were evaluated. A synergistic effect between the hydrogenation of nitrobenzene and the degradation was found to drastically enhance the conversion rates. The presence of dissolved oxygen promoted the oxidation reactions, reaching more than 90% nitrobenzene removal at 1.7 V and pH 14. The degradation of the organic by-products was attributed to the formation of the superoxide radical (O2*-) as the main oxidant species. A degradation mechanism was proposed based on the detected intermediates and the decoupling of electrochemical surface reactions observed by EIS at different solution pH.

A novel S-scheme Ws2/BiYWO6 electrostatic heterostructure for enhanced photocatalytic degradation performance towards the degradation of Rhodamine B.

Constructing S-scheme heterojunction between two semiconductor materials is an effective route to increase the photocatalytic degradation efficiency. Here, a novel S-scheme WS2/BiYWO6 heterojunction photocatalyst was prepared by wet chemical route. At the same time, the photocatalytic degradation performance of the fabricated materials was analyzed by the degradation of Rhodamine B under visible light. Of all prepared WS2/BiYWO6 composites, the 20 wt.% WS2 loaded WS2/BiYWO6 composite exhibited an enhanced photocatalytic degradation ability than other prepared photocatalysts. Here, O2·- and ·OH radicals are performing a pivotal role in the Rhodamine B degradation and the optimized composite shows greater photocurrent intensity than pure BiYWO6 and WS2, respectively. Also, the synthesized photocatalyst maintains its stability with negligible changes even after three cycles. Thereby, the constructed S-scheme WS2/BiYWO6 heterojunction is a potential material for the wastewater remediation.

Noble metals (Pd, Ag, Pt, and Au) doped bismuth oxybromide photocatalysts for improved visible light-driven catalytic activity for the degradation of phenol.

The doping of noble metals onto the semiconductor metal oxides has a great impact on the intrinsic properties of the materials. This present work reports the synthesis of noble metals doped BiOBr microsphere by a solvothermal method. The various characteristic findings reveal the effective incorporation of Pd, Ag, Pt, and Au onto the BiOBr and the performance of synthesized samples was test for the degradation of phenol over visible light. The Pd-doped BiOBr material showed enhanced phenol degradation efficacy, which is ∼4-fold greater than pure BiOBr. This improved activity was on reason of good photon absorption, lower recombination rate, and higher surface area facilitated by surface plasmon resonance. Moreover, Pd-doped BiOBr sample displayed good reusability and stability after 3 cycles of run. A plausible charge transfer mechanism for phenol degradation is disclosed in detail over Pd-doped BiOBr sample. Our findings disclose that the incorporation of noble metal as the electron trap is a feasible approach to enhance visible light activity of BiOBr photocatalyst used in phenol degradation. This work represents new vision interested in the outline and development of noble metal doped semiconductor metal oxides as a visible light material for the elimination of colorless toxins from untreated wastewater.

A density functional theory study on how γ-Al2O3 - Boehmite transformation affects carbon evolution during aqueous-phase reaction.

Gamma-alumina (γ-Al2O3), one of the most common materials, is commercially used in many catalytic applications, including the active catalyst and support. However, the problem of fast deactivation makes the utilization of the γ-Al2O3 challenging. This work elucidates the mechanism of coke formation consisting of coke deposition and evolution on γ-Al2O3(110) surfaces in differential conditions, including; clean and hydroxylation γ-Al2O3(110) in terms of partial and fully hydroxylation of OH/γ-Al2O3(110) and AlOOH(010), respectively. We demonstrated that the γ-Al2O3(110) surface is proper for atomic coke deposition and dimerization in the initial state, where the presence of OH species promotes the coke evolution to higher coke, Cn (where n ≥ 3). Also, the higher coke formation thermodynamically preferred the cyclic form to the aliphatic one. The electron transfer from substrates to adsorbed coke illustrates the role of the electron donor of catalyst surfaces corresponding to the electron acceptor of adsorbed cokes.

Influence of Highly Stable Ni2+ Species in Ni Phyllosilicate Catalysts on Selective Hydrogenation of Furfural to Furfuryl Alcohol.

Enhancing the catalytic performance of non-noble Ni catalysts in the selective hydrogenation of furfural to furfuryl alcohol (FA) in terms of furfural conversion, selectivity, and good recyclability is challenging. Here, spherical nickel phyllosilicate catalysts (Ni_PS) with fibrous-like structures are prepared via a modified sol-gel method with Ni loadings of 2-30 wt %. Upon exposure to air, all the reduced Ni_PS catalysts exhibit more than 80% Ni0/Niphyllosilicate species on the surface, whereas a large portion of Ni oxide species (>55%) is presented on the impregnated catalyst. The Ni2+ species in nickel phyllosilicate catalysts are active and highly stable during reduction, reaction, and regeneration, yielding stable catalytic performance for multiple recycle tests in furfural hydrogenation to FA. Furfural conversion over the Ni_PS catalysts increased monotonically with increasing Ni loading without an FA selectivity drop. The presence of both metallic Ni0 and Niphyllosilicate also produces a synergistic promotional effect for FA formation.

Catalytic deoxygenation of fatty acids via ketonization and α-carbon scissions over layered alkali titanate catalysts under N2.

The ketonization of fatty acid with subsequent McLafferty rearrangement of the fatty ketone allows the deoxygenation to hydrocarbons. Here, we report the cascade reaction of palmitic acid (C16) to hydrocarbons (≤C14) over lepidocrocite-type alkali titanate K0.8Zn0.4Ti1.6O4, K0.8Mg0.4Ti1.6O4, and K0.8Li0.27Ti1.73O4 and the reassembled TiO2 catalysts at ≤400 °C under atmospheric N2 in a continuous fixed-bed flow reactor. The C16 acid is coupled to C31 ketone prior to the scissions mostly to a C17 methyl ketone and C14 hydrocarbons (i.e., the McLafferty rearrangement). The hydrocarbons yield increases with temperature and is proportional to partial charge at the O atom, suggesting that basic sites are responsible for C31 ketone scissions. The layered alkali titanate catalysts with two-dimensional (2D) space inhibit diffusion of the ketone primarily formed and promote its scissions to hydrocarbons within the confined space. Otherwise, low hydrocarbons yield (but high ketone yield) is obtained over TiO2 and the Mg/Al mixed oxide catalysts possessing no interlayer space. Meanwhile, the semi-batch experiment with pre-intercalated palmitic acid favors a direct deoxygenation, demonstrating the essential role of reaction mode toward ketone scission reaction pathway. Over K0.8Li0.27Ti1.73O4, the complete palmitic acid conversion leads to ∼47% hydrocarbons yield, equivalent to ∼80% reduction of the oxygen content in the feed under N2.

Optimal Conditions for Butanol Production from Ethanol over MgAlO Catalyst Derived from Mg-Al Layer Double Hydroxides.

The MgAlO catalyst was obtained from thermal decomposition of the MgAl-LDH catalyst having Mg/Al molar ratio of 5. The catalytic Guerbet reaction of ethanol was investigated to determine the effect of WHSV and nitrogen flow rate on butanol production and product distribution. It was performed in a fixed-bed microreactor under continuous flow of vaporized ethanol mixed with N2. The MgAlO catalyst had high total basic sites and high total acid sites that were crucial for ethanol Guerbet reaction. The MgAlO catalyst showed the highest butanol selectivity at 300℃ under WHSV = 3.10 h-1 and nitrogen flow rate = 3,600 mL/h, and the highest butanol yield at 400℃ under WHSV = 3.10 h-1 and nitrogen flow rate = 900 mL/h. It can be summarized that in order to enhance the butanol yield, the low WHSV is preferred to increase the contact time of ethanol and catalyst under moderate temperature.