Good Catalyst Research Articles

Single-Atom Substituents in Copper Surfaces May Adsorb Multiple CO Molecules.

Copper is a good CO2 electroreduction catalyst as products beyond CO form, but efficiency and selectivity is low. Experiments have shown that an admixture of other elements can help, and computational screening studies have pointed out various promising candidates based on the adsorption of a single CO molecule as a descriptor. Our calculations of CO adsorption on surfaces where a first row transition metal atom replaces a Cu atom show that multiple CO molecules, not just one, bind to the substitutional atom. For Fe, Co, and Ni atoms, a decrease in binding energy is found, but the reverse trend, namely, increasing bond strength, is found for V, Cr, and Mn and the first three CO molecules. Magnetic moment, charge, and position of the substitutional atom are also strongly affected by the CO adsorption in most cases. Magnetic moment is stepwise reduced to zero, and the outward displacement of the substitutional atom increased.

Creating a good ammonia catalyst from an unreactive metal

Creating a good ammonia catalyst from an unreactive metal

Jet fuel production via palm oil hydrodeoxygenation over bifunctional zeolite mixture supported Ni catalyst: Effect of Si/Al ratio

The influence of the Si/Al ratio of ZSM-5 on 10 wt% Ni/ZSM-5.SAPO-11 catalysts were investigated through the palm oil hydrodeoxygenation (HDO) process, based on the product selectivity of alternative jet fuel. This study utilizes a 1 L batch reactor at 60 bar and 350 °C for palm oil hydrodeoxygenation over 10 wt% Ni/ZSM-5.SAPO-11 catalysts. Si/Al ratio of 50 produces a 10 wt% Ni/ZSM-5.SAPO-11 catalyst with the optimum physicochemical properties for palm oil hydrodeoxygenation. TGA/DTG analysis of the spent catalyst shows that the catalyst has good thermal and catalyst stability with minor carbon deposition. GC/MS analysis also demonstrated a 100 % palm oil conversion to alternative jet fuel. The highest jet fuel yield of 51 % was attained with a Si/Al ratio of 50. The physicochemical properties of alternative jet fuel samples were measured to ensure that the conventional fuel standard limits were appropriately followed. These results indicated that such types of bifunctional Ni-based catalysts have the potential to be used in the conversion of triglycerides to alternative jet fuel.

Influence of red mud as a catalyst in the thermocatalytic reforming process

AbstractThis work studies red mud, a residue from the processing of bauxite, as a support catalyst in the thermocatalytic reforming (TCR) process, using wood, digestate, and straw as case studies. Thermocatalytic reforming is a thermochemical process for the conversion of biomass into biofuels, combining intermediate pyrolysis and catalytic reforming and resulting in high‐quality biofuels. The quantity and quality of the catalyst in the postreformer is vital as it influences the reactions taking place in it. Normally, nonreactive components of the char produced in the process act as the catalyst in the postreformer but adding a support catalyst may improve the products. In this work, red mud is introduced in the process by mixing it with the feedstock in a ratio of 1:3. The results, in comparison with normal TCR experiments on the same feedstock materials, show that the introduction of red mud into the process generally reduces the biochar yield and generally increases the biogas and product water yields, and the bio‐oil yield remains constant. Its introduction also increases the hydrogen fraction of the gas and tends to reduce the nitrogen and sulfur content of the products, thus improving their quality. These observations are consistent across feedstock materials and postreformer temperatures. The results therefore suggest that red mud is a good support catalyst for increasing the gas yield, increasing the hydrogen fraction of the gas, and improving the quality of the products from the TCR process.

Green catalyst innovation: Enhanced Fischer-Tropsch synthesis using potassium-promoted cobalt catalysts supported on pyrolyzed peanut shells and Cladophora Glomerata modified biochars

This paper explores pyrolysis potential for effective modified biochar (MB) production, serving as a green and novel carbon-based catalyst support in Fischer-Tropsch to olefins synthesis. For this purpose, the MB produced from the pyrolysis of pre-treated Peanut shell (PS) and Cladophora glomerata algae (CG) was used as a high porosity support for cobalt catalyst synthesis. The impregnation technique was applied to prepare the cobalt catalysts, and the catalysts were promoted with potassium. Various methods examine catalysts physico-chemical properties. After 10 h of reduction at 400 °C, the catalysts' activity and selectivity were studied in a fixed-bed reactor. TEM images show that the metal particles are suitably distributed on the porous surface of the modified biochars. The majority of the particles were between 5 and 15 nm in size. Also, TPR results indicate a suitable metal dispersion of about 10% and good catalyst reducibility have been achieved. The cobalt catalysts produced on MBs of CG and PS exhibited FT rates of 0.245 and 0.223 (g HC/g cat.h), with CO conversion rates of 50.25% and 45.68% in each case. Finally, K-promoted cobalt catalysts supported on MBs of CG and PS showed the α-olefins selectivities of 38.67% and 35.49% for C2-C13 hydrocarbons, respectively.

Oxygen-Deficient FeNbO4-x In-Situ Growth in Honey-Derived N-Doping Porous Carbon for Overall Water Splitting.

It is still a great challenge to reasonably design green, low cost, high activity and good stability catalysts for overall water splitting (OWS). Here, we introduce a novel catalyst with ferric niobate (FeNbO4) in-situ growing in honey-derived porous carbon of high specific surface area, and its catalytic activity is further enhanced by micro-regulation (oxygen vacancy and N-doping). From the experimental results and density functional theory (DFT) calculations, the oxygen vacancy in catalyst FeNbO4-x@NC regulates the local charge density of active site, thus increasing conductivity and optimizing hydrogen/oxygen species adsorption energy. FeNbO4 in-situ grows within N-doping honey-derived porous carbon, which can enhance active specific surface area exposure, strengthen gaseous substances escape rate, and accelerate electrons/ions transfer and electrolytes diffusion. Moreover, in-situ Raman also confirms O-species generation in oxygen evolution reaction (OER). As a result, the catalyst FeNbO4-x@NC shows good electrochemical performance in OER, HER and OWS.

Key Ingredients for the Screening of Single Atom Catalysts for the Hydrogen Evolution Reaction: The Case of Titanium Nitride.

A computational screening of Single Atom Catalysts (SACs) bound to titanium nitride (TiN) is presented, for the Hydrogen Evolution Reaction (HER), based on density functional theory. The role of fundamental ingredients is explored to account for a reliable screening of SACs. Namely, the formation of H2-complexes besides the classical H* one impacts the predicted HER activity, in line with previous studies on other SACs. Also, the results indicate that one needs to adopt self-interaction-corrected functionals. Finally, predicting an active catalyst is of little help without an assessment of its stability. Thus, it is included in the theoretical framework the analysis of the stability of the SACs in working conditions of pH and voltage. Once unconventional intermediates and stability are considered in a self-interaction corrected scheme, the number of potential good catalysts for HER is strongly reduced since i) some potentially good catalysts are not stable against dissolution and ii) the formation of unconventional intermediates leads to thermodynamic barriers. This study highlights the importance of including ingredients for the prediction of new systems, such as the formation of unconventional intermediates, estimating the stability of SACs, and the adoption of self-interaction corrected functionals. Also, this study highlights some interesting candidates deserving of dedicated work.

Modulation of energy barrier of reaction steps over S-doped Ni(OH)2/Cu composites to achieve high-performance urea electrolysis catalysts

Ni(OH)2 has been found a cost-effective and promising electrocatalyst for urea oxidation reaction (UOR). However, HER activity is challenging due to its weak adsorption of active H atoms, poor water dissociation, and low conductivity. In this study, heteroatomic S-doped Ni(OH)2/Cu composite has been synthesized using the one-pot electrodeposition process. The incorporation of S atoms significantly enhanced the electron transfer rate and adsorption of active H atoms, which promoted the UOR and HER process. Similarly, the metallic Cu with S-doped Ni(OH)2 also exhibited the synergistic effect and promoted water dissociation, adsorption of active H atoms. As expected, S-doped Ni(OH)2/Cu composites exhibit remarkable urea electrolysis activity with a small cell voltage of 1.35 V to approach the current density of 10 mA cm−2. Results indicate that the adopted strategy has been found effective and the prepared composite is a good bifunctional urea electrolysis catalyst.

The untold story of starch as a catalyst for organic reactions.

Starch is one of the members of the polysaccharide family. This biopolymer has shown many potential applications in different fields such as catalytic reactions, water treatment, packaging, and food industries. In recent years, using starch as a catalyst has attracted much attention. From a catalytic point of view, starch can be used in organic chemistry reactions as a catalyst or catalyst support. Reports show that as a catalyst, simple starch can promote many heterocyclic compound reactions. On the other hand, functionalized starch is not only capable of advancing the synthesis of heterocycles but also is a good candidate catalyst for other reactions including oxidation and coupling reactions. This review tries to provide a fair survey of published organic reactions which include using starch as a catalyst or a part of the main catalyst. Therefore, the other types of starch applications are not the subject of this review.

Blue Economic Beacon: Red And White Leads The Way Through Niche Diplomacy

This research has a specific objective to analyze the Indonesian government's strategy in realizing sustainable marine development based on its role as a middle power country. The author uses the theoretical framework of middle power identity and niche diplomacy to analyze the problems in this study. This research is a type of qualitative research that is explained using the explanatory method. Based on the results of the research, the Indonesian government's strategy is to prioritize sustainable marine development in national marine policy and also commit to contributing to the world's sustainable marine development with the blue economy principle. This commitment will be realized by increasing cooperation in the marine sector at the bilateral, multilateral and regional levels. Specifically, the form of the realization of this commitment is that Indonesia has become the strategy of the Indonesian government to realize sustainable marine development is to become the initiator of the formation of cooperation forums (coalition building), to become the contact person for countries in the interest of sustainable marine development (bridge builder), and to uphold international norms in the marine sector for the common good (catalyst).

Photoexcited Hot Electron Catalysis in Plasmon-Resonant Grating Structures with Platinum, Nickel, and Ruthenium Coatings.

We report the electrochemical potential dependence of photocatalysis produced by hot electrons in plasmon-resonant grating structures. Here, corrugated metal surfaces with a period of 520 nm are illuminated with 785 nm wavelength laser light swept as a function of incident angle. At incident angles corresponding to plasmon-resonant excitation, we observe sharp peaks in the electrochemical photocurrent and dips in the photoreflectance consistent with the conditions under which there is wavevector matching between the incident light and the spacing between the lines in the grating. In addition to the bare plasmonic metal surface (i.e., Au), which is catalytically inert, we have measured grating structures with a thin layer of Pt, Ru, and Ni catalyst coatings. For the bare Au grating, we observe that the plasmon-resonant photocurrent remains relatively featureless over the applied potential range from -0.8 to +1.2 V vs NHE. For the Pt-coated grating, we observe a sharp peak around -0.3 V vs NHE, three times larger than the bare Au grating, and near complete suppression of the oxidation half-reaction, reflecting the reducing nature of Pt as a good hydrogen evolution reaction catalyst. The photocurrent associated with the Pt-coated grating is less noisy and produces higher photocurrents than the bare Au grating due to the faster kinetics (i.e., charge transfer) associated with the Pt-coated surface. The plasmon-resonant grating structures enable us to compare plasmon-resonant excitation with that of bulk metal interband absorption simply by rotating the polarization of the light while leaving all other parameters of the experiment fixed (i.e., wavelength, potential, electrochemical solution, sample surface, etc.). A 64X plasmon-resonant enhancement (i.e., p-to-s polarized photocurrent ratio) is observed for the Pt-coated grating compared to 28X for the bare grating. The nickel-coated grating shows an increase in the hot-electron photocurrent enhancement in both oxidation and reduction half-reactions. Similarly, Ru-coated gratings show an increase in hot-electron photocurrents in the oxidation half-reaction compared to the bare Au grating. Plasmon-resonant enhancement factors of 36X and 15X are observed in the p-to-s polarized photocurrent ratio for the Ni and Ru gratings, respectively.

CO2 Hydrogenation to CH3OH on Metal-Doped TiO2(110): Mechanisms, Strain Effect and a New Thermodynamic-Kinetic Relation.

Surface strain and linear thermodynamic-kinetic relation are interesting topics in catalysis. Development of low temperature methanol catalysts of high activity and selectivity is of particularly importance for conversion of CO2 to methanol. In the present paper CO2 hydrogenation to methanol on Znx@TiO2(110) (x=0-2) was explored using density functional calculations and microkinetic simulations. The reaction mechanisms on the three model systems were determined and it is shown that Zn2@TiO2(110) is the most active. The most favorable pathway on Zn2@TiO2(110) is identified and CO2+H to HCOO is found to be the rate-controlling step. It is demonstrated that there is a linear relation (named AEB relation) between the adsorption energies of the initial states and the barriers for the controlling step on the 18 systems studied. Calculations on strained surfaces show that the AEB relation exists within ±1 % strain. Sr2@TiO2(110) and -1 % strained CaZn and ZnCu doped TiO2(110) are potential good low temperature catalysts and deserve experimental testing.

Interface engineering of 1D/2D FeVO4/MoS2 hetero-structured nanocomposite with effective interfacial charge transfer: Facile synthesis and antibiotic drug degradation

The rapid accumulation of organic contaminants in wastewater is a considerable environmental concern. We are investigating nanoscale FeVO4 and MoS2 structures for enhanced removal of organic pollutants to overcome this challenge. The FeVO4/MoS2 nanocomposite was synthesized via a hydrothermal technique. This study looks at how the FeVO4/MoS2 nanocomposite could be explored as a good catalyst for the degradation of ciprofloxacin drug through Photo-Fenton process. The synergy between FeVO4 and MoS2 and hydroxyl radicals leads to accelerated degradation. Our findings imply that FeVO4/MoS2 nanocomposites could remove pharmaceutical pollutants from wastewater sources, contributing to water treatment technology.

Deciphering the Pivotal Reaction Conditions for Hydrogen Production from Tar Catalytic Cracking by Perovskite

The catalytic cracking of pyrolysis gasification tar into H2 has garnered significant attention due to its exceptional conversion efficiency. In this study, the effects of pollutant concentration, residence time, weight hourly space velocity (WHSV), and reaction temperature on the hydrogen performance of LaFe0.5Ni0.5O3 perovskite were comprehensively investigated. Results revealed that moderate pollutant concentration (0.3 g/L), low-medium residence time (250 SCCM), and low WHSV (0.24 gtoluene/(gcat·h)) facilitated efficient interaction between LaFe0.5Ni0.5O3 and toluene, thus achieving high hydrogen production. An increase in reaction temperature had minimal effect on the hourly hydrogen production above 700 °C but caused a significant increase in methane production. Additionally, the effects of oxygen evolution reactions, methane reactions, and methane catalytic cracking reactions of perovskite induced by different reaction conditions on tar cracking products were discussed in detail. Compared to previous reports, the biggest advantages of this system were that the hydrogen production per gram of tar was as high as 1.002 L/g, and the highest hydrogen content in gas-phase products reached 93.5%, which can maintain for approximately 6 h. Finally, LaFe0.5Ni0.5O3 showed good thermal stability, long-term stability, and catalyst reactivation potential.

Wet peroxide oxidation process catalyzed by Cu/Al2O3: phenol degradation and Cu2+ dissolution behavior.

Catalytic wet peroxide oxidation (CWPO) has become an important deep oxidation technology for organics removal in wastewater treatments. Supported Cu-based catalysts belong to an important type of CWPO catalyst. In this paper, two Cu catalysts, namely, Cu/Al2O3-air and Cu/Al2O3-H2 were prepared and evaluated through catalytic degradation of phenol. It was found that Cu/Al2O3-H2 had an excellent catalytic performance (TOC removal rate reaching 96%) and less metal dissolution than the Cu/Al2O3-air case. Moreover, when the organic removal rate was promoted at a higher temperature, the metal dissolution amounts was decreased. Combined with hydroxyl radical quenching experiments, a catalytic oxidation mechanism was proposed to explain the above-mentioned interesting behaviors of the Cu/Al2O3-H2 catalyst for CWPO. The catalytic test results as well as the proposed mechanism can provide better guide for design and synthesis of good CWPO catalysts.

Activation of Small Molecules by Modified Dodecaborate Anions.

Two of the basic requirements of a good catalyst are that molecules be bound to it with energies intermediate between physisorption and chemisorption and be simultaneously activated in the process. Using density functional theory, we have studied the interaction of small molecules such as H2, O2, N2, CO2, CO, and NH3 with modified dodecaborate anion [B12H12]2-, namely, [B12X11]- and [B12X11]2- (X = H, F, CN). Calculations of the structure, stability, and electronic properties of these species interacting with the above molecules show that they meet the above requirements. In addition, [B12X11]2- (X = F, CN) species are not only more stable than [B12X11]- species but also bind to O2 more strongly than their monoanion counterparts.

Understanding of ZnO‐Catalyzed Polyurethane Synthesis from Bisurea for Further Exploration of One‐Pot Synthesis and Property Evaluation Thereof

AbstractZnO is considered to be a good catalyst for the synthesis of polyurethanes (PUs) by alcoholysis of bisureas (BUs). ZnO tends to form Zn(NCO)2(NH3)2 in the presence of urea at high temperature, so does it in the alcoholysis of BUs. Here, attempt is made to understand the role Zn(NCO)2(NH3)2 plays in the alcoholysis of BUs. A loading of Zn(NCO)2(NH3)2 at 5 mol% is found to be sufficient to catalyze the polymerization and the reaction time is greatly cut from 40 h (catalyzed by ZnO) to 26 h, with similar chemical structures and properties. The tensile strength, elongation at break, and toughness for PU–Zn‐5 can reach 43.8 MPa, 330%, and 94.0 J cm−3, respectively. One‐pot synthetic strategy is then further introduced to improve the efficiency of the polymerization. Zn(NCO)2(NH3)2, BU, and PU can be synthesized in one‐pot, by adding ZnO, urea, diamine, LiBr, and diol sequentially. The feasibility of this one‐pot method is verified, indicated by the similar reaction time, chemical structures, molecular weight, thermal and mechanical properties. This one‐pot synthetic strategy offers an efficient way to synthesize PUs directly and simply from urea, diamines, and diols, which is beneficial for improving the molecular diversity of PUs.

Synthesis, Optical, Dielectric, SHG, Magnetic and Visible Light Driven Catalytic Studies on Compounds Belonging to the Swedenborgite Structure.

A new compound, InBaZn3GaO7, with swedenborgite structure along with transition metal (TM) substituted variants have also been prepared. The structure contains layers of tetrahedral ions (Zn2+/Ga3+) connected by octahedrally coordinated In3+ ion forming the three-dimensional structure with voids where the Ba2+ ions occupy. The TM substituted compounds form with new colors. The origin of the color was understood based on the ligand-field transitions. The near IR reflectivity studies indicate that the Ni - substituted compounds exhibit good near - IR reflectivity behavior, making them possible candidates for 'cool pigments'. The temperature dependent dielectric studies indicate that the InBaZn3GaO7 compound undergoes a phase transition at ~360 °C. The compounds are active towards second harmonic generation (SHG). Magnetic studies show the compounds, InBaZn2CoFeO7 and InBaZn2CuFeO7 to be anti-ferromagnetic in nature. The copper containing compounds were found to be good catalysts, under visible light, for the oxidation of aromatic alkenes. The many properties observed in the swedenborgite structure-based compounds suggests that the mineral structure offers a fertile ground to investigate newer compounds and properties.

A novel CeO2 nanowire catalyst prepared by the freeze-drying method with significantly improved catalytic performance for toluene oxidation

A wire like CeO2 catalyst (CeO2-w) was obtained after the calcination of the precursor at 400 °C, which was prepared by the freeze-drying method for the first time. It shows good performance for catalytic oxidation of toluene with T90 of 220 °C, which is much better than the CeO2 catalysts with other structures prepared by the different methods. The good performance of CeO2-w is due to the bigger pore volume, more active oxygen species, more oxygen vacancies, better low temperature reducibility, higher surface area normalized reaction rates and lower Ea value. Additionally, the CeO2-w catalyst exhibits good water resistance and catalyst stability. In situ DRIFTS indicates the catalytic oxidation of toluene on CeO2-w undergoes the progress of toluene → benzaldehyde → benzoic acid → maleic acid → CO2 and H2O. This work affords a new idea to prepare high active CeO2 nanowire catalysts for catalytic oxidation of toluene, and open an efficient way for the construction of CeO2 based composite catalysts for VOCs degradation.

Developing high-effective Pt-based high-entropy-alloy electrocatalyst for direct ethylene glycol fuel cells

High entropy alloy (HEA) would be a good approach to improve electrocatalytic utilization of precious metals. Herein, a HEA catalyst of PtBiNiCoSn/C was used in the ethylene glycol oxidation reaction (EGOR) and finally applied to a direct ethylene glycol fuel cell (DEGFC). The results showed that the EGOR current density reached 1.406 A mg‐−1Pt, which exceeded those Pt/C references by 6.39 times. The remaining current density after 3000 s of chronoamperometry (CA) analysis is 0.208 A mg‐−1Pt, which is likewise significantly greater than Pt/C. Notably, the power density reached 8.49 mW cm−2 when combined into the DEGFC anode. This work provides a good HEA catalyst in DEGFC, would promote the widespread use of HEA materials in other electrocatalysis.