Inorganic Supports Research Articles

Green synthesis of the ZnO/ZSM-5 composite by using Convolvulus persicus extract: As an efficient and reusable catalyst in the Biginelli reaction

The active catalytic materials in stable inorganic supports are increasingly developing for the creation of ultra-stable catalysts with excellent performance. Here, the ZnO was supported on the surface of ZSM-5-type zeolite using Convolvulus persicus extract as a mild, efficient, cost‐effective, and eco‐friendly approach. The structure of the synthesized nanocatalyst was characterized using different techniques including UV, FT-IR, XRD, FE-SEM, EDS/Map, TGA, BET, and ICP-OES. The application of the ZnO/ZSM-5 as a catalyst was investigated in the Biginelli reaction between urea/thiourea, ethyl acetoacetate, and various aldehydes. Based on the results, ZnO/ZSM-5 exhibited good catalytic behavior, and the products were produced in excellent yields (90–95 %) in EtOH. This catalyst has notable benefits such as easy recovery and reusability (at least for five consecutive runs), simple work‐up, and high product yields.

Nanostructured Aluminum Oxyhydroxide-A Prospective Support for Functional Porphyrin-Based Materials.

A method for the grafting of unsymmetrical A2BC-type 5,15-bis(4-butoxyphenyl)-10-(4-carboxyphenyl)-20-(phenanthrenoimidazolyl)-porphyrin onto the surface of nanostructured aluminum oxyhydroxide modified with a single SiO2 layer (NAOM) was successfully developed. A straightforward procedure towards surface modification of NAOM allowed us to prepare a new porphyrin-containing hybrid material. The obtained 3D heterostructure was extensively characterized using XPS, TEM and diffuse reflectance spectroscopy. Structural and morphological peculiarities of the inorganic support before and after the immobilization procedure were studied and discussed in detail. The stability of the material against leaching and the porphyrin immobilization ratio ca. 14% by weight were also revealed.

Ecological hybrid pigments with improved thermal, light, and chemical stability based on purpurin dye and different minerals for applications in polymer materials

A facile and cost-effective route was developed for the production of high-performance hybrid pigments by the stabilization of the natural red dye (purpurin) on mineral supports. For the first time, hydrotalcite (LDH), sepiolite (SEP), and aluminum-magnesium hydroxycarbonate (LH30) with different chemical compositions and structures were used as inorganic supports for purpurin. The physico-chemical properties of the prepared pigments were characterized by time-of-flight secondary ion mass spectrometry (ToF-SIMS), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), color measurements, release kinetic experiments, and thermogravimetric analysis (TGA). Purpurin molecules were confirmed to have been successfully incorporated into the inorganic supports via interactions between the purpurin chromophore and Mg2+, Zn2+ and/or Al3+ ions from the mineral host. The interactions resulted in hybrid pigments with higher thermal stability and lower tendency to migrate, without changing the morphology of the minerals. The hybrid pigments were applied as new colorants for ethylene-norbornene copolymer. The polymer composites were subjected to long-term UV irradiation followed by color and mechanical measurements. The results suggest that purpurin-based hybrid pigments can act as durable and effective colorants. This work provides a novel approach for preparing stable and multifunctional hybrid pigments based on natural dyes and mineral supports.

Role of potash fertilization through organic and inorganic sources on growth and yield of turmeric

Aim: To investigate the possibility of substitution of inorganic inputs through organics and to evaluate the effects of bioorganic inputs on microbial population of soil. Methodology: A field experiment of RBD with 13 treatments and 3 replication using combination of organic manures viz., compost/vermicompost, potassic mobilising inoculants along with graded (100, 75 and 50%) levels of inorganic potassium were tried for partial substitution of inorganic potassium with organic source in turmeric cv. Suguna. Results: Considering the yield, the vermicompost + inorganic K (100%) + K mobiliser (32.35 t ha-1) was the best treatment, followed by Compost + K 100% + KM (31.13 t ha-1). Interpretation: These results indicate that soils were less fertile due to deficit in soil nutrients. Recommended doses of organic bio-fertilizer and inorganic fertilizer should be practiced for reclamation of soil status. Application of potassic mobilizer as biofertilizer in turmeric can reduce the application of inorganic potassium and support eco-friendly crop production. Key words: Compost, Curcuma longa, Organic manures, Potassic mobilizer, Turmeric, Vermicompost

Shaping Silver Nanoparticles' Size through the Carrier Composition: Synthesis and Antimicrobial Activity.

The increasing resistance of bacteria to conventional antibiotics represents a severe global emergency for human health. The broad-spectrum antibacterial activity of silver has been known for a long time, and silver at the nanoscale shows enhanced antibacterial activity. This has prompted research into the development of silver-based nanomaterials for applications in clinical settings. In this work, the synthesis of three different silver nanoparticles (AgNPs) hybrids using both organic and inorganic supports with intrinsic antibacterial properties is described. The tuning of the AgNPs' shape and size according to the type of bioactive support was also investigated. Specifically, the commercially available sulfated cellulose nanocrystal (CNC), the salicylic acid functionalized reduced graphene oxide (rGO-SA), and the commercially available titanium dioxide (TiO2) were chosen as organic (CNC, rGO-SA) and inorganic (TiO2) supports. Then, the antimicrobial activity of the AgNP composites was assessed on clinically relevant multi-drug-resistant bacteria and the fungus Candida albicans. The results show how the formation of Ag nanoparticles on the selected supports provides the resulting composite materials with an effective antibacterial activity.

NiO and ZrO2 impregnation in KIT-6 by excess solvent and mechanochemistry: A comparison

Metal oxides have been widely used in heterogeneous catalysis. One of the most used methods currently to impregnate metallic oxides in inorganic supports is the wet method, however, this has some disadvantages. In this work, the impregnation of NiO and ZrO2 in KIT-6 was carried out by the excess solvent and mechanochemical method to compare the most advantageous method. The obtained materials were characterized by X-ray diffraction analysis (XRD), X-ray fluorescence spectrometry (XRF), scanning electron microscopy (SEM) and N2 adsorption and desorption. The results revealed that the impregnation did not modify the typical structure of the support. Moreover, the insertion of the oxides promoted a decrease in the specific area and in the total volume of pores. The catalysts showed similar characteristics for both methods. However, when considering time and other subsequent steps, the mechanochemical method was considered more advantageous.

Correlating O-Vacancy and Hydrogen Spillover with Activity and Selectivity in Furfural Hydrogenation Using Nanocatalysts Comprised of Ru Nanoparticles Supported on TiO2–SiO2

The nanoengineering of efficient and stable nanocatalysts is highly desired for sustainable biomass valorization toward the selective hydrogenation of furfural. The interaction of supports with metallic nanoparticles and oxygen vacancies has a significant role in the catalytic activity of oxide nanocatalysts. Here, by combining density functional theory (DFT) calculations and catalytic experimental data, we demonstrated that the presence of TiO2 in Ru–SiO2 catalysts might allow an association between oxygen vacancies and the hydrogen spillover effect. Specifically, Ru–TiO2–SiO2 and Ru–SiO2 nanocatalysts displayed improved activities and selectivities toward the reaction mentioned above. The nanomaterials were prepared by a simple, versatile, and single-step modified sol–gel process build upon two different stabilizing agents (P123 and CTAB), which afforded entirely covered surfaces of TiO2–SiO2 and SiO2 supports with uniform small Ru nanoparticles generated in situ. The Ru-TSdc nanocatalyst displayed several interesting promising nanoscale features for hydrogenation of furfural: (i) uniform distribution of Ru, Ti, and Si elements over the entire catalyst surface, (ii) deposition of small Ru nanoparticles with no significant particle agglomeration, (iii) facilitated hydrogen spillover from Ru NPs to the TiO2 support, and (iv) a significant amount of oxygen vacancies at the nanoparticle surface. For these reasons, the Ru-TSdc sample afforded the optimal performance toward the selective hydrogenation of furfural (up to 99% of selectivity), maintaining good conversions in certain reaction conditions. This work demonstrates how the catalytic activity of metallic nanoparticles could be improved by the structural addition of a reducible oxide, leading to more efficient inorganic supports and for preparing nanocatalysts.

Development and characterization of novel low-cost engineered pine needle biochar and montmorillonite clay based proton exchange membrane for microbial fuel cell

Microbial fuel cells (MFC) are a potential method for treating wastewater and recovering energy. Proton exchange membranes (PEM) are one of the MFC's main parts and have a big impact on both how well it works and how much it costs. In this paper, low cost and affordable membrane was developed from forestry waste pine needles. Pine needle (PN) biochar was prepared by pyrolysis at 600 °C and then sulphonation was done. Sulphonated pine needle biochar (SPB) was mixed with montmorillonite clay (MMT) as inorganic support for preparing membrane. Conductivity, ion exchange capacity, and proton mass transfer coefficient of different membranes were evaluated and found to be 2.53 ± 0.23 S/cm × 10−4, 3.27 meq/g, and 11.35 × 10−5, respectively for SPB30-MMT. Compared to bare MMT membrane (6.13 %), SPB30-MMT membrane had a greater water uptake capacity (31.95 %). These membranes were examined by deploying in MFCs and gave 86 % chemical oxygen demand removal efficiency and 297 mV voltage output, simultaneously. This study indicates that PN biochar-based membranes could be an affordable option for producing bioelectricity through microbial fuel cells.

Novel Catalyst Composites of Ni- and Co-Based Nanoparticles Supported on Inorganic Oxides for Fatty Acid Hydrogenations.

In the quest to develop nanometrically defined catalytic systems for applications in the catalytic valorization of agri-food wastes, small Ni-based nanoparticles supported on inorganic solid supports have been prepared by decomposition of organometallic precursors in refluxing ethanol under H2 atmosphere, in the presence of supports exhibiting insulating or semi-conductor properties, such as MgAl2O4 and TiO2, respectively. The efficiency of the as-prepared Ni-based nanocomposites has been evaluated towards the hydrogenation of unsaturated fatty acids under solvent-free conditions, with high selectivity regarding the hydrogenation of C=C bonds. The influence of the support on the catalytic performance of the prepared Ni-based nanocomposites is particularly highlighted.

Immobilized Polyolefin Catalysts: Organic Versus Inorganic Supports

Annals of Chemical Science Research Immobilized Polyolefin Catalysts: Organic Versus Inorganic Supports Xiong Wang1*, Guangquan Li1, Pinglin He2, Dewen Chen3 and Wenqian Kang1 1Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, China 2Polyolefin Operation Department II, Lanzhou Petrochemical Company, PetroChina, China 3Chemical Operation Department I, Lanzhou Petrochemical Company, PetroChina, China *Corresponding author:Xiong Wang, Lanzhou Petrochemical Research Center, Petrochemical Research Institute, PetroChina, Lanzhou 730060, China Submission: March 21, 2023;Published: March 29, 2023 DOI: 10.31031/ACSR.2023.03.000572 Volume3 Issue5March , 2023

Metalloporphyrin-based multifunctional catalysts for one-pot assisted Tandem reaction

Multicomponent and multifunctional solid catalysts based on the tetra-anionic manganese(III)porphyrin Na4[Mn(TDFSPP)(Oac)] (MnP) immobilized on inorganic supports composed of silica/WO3/layered material were idealized, prepared and investigated as catalyst solids for heterogeneous process in one-pot cyclohexane oxidation to cyclohexanol and cyclohexanone followed by ketalization of the cyclohexanone carbonyl group to dimethyl cyclohexanone ketal with methanol. We expected that the MnP would catalyze cyclohexane oxidation, and that the acid sites of the silica/WO3/layered material would assist cyclohexanone/methanol ketalization. After establishing the optimal conditions for the single organic reactions separately, we proposed the proof-of-concept one-pot assisted Tandem reaction of cyclohexane oxidation to cyclohexanol and cyclohexanone with PhIO catalyzed by silica/WO3/layered material/MnP and ketalization of the cyclohexanone carbonyl groups with methanol to obtain dimethyl cyclohexanone ketal as final product.

THE ROLE OF THE ORGANIC FERTILIZER PROCESSING UNIT (UPPO) ON RICE FARMERS' INCOME IN DELI SERDANG DISTRICT

In efforts to minimize the use of inorganic fertilizers and support farmers in using and supplying organic fertilizers independently, the government facilitates providing assistance in the form of Organic Fertilizer Processing Units (UPPO). It is hoped that the availability of organic fertilizers can lead to organic farming. This study aims to determine the role of UPPO on the income of lowland rice farmers in Deli Serdang district and to analyze other factors besides UPPO that affect farmers' income. This research was conducted on eight beneficiary farmer groups spread over seven sub-districts in Deli Serdang district with a total population of 70 farmers. The research method uses analysis of validity and reliability tests, classical assumption tests, and regression analysis. The results showed that all research variables separately had a significant effect on farmers' income.

Hydrogen-sieving zeolitic films by coating zeolite nanosheets on porous polymeric support

The synthesis of high-performance gas-sieving zeolitic film is challenging because it involves seeded secondary growth which is complex and difficult to reproduce. Additionally, expensive asymmetric inorganic porous supports are often needed for calcination of the zeolite films. Herein, scalable preparation of H2-sieving RUB-15 nanosheet films is reported bypassing the need for secondary growth and expensive supports. A novel, low-cost, thermally-robust, porous polybenzimidazole copolymer (PBI-AM Fumion®) support is prepared which allows deposition of thin, compact, and oriented RUB-15 nanosheets films without cracks or pinhole defects. The film hosts two transport pathways, H2-sieving six-membered silicate rings in the nanosheets and nonselective intersheet gaps maintained by the organic guest species in the gallery spacing. The latter is eliminated by a low-temperature (330 °C) calcination where the crystalline order in the nanosheets is preserved. The resulting zeolitic films yielded H2 permeances of 100–400 GPU and H2/CO2 selectivities above 20 at temperatures above 200 °C. The facile and scalable fabrication procedure with an attractive H2-sieving performance at elevated temperatures make these membranes promising for pre-combustion carbon capture.

Cover Feature: Single‐Atom Materials as Electrochemical Sensors: Sensitivity, Selectivity, and Stability (Anal. Sens. 3/2023)

The cover feature image shows electrochemical sensing using single-atom materials (SAMs) featuring isolated metal sites embedded inside inorganic or organic supports. Thanks to the well-defined active sites, SAMs have demonstrated expectational performance. The current research progress of metal-inorganic/organic SAMs is discussed, providing an introductive outline of the rational sensor design toward higher sensitivity, selectivity, and stability. Cover design by Weiran Zheng. More information can be found in the Review by Weiran Zheng.

Simultaneous reduction of 4-nitrophenol, 4-nitroaniline and methylene blue organic pollutants via TiO2 supported Pd(II) complex catalyst bearing 2-(6-methylpyridin-2-yl)-1H-benzimidazole type ligand

In this study, 2-(6-methylpyridin-2-yl)-1H-benzimidazole derivative ligand (L) and its Pd(II) complex (Pd(L)Cl2) were synthesized and characterized by spectroscopic techniques. The crystal structure of L was characterized by X-ray diffraction method, and the structural, spectroscopic and electronic properties were obtained using density functional method (DFT). The catalyst material of the Pd(II) complex was prepared by attaching the complex to the titanium dioxide (TiO2) inorganic support material at a ratio 15 % (15 % Pd(L)Cl2-TiO2). 15 % Pd(L)Cl2-TiO2 catalyst material was characterized by FT-IR, TG, SEM-EDX and XRD analysis methods and used as catalyst in the catalytic reduction of 4-nitrophenol (4-NP), 4-nitroaniline (4-NA) and methylene blue (MB) organic pollutants. High conversion values were obtained for the reduction of 4-NP, 4-NA and MB substrates by 15 % Pd(L)Cl2-TiO2 catalyst material as a synergistic result of the unique catalytic properties of the Pd metal and the photocatalyst property of the TiO2 semiconductor that used as the inorganic support material.

The Impact of Functionality and Porous System of Nanostructured Carriers Based on Metal–Organic Frameworks of UiO-66-Type on Catalytic Performance of Embedded Au Nanoparticles in Hydroamination Reaction

New methods for the preparation of metal–organic frameworks UiO-66 and NH2-UiO-66 with a hierarchical porous structure were developed using the MW-assisted technique under atmospheric pressure. The synthesized nanostructured meso-UiO-66 and meso-NH2-UiO-66 matrices were utilized as Au nanoparticle carriers. The resulting Au@meso-UiO-66 and Au@NH2-UiO-66 nanohybrids were studied in the reaction of phenylacetylene hydroamination with aniline into imine ([phenyl-(1-phenylethylydene)amine]) for the first time. Their catalytic behavior is significantly determined by a combination of factors, such as a small crystal size, micro–mesoporous structure, and functionality of the UiO-66 and NH2-UiO-66 carriers, as well as a high dispersion of embedded gold nanoparticles. The Au@meso-UiO-66 and Au@NH2-UiO-66 nanocatalysts demonstrate high activities (TOF), with conversion and selectivity values over 90. This excellent catalytic performance is comparable or even better than that demonstrated by heterogeneous systems based on conventional inorganic and inorganic supports known from the literature.

Study on the Roles of Water in Solid Amine-Based Direct Air Capture of CO2

Climate change triggered by the increasing amount of CO2 released into the atmosphere has become a global priority. Direct Air Capture (DAC) of CO2 has been regarded as one of the disruptive technologies to realize negative emission. Among the multiple strategies employed, adsorption on solid amines is a promising choice owing to its low energy requirements. Since the water vapor ubiquitously exists in ambient air, understanding the role it plays in DAC by the amine-functionalized solid sorbents is of vital importance. Due to the diversity in amine and support features, both promotion and deterioration of water impact on CO2 adsorption were revealed. Herein we present a multifaceted review of the trends and innovations in DAC by solid amines under humid conditions. The effect of water was discussed over four groups of materials, based on the support categories, i.e., (a) mesoporous silica, (b) mesoporous alumina, (c) mesoporous carbon and other inorganic supports, and (d) cellulose and other organic supports.

Inorganic non-carbon supported Pt catalysts and synergetic effects for oxygen reduction reaction

In oxygen reduction reaction, Pt/C catalysts are prone to carbon corrosion, resulting in reduced activity. The use of non-carbon inorganic supports not only improves corrosion resistance, but also provides synergetic effects to increase activity and stability.

Organic-inorganic interface chemistry for sustainable materials

Abstract This mini-review focuses on up-to-date advances of hybrid materials consisting of organic and inorganic components and their applications in different chemical processes. The purpose of forming such hybrids is mainly to functionalize and stabilize inorganic supports by attaching an organic linker to enhance their performance towards a target application. The interface chemistry is present with the emphasis on the sustainability of their components, chemical changes in substrates during synthesis, improvements of their physical and chemical properties, and, finally, their implementation. The latter is the main sectioning feature of this review, while we present the most prosperous applications ranging from catalysis, through water purification and energy storage. Emphasis was given to materials that can be classified as green to the best in our consideration. As the summary, the current situation on developing hybrid materials as well as directions towards sustainable future using organic-inorganic hybrids are presented.

Tunable Latency of Hydrosilylation Catalyst by Ligand Density on Nanoparticle Supports.

Functionalizing inorganic particles with organic ligands is a common technique for heterogenizing organometallic catalysts. We describe how coordinating molecular platinum to silica nanoparticles functionalized with a high density of norbornene ligands causes unexpected latency of the catalytic activity in hydrosilylation reactions when compared to an identical reaction in which the norbornene is not tethered (2 % vs 97 % conversion in 1 h). Performing the hydrosilylation at elevated temperature (70 °C) suppresses this activity delay, suggesting the usefulness of this technique towards temperature-triggered catalysis. We demonstrate that this latency is related to ligand density on the particle surface, chemical structure of the norbornene, and silica nanoparticle topology. We also establish the benefit of this latency for triggered curing of silicone elastomers. Overall, our work establishes the non-innocent role of inorganic supports when functionalized with organometallic complexes.