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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Energy and Catalysis".

Deadline for manuscript submissions: closed (31 May 2023) | Viewed by 21196

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Prof. Dr. Zuzeng Qin

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School of Chemistry and Chemical Engineering, Guangxi Colleges and Universities Key Laboratory of New Chemical Application Technology in Resources, Guangxi University, Nanning, China
Interests: environmentally friendly catalytic processes; 2D materials; synthesis and separation of fine chemicals; photocatalysis; thermocatalysis; CO₂ conversion; H₂ production; heterogeneous catalysis
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Dear Colleague,

The recent development of nanotechnology has laid the foundation for the design and preparation of various nanostructured materials. Nanostructured materials surpass classical bulk-structured materials due to their unique chemical, physical, electrical, and mechanical properties, and their excellent tunability. Among them, the nanostructural design of catalysts is the most popular topic at the forefront of catalysis research. In the fields of thermocatalytics, electrocatalysis, and photocatalysis, nanomaterial-based catalysts have attracted much attention due to their relatively high efficiency and stability. The nanostructural design of catalysts focuses on composition regulation, size optimization, morphology control, structural engineering, interface engineering, etc., as well as the excellent catalytic performance brought by nano-scale catalysts. At present, the control and design of specific properties (morphology, size, porosity, electrical conductivity, optical properties, photoelectric properties, chemical activity, etc.) of the nanometer material is full of challenges.

This Special Issue will introduce the latest advances and prospects in nanostructural design of catalysts, including the design, preparation, characterization, and computational modeling of nanocatalysts, as well as the catalytic activity and mechanisms of catalytic reactions.

Prof. Dr. Zuzeng Qin
Guest Editor

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Published Papers (10 papers)

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Editorial

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4 pages, 204 KiB

Open AccessEditorial

Nanostructure Design of Catalysts: Latest Advances and Prospects

by Zuzeng Qin

Nanomaterials 2023, 13(13), 1980; https://doi.org/10.3390/nano13131980 - 30 Jun 2023

Cited by 3 | Viewed by 1263

Abstract

The recent development of nanotechnology has laid the foundation for the design and preparation of various nanostructured materials [...] Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

Research

Jump to: Editorial

20 pages, 7923 KiB

Open AccessArticle

Electrocatalytic Oxygen Reduction Reaction of Graphene Oxide and Metal-Free Graphene in an Alkaline Medium

by Saravanan Nagappan, Malarkodi Duraivel, SeongHoon Han, Mohammad Yusuf, Manjiri Mahadadalkar, KyeongMun Park, Amarajothi Dhakshinamoorthy, Kandasamy Prabakar, Sungkyun Park, Chang-Sik Ha, Jae-Myung Lee and Kang Hyun Park

Nanomaterials 2023, 13(8), 1315; https://doi.org/10.3390/nano13081315 - 8 Apr 2023

Cited by 8 | Viewed by 2827

Abstract

Graphene is a well-known two-dimensional material with a large surface area and is used for numerous applications in a variety of fields. Metal-free carbon materials such as graphene-based materials are widely used as an electrocatalyst for oxygen reduction reactions (ORRs). Recently, more attention has been paid to developing metal-free graphenes doped with heteroatoms such as N, S, and P as efficient electrocatalysts for ORR. In contrast, we found our prepared graphene from graphene oxide (GO) by the pyrolysis method under a nitrogen atmosphere at 900 °C has shown better ORR activity in aqueous 0.1 M potassium hydroxide solution electrolyte as compared with the electrocatalytic activity of pristine GO. At first, we prepared various graphene by pyrolysis of 50 mg and 100 mg of GO in one to three alumina boats and pyrolyzed the samples under a N₂ atmosphere at 900 °C. The prepared samples are named G50-1B to 3B and G100-1B and G100-2B. The prepared GO and graphenes were also analyzed under various characterization techniques to confirm their morphology and structural integrity. The obtained results suggest that the ORR electrocatalytic activity of graphene may differ based on the pyrolysis conditions. We found that G100-1B (E_onset, E_1/2, J_L, and n values of 0.843, 0.774, 4.558, and 3.76) and G100-2B (E_onset, E_1/2, and J_L values of 0.837, 0.737, 4.544, and 3.41) displayed better electrocatalytic ORR activity, as did Pt/C electrode (E_onset, E_1/2, and J_L values of 0.965, 0.864, 5.222, and 3.71, respectively). These results display the wide use of the prepared graphene for ORR and also can be used for fuel cell and metal–air battery applications. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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14 pages, 3934 KiB

Open AccessArticle

Characterization of Modified Mechanically Activated Cassava Starch Magnetic Porous Microspheres and Its Adsorption for Cd(II) Ions

by Xinling Xie, Xiaona Zhao, Xuan Luo, Youquan Zhang, Zuzeng Qin and Hongbing Ji

Nanomaterials 2023, 13(3), 513; https://doi.org/10.3390/nano13030513 - 27 Jan 2023

Cited by 3 | Viewed by 1509

Abstract

The magnetic polymer microsphere is a promising adsorbent due to its high adsorption efficiency and good regeneration ability from wastewater. Cassava starch magnetic porous microspheres (AAM-MSMPMs) were synthesized by graft copolymerization in inverse emulsion. Mechanically activated cassava starch (MS) was used to graft skeletons, vinyl monomers [acrylic acid (AA) and acrylamide (AM)] as copolymerized unsaturated monomers, methyl methacrylate (MMA) as the dispersing agent, and polyethylene glycol/methanol (PEG2000/MeOH) as the porogen. It was found that the AAM-MSMPM adsorbent is superparamagnetic, the saturation magnetization is 14.9 emu·g^–1, and it can be rapidly and directionally separated from Cd(II) ions in aqueous solution. The FTIR indicated that the carboxyl and hydroxyl groups were grafted into MS. The AAM-MSMPM had good speroidization and a uniform size. After the porogen was added, the particle size of the AAM-MSMPM decreased from 19.00 to 7.00 nm, and the specific surface area increased from 7.00 to 35.00 m²·g^–1. The pore volume increased from 0.03 to 0.13 cm³·g^–1. The AAM-MSMPM exhibited a large specific surface area and provided more adsorption active sites for Cd(II) ions. The maximum adsorption capacity of the AAM-MSMPM for Cd(II) ions was 210.68 mg·g^–1, i.e., 81.02% higher than that without porogen. Additionally, the Cd(II) ion adsorption process on the AAM-MSMPM can be described by Langmuir isothermal and pseudo-second-order kinetic models. A chemical reaction dominated the Cd(II) ion adsorption process on the AAM-MSMPM, and chemisorption was the rate-controlling step during the Cd(II) ion adsorption process. The AAM-MSMPM still had excellent stability after five consecutive reuses. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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14 pages, 2831 KiB

Open AccessArticle

Novel PEPPSI-Type NHC Pd(II) Metallosurfactants on the Base of 1H-Imidazole-4,5-dicarboxylic Acid: Synthesis and Catalysis in Water–Organic Media

by Vladimir Burilov, Dmitriy Radaev, Elza Sultanova, Diana Mironova, Daria Duglav, Vladimir Evtugyn, Svetlana Solovieva and Igor Antipin

Nanomaterials 2022, 12(22), 4100; https://doi.org/10.3390/nano12224100 - 21 Nov 2022

Cited by 6 | Viewed by 1709

Abstract

Carrying out organic reactions in water has attracted much attention. Catalytic reactions in water with metallosurfactants, which have both a metallocenter and the surface activity necessary for solubilizing hydrophobic reagents, are of great demand. Herein we proposed new approach to the synthesis of NHC PEPPSI metallosurfactants based on the sequential functionalization of imidazole 4,5-dicarboxylic acid with hydrophilic oligoethylene glycol and lipophilic alkyl fragments. Complexes of different lipophilicity were obtained, and their catalytic activity was studied in model reduction and Suzuki–Miyaura reactions. A comparison was made with the commercial PEPPSI-type catalytic systems designed by Organ. It was found that the reduction reaction in an aqueous solution of the metallosurfactant with the tetradecyl lipophilic fragment was three times more active than the commercially available PEPPSI complexes, which was associated with the formation of stable monodisperse aggregates detected by DLS and TEM. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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25 pages, 4618 KiB

Open AccessArticle

Assessment of the Catalytic Performances of Nanocomposites Materials Based on 13X Zeolite, Calcium Oxide and Metal Zinc Particles in the Residual Biomass Pyrolysis Process

by Elena David and Janez Kopac

Nanomaterials 2022, 12(21), 3841; https://doi.org/10.3390/nano12213841 - 31 Oct 2022

Cited by 2 | Viewed by 1708

Abstract

Nanocomposites based on 13X zeolite (13XZ), calcium oxide (CaO) and metal zinc particles (Zn) were prepared. The resulting nanocomposites were characterized by different techniques. Then, a comparative study on catalytic and noncatalytic pyrolysis of biomass waste was performed to establish the influence of nanocomposites used as catalysts on the yields and characteristics of liquid and solid products. Residual rapeseed biomass (RRB) was employed for pyrolysis experiments and a fixed bed reactor was used. By introducing CaO and metal zinc particles into 13X zeolite mass, the surface area (S_BET) of nanocomposites was reduced, and this decrease is due to the introduction of nano-calcium carbonate and nano-zinc particles, which occupied an important space into zeolite structure. By adding CaO to 13XZ, the pore structure was changed and there was a decrease in the micropores volume. The analysis of the pore area distribution showed a hierarchical pore structure for nanocomposites. The elements composition showed that the main elements contained in nanocomposites are Si, Al, Ca and Zn, confirming the preservation of the zeolite structure. Using these nanocomposites as catalysts in pyrolysis process, the residual biomass could be valorized, producing bio-oil and biochar for the management and sustainability of this low-value waste. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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20 pages, 8749 KiB

Open AccessArticle

Catalytic Ozonation of Ibuprofen in Aqueous Media over Polyaniline–Derived Nitrogen Containing Carbon Nanostructures

by Angel-Vasile Nica, Elena Alina Olaru, Corina Bradu, Anca Dumitru and Sorin Marius Avramescu

Nanomaterials 2022, 12(19), 3468; https://doi.org/10.3390/nano12193468 - 4 Oct 2022

Cited by 8 | Viewed by 1887

Abstract

Catalytic ozonation is an important water treatment method among advanced oxidation processes (AOPs). Since the first development, catalytic ozonation has been consistently improved in terms of catalysts used and the optimization of operational parameters. The aim of this work is to compare the catalytic activity of polyaniline (PANI) and thermally treated polyaniline (PANI 900) in the catalytic ozonation of ibuprofen solutions at different pH values (4, 7, and 10). Catalysts were thoroughly characterized through multiple techniques (SEM, Raman spectroscopy, XPS, pHPZC, and so on), while the oxidation process of ibuprofen solutions (100 mgL⁻¹) was assessed by several analytical methods (HPLC, UV254, TOC, COD, and BOD5). The experimental data demonstrate a significant improvement in ibuprofen removal in the presence of prepared solids (20 min for PANI 900 at pH10) compared with non-catalytic processes (56 min at pH 10). Moreover, the influence of solution pH was emphasized, showing that, in the basic region, the removal rate of organic substrate is higher than in acidic or neutral range. Ozone consumption mgO₃/mg ibuprofen was considerably reduced for catalytic processes (17.55—PANI, 11.18—PANI 900) compared with the absence of catalysts (29.64). Hence, beside the ibuprofen degradation, the catalysts used are very active in the mineralization of organic substrate and/or formation of biodegradable compounds. The best removal rate of target pollutants and oxidation by-products was achieved by PANI 900, although raw polyaniline also presents important activity in the oxidation process. Therefore, it can be stated that polyaniline-based catalysts are effective in the oxidation processes. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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12 pages, 3215 KiB

Open AccessArticle

Tug-of-War Driven by the Structure of Carboxylic Acids: Tuning the Size, Morphology, and Photocatalytic Activity of α-Ag₂WO₄

by Lara Kelly Ribeiro, Amanda Fernandes Gouveia, Francisco das Chagas M. Silva, Luís F. G. Noleto, Marcelo Assis, André M. Batista, Laécio S. Cavalcante, Eva Guillamón, Ieda L. V. Rosa, Elson Longo, Juan Andrés and Geraldo E. Luz Júnior

Nanomaterials 2022, 12(19), 3316; https://doi.org/10.3390/nano12193316 - 23 Sep 2022

Cited by 11 | Viewed by 2111

Abstract

Size and morphology control during the synthesis of materials requires a molecular-level understanding of how the addition of surface ligands regulates nucleation and growth. In this work, this control is achieved by using three carboxylic acids (tartaric, benzoic, and citric) during sonochemical syntheses. The presence of carboxylic acids affects the kinetics of the nucleation process, alters the growth rate, and governs the size and morphology. Samples synthesized with citric acid revealed excellent photocatalytic activity for the degradation process of Rhodamine B, and recyclability experiments demonstrate that it retains 91% of its photocatalytic activity after four recycles. Scavenger experiments indicate that both the hydroxyl radical and the hole are key species for the success of the transformation. A reaction pathway is proposed that involves a series of dissolution−hydration–dehydration and precipitation processes, mediated by the complexation of Ag⁺. We believe these studies contribute to a fundamental understanding of the crystallization process and provide guidance as to how carboxylic acids can influence the synthesis of materials with controlled size and morphology, which is promising for multiple other scientific fields, such as sensor and catalysis fields. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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10 pages, 3448 KiB

Open AccessArticle

One-Pot Preparation of HTPB/nNi and Its Catalyst for AP

by Shuxia Bao, Tingrun Li, Chunyu Guo, Yangyang Zhao, Huijuan Zhang, Ruifeng Wu and Heping Shi

Nanomaterials 2022, 12(15), 2669; https://doi.org/10.3390/nano12152669 - 3 Aug 2022

Cited by 1 | Viewed by 2034

Abstract

The liquid phase reduction method is a common method used for preparing nano-nickel powder (nNi). However, the nNi surface is easily oxidized to form nickel oxide film, which affects its performance. In this work, nNi was prepared using anhydrous ethanol as a solvent and hydrazine hydrate as a reducing agent. Furthermore, HTPB/nNi composites were prepared using hydroxyl-terminated polybutadiene (HTPB) as a coating agent. The structure and morphology of the samples are characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The catalytic behavior of HTPB/nNi on the thermal decomposition of ammonium perchlorate (AP) is studied by differential scanning calorimetry (DSC) and thermogravimetric analyzer (TG). The results show that HTPB/nNi has little effect on the low temperature thermal decomposition of AP, but the peak of high temperature thermal decomposition advances from 456 °C to 332 °C. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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21 pages, 6481 KiB

Open AccessArticle

Bagasse Cellulose Composite Superabsorbent Material with Double-Crosslinking Network Using Chemical Modified Nano-CaCO₃ Reinforcing Strategy

by Xinling Xie, Li Ma, Yongmei Chen, Xuan Luo, Minggui Long, Hongbing Ji and Jianhua Chen

Nanomaterials 2022, 12(9), 1459; https://doi.org/10.3390/nano12091459 - 25 Apr 2022

Cited by 10 | Viewed by 2652

Abstract

To improve the salt resistance of superabsorbent materials and the gel strength of superabsorbent materials after water absorption, a bagasse cellulose-based network structure composite superabsorbent (CAAMC) was prepared via graft copolymerization of acrylamide/acrylic acid (AM/AA) onto bagasse cellulose using silane coupling agent modified nano-CaCO₃ (MNC) and N,N′-methylene bisacrylamide (MBA) as a double crosslinker. The acrylamide/acrylic acid was chemically crosslinked with modified nano-CaCO₃ by C-N, and a stable double crosslinked (DC) network CAAMC was formed under the joint crosslinking of N,N′-methylene bisacrylamide and modified nano-CaCO₃. Modified nano-CaCO₃ plays a dual role of crosslinking agent and the filler, and the gel strength of composite superabsorbent is two times higher than that of N,N′-methylene bisacrylamide single crosslinking. The maximum absorbency of CAAMC reached 712 g/g for deionized water and 72 g/g for 0.9 wt% NaCl solution. The adsorption process of CAAMC was simulated by materials studio, and the maximum adsorption energy of amino and carboxyl groups for water molecules is −2.413 kJ/mol and −2.240 kJ/mol, respectively. According to the results of CAAMC soil water retention, a small amount of CAAMC can greatly improve the soil water retention effect. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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15 pages, 5683 KiB

Open AccessArticle

Preparation and Drug-Loading Properties of Amphoteric Cassava Starch Nanoparticles

by Xinling Xie, Youquan Zhang, Yong Zhu and Yiling Lan

Nanomaterials 2022, 12(4), 598; https://doi.org/10.3390/nano12040598 - 10 Feb 2022

Cited by 8 | Viewed by 2388

Abstract

Based on the characteristics of charge reversal around the isoelectric point (pI) of amphoteric starch-containing anionic and cationic groups, amphoteric cassava starch nanoparticles (CA-CANPs) are prepared by a W/O microemulsion crosslinking method using (3-chloro-2-hydroxypropyl) trimethyl ammonium chloride as a cationic reagent and POCl₃ as an anionic reagent, and the effects of preparation conditions on the particle size of the CA-CANPs are studied in detail in the present study. CA-CANPs with a smooth surface and an average diameter of 252 nm are successfully prepared at the following optimised conditions: a crosslinking agent amount of 15 wt%, an aqueous starch concentration of 6.0 wt%, an oil–water ratio of 10:1, a total surfactant amount of 0.20 g·mL⁻¹, and a CHPTAC amount of 4.05 wt%. The pH-responsive value of the CA-CANPs can be regulated by adjusting the nitrogen–phosphorus molar ratio in the CA-CANPs. By using CA-CANPs with a pI of 6.89 as drug carriers and the paclitaxel (PTX) as a model drug, the maximum loading rate of 36.14 mg·g⁻¹ is achieved, and the loading process is consistent with the Langmuir isotherm adsorption, with the calculated thermodynamic parameters of ΔH° = −37.91 kJ·mol⁻¹, ΔS° = −10.96 J·mol⁻¹·K⁻¹ and ΔG° < 0. By testing the release rate in vitro, it is noted that the release rates of PTX in a neutral environment (37.6% after 96 h) and a slightly acidic environment (58.65% after 96 h) are quite different, suggesting that the CA-CANPs have the possibility of being a targeted controlled-release carrier with pH responsiveness for antitumor drugs. Full article

(This article belongs to the Special Issue Nanostructures Design for Catalyst: Latest Advances and Prospects)

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