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Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: 31 May 2024 | Viewed by 6555

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Prof. Dr. Zeba N. Siddiqui

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Green Chemistry Laboratory, Organic Chemistry Division, Department of Chemistry, Aligarh Muslim University, Aligarh 202002, India
Interests: green chemistry; heterogeneous catalysis; heterocyclic chemistry; synthetic organic chemistry

Prof. Dr. Saeed M. Al-Zahrani

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SABIC Polymer Research Center (SPRC), Department of Chemical Engineering, College of Engineering, King Saud University, Riyadh 11421, Saudi Arabia
Interests: catalysis; catalyst characterization; composites; nanocomposites; structure–property relationship; physical characterization; mechanical characterization; morphological characterization; applications of composites
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Prof. Dr. Ajay Kumar Mishra

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Department of Chemistry, Durban University of Technology, Steve Biko Road, Durban 4001, South Africa
Interests: nanoscience/nanotechnology; nanocomposites; functional materials; industrial waste; wastewater treatment

Special Issue Information

Dear Colleagues,

Since the term “catalysis” was coined more than a hundred years ago, catalysts have been used in almost all kinds of chemical transformations. The growing global demand for environmentally friendly and cost-effective protocols, especially for industrial purposes, has inspired an increased interest in the development of novel recyclable catalysts. Over the past few decades, many nanomaterial-based heterogeneous catalysts with plenty of advantages over homogeneous catalysts in terms of cost, reusability, and eco-friendliness have been used. Nanomaterials such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and covalent organic polymers (COPs) have been used for this purpose, either as support materials or as catalysts. Furthermore, ionic liquids (ILs), hetero-poly acids (HPAs), and metal nanoparticles (MNPs) have also been used for developing nanomaterial-based heterogeneous catalysts. Various techniques including Fourier Transform Infrared (FTIR), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Powder X-ray diffraction (PXRD), Brunauer–Emmett–Teller (BET), Energy Dispersive X-ray (EDX), and Thermal Gravimetric (TG) analyses have been employed for the characterization of nanomaterial-based catalysts. In view of the increasing importance of and concern about advanced nanomaterial-based catalysts, we encourage manuscripts covering progress in the design and synthesis of advanced nanomaterial-based catalysts, their characterization through cutting-edge techniques, and their application in catalysis with a thorough understanding of the reaction mechanism.

Prof. Dr. Zeba N. Siddiqui
Prof. Dr. Saeed M. Al-Zahrani
Prof. Dr. Ajay Kumar Mishra
Guest Editors

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Keywords

metal organic framework
covalent organic framework
covalent organic polymer
ionic liquid
metal nano particle

Published Papers (7 papers)

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Research

16 pages, 8280 KiB

Open AccessArticle

Efficient Catalytic Degradation of Methyl Orange by Various ZnO-Doped Lignin-Based Carbons

by Zhihao Tang, Yonggang Yang and Weiqi Wei

Molecules 2024, 29(8), 1817; https://doi.org/10.3390/molecules29081817 - 17 Apr 2024

Viewed by 385

Abstract

Herein, a series of ZnO-doped lignin-based carbons (LC/ZnO) were successfully prepared from different types of lignin and used for methyl orange (MO) photocatalytic degradation. The apparent morphology, internal structure, and photoelectric properties of prepared LC/ZnO composites and their effects on subsequent MO photocatalytic degradation were investigated by various characterization techniques. The results showed that the LC/ZnO composites that were prepared in this work mainly consisted of highly dispersed ZnO nanoparticles and lignin-based carbon nano-sheets, which were beneficial for subsequent photogenerated electrons and holes formation, dispersion, and migration. The MO could be significantly degraded with various ZnO-doped lignin-based carbons, especially over the LC_SL/ZnO, and the maximum degradation rate was 96.9% within 30 min under the simulated 300w sunlight exposure. The experiments of free radical elimination showed that the photocatalytic degradation of MO over LC/ZnO were a result of the co-action of multiple free radicals, and h⁺ might play the predominant roles in MO degradation. In addition, the pH of the solution had little effect on MO degradation, and the MO could be effectively degraded even in an alkaline solution of pH = 12.0. The cycling experiments showed that the prepared LC/ZnO had a good stability for MO photodegradation, especially for LC_SL/ZnO, even after 5 times recycling, and the degradation rate of MO only dropped from 97.0% to 93.0%. The research not only provided a fundamental theory for the efficient photocatalytic degradation of MO by LC/ZnO composites, but also offered a new insight into lignin valorization. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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9 pages, 2431 KiB

Open AccessCommunication

Synthesis of CoMoO₄ Nanofibers by Electrospinning as Efficient Electrocatalyst for Overall Water Splitting

by Jiahui Fan, Xin Chang, Lu Li and Mingyi Zhang

Molecules 2024, 29(1), 7; https://doi.org/10.3390/molecules29010007 - 19 Dec 2023

Cited by 1 | Viewed by 780

Abstract

To improve the traditional energy production and consumption of resources, the acceleration of the development of a clean and green assembly line is highly important. Hydrogen is considered one of the most ideal options. The method of production of hydrogen through water splitting constitutes the most attractive research. We synthesized CoMoO₄ nanofibers by electrospinning along with post-heat treatment at different temperatures. CoMoO₄ nanofibers show a superior activity for hydrogen evolution reaction (HER) and only demand an overpotential of 80 mV to achieve a current density of 10 mA cm^–2. In particular, the CoMoO₄ catalyst also delivers excellent performances of oxygen evolution reaction (OER) in 1 M KOH, which is a more complicated process that needs extra energy to launch. The CoMoO₄ nanofibers also showed a superior stability in multiple CV cycles and maintained a catalytic activity for up to 80 h through chronopotentiometry tests. This is attributed mainly to a synergistic interaction between the different metallic elements that caused the activity of CoMoO₄ beyond single oxides. This approach proved that bimetallic oxides are promising for energy production. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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34 pages, 11463 KiB

Open AccessArticle

Preparation and Property Characterization of Sm₂EuSbO₇/ZnBiSbO₅ Heterojunction Photocatalyst for Photodegradation of Parathion Methyl under Visible Light Irradiation

by Jingfei Luan, Liang Hao, Ye Yao, Yichun Wang, Guangmin Yang and Jun Li

Molecules 2023, 28(23), 7722; https://doi.org/10.3390/molecules28237722 - 22 Nov 2023

Cited by 2 | Viewed by 767

Abstract

An unprecedented photocatalyst, Sm₂EuSbO₇, was successfully fabricated in this paper, through a high-temperature solid-state calcination method, which represented its first ever synthesis. Additionally, using the solvothermal method, the Sm₂EuSbO₇/ZnBiSbO₅ heterojunction photocatalyst (SZHP) was fabricated, marking its debut in this study. XRD analysis confirmed that both Sm₂EuSbO₇ and ZnBiSbO₅ exhibited pyrochlore-type crystal structures with a cubic lattice, belonging to the Fd3m space group. The crystal cell parameter was determined to be 10.5682 Å or 10.2943 Å for Sm₂EuSbO₇ or ZnBiSbO₅, respectively. The band gap width measured for Sm₂EuSbO₇ or ZnBiSbO₅ was 2.73 eV or 2.61 eV, respectively. Under visible light irradiation for 150 min (VLTI-150 min), SZHP exhibited remarkable photocatalytic activity, achieving 100% removal of parathion methyl (PM) concentration and 99.45% removal of total organic carbon (TOC) concentration. The kinetic constant (k) for PM degradation and visible light illumination treatment was determined to be 0.0206 min⁻¹, with a similar constant k of 0.0202 min⁻¹ observed for TOC degradation. Remarkably, SZHP exhibited superior PM removal rates compared with Sm₂EuSbO₇, ZnBiSbO₅, or N-doped TiO₂ photocatalyst, accompanied by removal rates 1.09 times, 1.20 times, or 2.38 times higher, respectively. Furthermore, the study investigated the oxidizing capability of free radicals through the use of trapping agents. The results showed that hydroxyl radicals had the strongest oxidative capability, followed by superoxide anions and holes. These findings provide a solid scientific foundation for future research and development of efficient heterojunction compound catalysts. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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18 pages, 5048 KiB

Open AccessArticle

Applicability of Titanium-Based Catalysts in the Photocatalytic Degradation of 2,3,7,8-Tetrachlorodibenzofuran

by Fatin Samara, Rasha Darra, Ahmed A. Mohamed, Waqas Ahmad, Nedal Abu-Farha, Haesung Lee, Changseok Han and Sofian Kanan

Molecules 2023, 28(22), 7488; https://doi.org/10.3390/molecules28227488 - 08 Nov 2023

Viewed by 848

Abstract

Polychlorinated dibenzofurans (PCDFs) are persistent toxic compounds that are ubiquitous in the environment. Nanocomposites of titanium(IV) oxide-vanadium(III) oxide (

{Ti}_{3} V_{2} O_{7}

) and titanium(IV) oxide-silicon dioxide (

{Ti}_{2} {Si}_{7} O_{30}

) were prepared and spectroscopically analyzed [...] Read more.

Polychlorinated dibenzofurans (PCDFs) are persistent toxic compounds that are ubiquitous in the environment. Nanocomposites of titanium(IV) oxide-vanadium(III) oxide (

{Ti}_{3} V_{2} O_{7}

) and titanium(IV) oxide-silicon dioxide (

{Ti}_{2} {Si}_{7} O_{30}

) were prepared and spectroscopically analyzed as potential decontaminants for dioxin-like materials. The analysis confirmed a homogeneous morphology with nanoscale particle size. The Ti-Si sample was found to have a high surface area compared to the Ti-V composite. Vanadium(III) oxide (V₂O₅) and silicon dioxide (SiO₂) were chosen as materials for the formation of heterogeneous compounds with titanium(IV) oxide (TiO₂) because they possess a suitable band alignment with TiO_2, thus forming effective photocatalysts. This study evaluated the photodegradation of 2,3,7,8-tetrachlorodibenzo-furan (TCDF) in the presence of Ti-Si and Ti-V oxide composites, which was tested using high- (254 nm) and midenergy (302 nm) UV irradiation sources. While Ti-Si showed success in the photodegradation of 2,3,7,8-TCDF dissolved in a (1:1) methanol–tetrahydrofuran (MeOH-THF) solution, the Ti-V composite proved to be a powerful material in adsorbing TCDF with a high capacity immediately upon mixing. Ti-Si oxide was found to decompose TCDF under the two irradiation sources with 98–99% degradation occurring after 70 min. The use of 254 nm as an irradiation source in the presence of Ti-Si was 4.3 times faster than the analogue reaction irradiated without a catalyst. Byproducts of the degradation were evaluated using gas chromatography–mass spectrometry (GC–MS), resulting in a lower chlorinated congener and less toxicity, as the main degradation product. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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24 pages, 6511 KiB

Open AccessArticle

Relation between Conventional and Starch-Assisted ASP Injection and Impact of Crystallinity on Flood Formation

by Hasanain A. Al-Jaber, Agus Arsad, Sulalit Bandyopadhyay, Mohd Zaidi Jaafar, Muhammad Tahir, Mustafa Jawad Nuhma, Abdulmunem R. Abdulmunem, Mohammad Yasin Abdulfatah and Hajar Alias

Molecules 2023, 28(18), 6685; https://doi.org/10.3390/molecules28186685 - 18 Sep 2023

Viewed by 908

Abstract

Alkaline–surfactant–polymer (ASP) flooding, a recognized method for oil recovery, encounters limited use due to its expense. In addition, ASP’s best composition and injection sequence still remains uncertain today. This study explores conventional ASP flooding using PT SPR Langgak’s special surfactants, simulating Langgak oilfield conditions in Sumatra, Indonesia. By comparing the outcomes of this flooding technique with that of starch-assisted ASP performed in another study, the benefits of adding starch nanoparticles to flooding are evident. Nano-starch ASP increased oil recovery by 18.37%, 10.76%, and 10.37% for the three configurations investigated in this study. Water flooding preceded ASP flooding, and flooding operations were carried out at 60 °C. This study employed sodium hydroxide (NaOH), sodium carbonate (Na₂CO₃), and specialized surfactants from PT SPR. The adopted polymer is solely hydrolyzed polyacrylamide (HPAM) at 2000 ppm. Starch nanoparticles underwent comprehensive characterization and focused more on charge stability. Purple yam nanoparticles (PYNPs) exhibited remarkable stability at −36.33 mV, unlike cassava starch nanoparticles (CSNPs’) at −10.68 mV and HPAM’s at −27.13 mV. Surface properties affect interactions with fluids and rocks. Crystallinity, a crucial characterization, was assessed using Origin software 2019b. CSNPs showed 24.15% crystallinity, surpassing PYNPs’ 20.68%. Higher crystallinity benefits CSNPs’ thermal stability. The amorphous behavior found in PYNPs makes them less suitable if applied in harsh reservoirs. This research correlated with prior findings, reinforcing starch nanoparticles’ role in enhancing oil recovery. In summary, this study highlighted conventional ASP flooding using HPAM as the sole polymer and compared it with three formations that used two starch nanoparticles included with HPAM, assessing their impact on charge stability, crystallinity, and recovery rate to emphasize their importance in the oil recovery industry. Starch nanoparticles’ benefits and limitations guided further investigation in this study. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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15 pages, 6847 KiB

Open AccessArticle

Synthesis of Flower-Like Cobalt–Molybdenum Mixed-Oxide Microspheres for Deep Aerobic Oxidative Desulfurization of Fuel

by Xinxiang Cao, Ruijian Tong, Jingyuan Wang, Lan Zhang, Yulan Wang, Yan Lou and Xiaomeng Wang

Molecules 2023, 28(13), 5073; https://doi.org/10.3390/molecules28135073 - 28 Jun 2023

Cited by 2 | Viewed by 957

Abstract

Flower-like cobalt–molybdenum mixed-oxide microspheres (CoMo-FMs) with hierarchical architecture were successfully synthesized via a hydrothermal process and subsequent calcination step. The characterization results show that CoMo-FMs were assembled from ultrathin mesoporous nanosheets with thicknesses of around 4.0 nm, providing the composite with a large pore volume and a massive surface area. The synthesized CoMo-FMs were employed as catalysts for the aerobic oxidative desulfurization (AODS) of fuel, and the reaction results show that the optimal catalyst (CoMo-FM-2) demonstrated an outstanding catalytic performance. Over CoMo-FM-2, various thiophenic sulfides could be effective removed at 80–110 °C under an atmospheric pressure, and a complete conversion of sulfides could be achieved in at least six consecutive cycles without a detectable change in chemical compositions. Further, the catalytic mechanism was explored by conducting systemic radical trapping and transformation experiments, and the excellent catalytic performance for CoMo-FMs should be mainly due to the synergistic effect of Mo and Co elements. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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10 pages, 2314 KiB

Open AccessCommunication

Modulating the Oxygen Reduction Reaction Performance via Precisely Tuned Reactive Sites in Porphyrin-Based Covalent Organic Frameworks

by Xiaoqing Liang, Zhi Zhao, Ruili Shi, Liting Yang, Bin Zhao, Huijie Qiao and Lipeng Zhai

Molecules 2023, 28(12), 4680; https://doi.org/10.3390/molecules28124680 - 09 Jun 2023

Cited by 3 | Viewed by 1389

Abstract

Covalent organic frameworks (COFs) have emerged as promising electrocatalysts due to their controllable architectures, highly exposed molecular active sites, and ordered structures. In this study, a series of porphyrin-based COFs (TAPP-x-COF) with various transition metals (Co, Ni, Fe) were synthesized via a facile post-metallization strategy under solvothermal synthesis. The resulting porphyrin-based COFs showed oxygen reduction reaction (ORR) activity with a trend in Co > Fe > Ni. Among them, TAPP-Co-COF exhibited the best ORR activity (E_1/2 = 0.66 V and jL = 4.82 mA cm⁻²) in alkaline media, which is comparable to those of Pt/C under the same conditions. Furthermore, TAPP-Co-COF was employed as a cathode in a Zn-air battery, demonstrating a high power density of 103.73 mW cm^–2 and robust cycling stability. This work presents a simple method for using COFs as a smart platform to fabricate efficient electrocatalysts. Full article

(This article belongs to the Special Issue Advanced Nanomaterials for Catalysis: Synthesis, Characterization and Application)

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