Heterogeneous Catalysis for Clean Energy Production and Carbon Dioxide Utilization

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Industrial Catalysis".

Deadline for manuscript submissions: closed (15 February 2024) | Viewed by 9467

Special Issue Editors


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Guest Editor
College of Liberal Arts and Sciences, Long Island University (Post), Brookville, NY 11548, USA
Interests: heterogeneous catalysis; carbon nanosphere; bimetallic catalysts; CO2 hydrogenation; dry reforming

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Guest Editor
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
Interests: biomass conversion; heterogeneous catalysis; catalyst rational design; micro-kinetics; in situ spectroscopy
College of Science & Mathematics, School of Health Professions, Rowan University, Glassboro, NJ 08028, USA
Interests: cellulose; sustainable fabrication; electrospinning; catalysis; nanofiber
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Special Issue Information

Dear Colleagues,

As a promising CO2 mitigation strategy for carbon capture and storage, CO2 utilization and production for clean energy are attracting increasing interest globally. This Special Issue will focus on experimental and theoretical investigations of novel heterogeneous catalysts for clean energy production and CO2 utilization. Clean energy includes, but is not limited to, energy derived from renewable and carbon-free sources. The CO2 utilization approaches cover electrochemical, catalytic, photocatalytic and photosynthetic, and biological process.

Both fundamental and applied research topics on heterogeneous catalysts for clean energy production and CO2 utilization, including catalyst efficiency and stability, are of interest. Related studies on new methodologies for in situ and operando catalyst characterization are also of interest. The goal is to compile a set of manuscripts that inform the state-of-the-art in heterogeneous catalysis for clean energy and CO2 utilization.

Dr. Cheng Zhang
Dr. Huixiang Li
Dr. Ping Lu
Guest Editors

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Keywords

  • heterogeneous catalysis
  • industrial catalysis
  • electrocatalysis
  • photocatalysis
  • clean energy
  • CO2 utilization
  • biomass conversion
  • in situ spectroscopy

Published Papers (7 papers)

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Research

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12 pages, 2344 KiB  
Article
Co-Encapsulation of Rhenium and Ruthenium Complexes into the Scaffolds of Metal–Organic Framework to Promote CO2 Reduction
by Zhifang Su, Baolan Yu, Jianxin Feng, Maoling Zhong, Xuan Li and Jianying Shi
Catalysts 2023, 13(12), 1510; https://doi.org/10.3390/catal13121510 - 14 Dec 2023
Viewed by 1015
Abstract
The molecular complexes of Re(4,4′-dcbpy)(CO)3Cl (dcbpy = dicarboxylicacid-2,2’-bipyridyl) and [Ru(dcbpy)3]2+ are co-assembled into UiO-66 scaffolds as structural imperfects for CO2 photocatalytic reduction (named as Re-Ru@U). The prepared catalysts are characterized by XRD, Fourier-Transform infrared (FTIR) spectra, X-ray [...] Read more.
The molecular complexes of Re(4,4′-dcbpy)(CO)3Cl (dcbpy = dicarboxylicacid-2,2’-bipyridyl) and [Ru(dcbpy)3]2+ are co-assembled into UiO-66 scaffolds as structural imperfects for CO2 photocatalytic reduction (named as Re-Ru@U). The prepared catalysts are characterized by XRD, Fourier-Transform infrared (FTIR) spectra, X-ray photoelectron spectra (XPS) and N2 adsorption–desorption isotherms. The intact structure of molecular complexes within the matrix are monitored by 1H nuclear magnetic resonance (NMR) spectra through a totally digesting catalyst. The optical properties are studied via absorption and photoluminescence spectra, and the single-electron reduction in Re and Ru complexes is detected by electron paramagnetic resonance (EPR) spectra. An excellent photocatalytic performance is obtained with steady and sustained CO evolution and a turnover number (TON) value of 15 (11 h). The CO activity irradiating by single wavelength presents the absorption-intensity-dependent changing tendency, where the absorption intensity is superposed by Re and Ru complexes. The two radicals related to Re and Ru, respectively, are simultaneously detected in the Re-Ru@U catalyst. It is suggested that the ReC2 component serves as both a photosensitizer and a catalyst, and the RuC2 component works as an additional photosensitizer to supply the second electron for CO2 reduction. The co-assembling of dual metals Re and Ru in the matrix promotes the electron transfer from the reductive Ru centres to one-electron-reduced Re centres and accounts for the superior activity of CO evolution. Our results demonstrate a strategy to develop the multimetallic catalysts via facile assembling into MOF scaffolds to promote photocatalytic performance. Full article
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11 pages, 3747 KiB  
Article
Enhancing the Activity of Cu-MOR by Water for Oxidation of Methane to Methanol
by Xi’an Guan, Yehong Wang, Xiumei Liu, Hong Du, Xinwen Guo and Zongchao Zhang
Catalysts 2023, 13(7), 1066; https://doi.org/10.3390/catal13071066 - 03 Jul 2023
Viewed by 1056
Abstract
As clean energy, methane has huge reserves and great development potential in the future. Copper zeolites are efficient in the oxidation of methane to methanol. Water has been confirmed as a source of oxygen to regenerate the copper-zeolite active sites to enable selective [...] Read more.
As clean energy, methane has huge reserves and great development potential in the future. Copper zeolites are efficient in the oxidation of methane to methanol. Water has been confirmed as a source of oxygen to regenerate the copper-zeolite active sites to enable selective anaerobic oxidation of methane to methanol. In this work, we report that the methanol yield increased from 36 μmol/g (Cu-MOR1) to 92 μmol/g (Cu-MOR1-water) as a result of water enhancing the activity of copper ion-exchange mordenite catalyst. We show for the first time that water could convert inactive copper species into active copper species during catalyst activation. A combination of the XPS, FTIR, and NMR results indicates that water dissociates and then converts ZCuIIZ into ZCuII(OH) (where Z indicates framework O (Ofw) bonded to one isolated Al in a framework T-site, i.e., 1Al) and simultaneously produces a Brönsted acid site during catalyst activation. This finding can be used to tune the state of copper species and design highly active copper-zeolite catalysts for methane oxidation to methanol. Full article
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17 pages, 6066 KiB  
Article
CO2 to Value-Added Chemicals: Synthesis and Performance of Mono- and Bimetallic Nickel–Cobalt Nanofiber Catalysts
by John Schossig, Akash Gandotra, Kevin Arizapana, Daniel Weber, Michael Wildy, Wanying Wei, Kai Xu, Lei Yu, Robert Chimenti, Islam Mantawy, Dong Choon Hyun, Wenshuai Chen, Cheng Zhang and Ping Lu
Catalysts 2023, 13(6), 1017; https://doi.org/10.3390/catal13061017 - 18 Jun 2023
Cited by 3 | Viewed by 1563
Abstract
In an epoch dominated by escalating concerns over climate change and looming energy crises, the imperative to design highly efficient catalysts that can facilitate the sequestration and transformation of carbon dioxide (CO2) into beneficial chemicals is paramount. This research presents the [...] Read more.
In an epoch dominated by escalating concerns over climate change and looming energy crises, the imperative to design highly efficient catalysts that can facilitate the sequestration and transformation of carbon dioxide (CO2) into beneficial chemicals is paramount. This research presents the successful synthesis of nanofiber catalysts, incorporating monometallic nickel (Ni) and cobalt (Co) and their bimetallic blend, NiCo, via a facile electrospinning technique, with precise control over the Ni/Co molar ratios. Application of an array of advanced analytical methods, including SEM, TGA–DSC, FTIR-ATR, XRD, Raman, XRF, and ICP-MS, validated the effective integration and homogeneous distribution of active Ni/Co catalysts within the nanofibers. The catalytic performance of these mono- and bimetallic Ni/Co nanofiber catalysts was systematically examined under ambient pressure conditions for CO2 hydrogenation reactions. The bimetallic NiCo nanofiber catalysts, specifically with a Ni/Co molar ratio of 1:2, and thermally treated at 1050 °C, demonstrated a high CO selectivity (98.5%) and a marked increase in CO2 conversion rate—up to 16.7 times that of monometallic Ni nanofiber catalyst and 10.8 times that of the monometallic Co nanofiber catalyst. This significant enhancement in catalytic performance is attributed to the improved accessibility of active sites, minimized particle size, and the strong Ni–Co–C interactions within these nanofiber structures. These nanofiber catalysts offer a unique model system that illuminates the fundamental aspects of supported catalysis and accentuates its crucial role in addressing pressing environmental challenges. Full article
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14 pages, 5706 KiB  
Article
α-NiS/g-C3N4 Nanocomposites for Photocatalytic Hydrogen Evolution and Degradation of Tetracycline Hydrochloride
by Huajin Qi, Chenyu Wang, Luping Shen, Hongmei Wang, Yuan Lian, Huanxia Zhang, Hongxia Ma, Yong Zhang and Jin Zhong Zhang
Catalysts 2023, 13(6), 983; https://doi.org/10.3390/catal13060983 - 08 Jun 2023
Cited by 5 | Viewed by 1125
Abstract
α-NiS/g-C3N4 nanocomposites were synthesized and used for photocatalytic hydrogen (H2) evolution and tetracycline hydrochloride (TC) degradation. The fabricated nanocomposites were characterized by XRD, XPS, SEM, TEM, UV-vis DRS, TRPL, and PEC measurements. Photocatalytic studies show that the hydrogen [...] Read more.
α-NiS/g-C3N4 nanocomposites were synthesized and used for photocatalytic hydrogen (H2) evolution and tetracycline hydrochloride (TC) degradation. The fabricated nanocomposites were characterized by XRD, XPS, SEM, TEM, UV-vis DRS, TRPL, and PEC measurements. Photocatalytic studies show that the hydrogen generation rate of the 15%-α-NiS/g-C3N4 nanocomposite reaches 4025 μmol·g−1·h−1 and TC degradation rate 64.6% within 120 min, both of which are higher than that of g-C3N4. The enhanced performance of the nanocomposite is attributed to the formation of a heterojunction between α-NiS and g-C3N4 that enhances visible light absorption, promotes the separation and transfer of charges, and inhibits the recombination of carriers. The photocatalytic mechanism of the α-NiS/g-C3N4 heterojunction nanocomposite is discussed in terms of relevant energy levels and charge transfer processes. Full article
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12 pages, 3002 KiB  
Article
Support Effect of Ga-Based Catalysts in the CO2-Assisted Oxidative Dehydrogenation of Propane
by Wei Zhou, Yulin Jiang, Zhiguo Sun, Shiqi Zhou, Erpai Xing, Yang Hai, Guanghao Chen and Yuetong Zhao
Catalysts 2023, 13(5), 896; https://doi.org/10.3390/catal13050896 - 16 May 2023
Cited by 2 | Viewed by 1585
Abstract
Carbon dioxide (CO2) assisted oxidative dehydrogenation of propane over Ga-modified catalysts is highly sensitive to the identity of support, but the underlying cause of support effects has not been well established. In this article, SSZ-13, SSZ-39, ZSM-5, silica and γ-Al2 [...] Read more.
Carbon dioxide (CO2) assisted oxidative dehydrogenation of propane over Ga-modified catalysts is highly sensitive to the identity of support, but the underlying cause of support effects has not been well established. In this article, SSZ-13, SSZ-39, ZSM-5, silica and γ-Al2O3 were used to load Ga species by incipient wet impregnation. The structure, textural properties, acidity of the Ga-based catalysts and the process of CO2-assisted oxidative dehydrogenation of propane were examined by X-ray diffraction (XRD), nitrogen physisorption (N2 physisorption), ammonia temperature-programmed desorption (NH3-TPD), pyridine chemisorbed Fourier transform infrared spectra (Py-FTIR), OH-FTIR and in situ FTIR. Evaluation of the catalytic performance combined with detailed catalyst characterization suggests that their dehydrogenation activity is positively associated with the number of acid sites in middle strength, confirming that the Lewis acid sites generated by Ga cations are the active species in the reaction. Ga/Na-SSZ-39(9) also has feasible acidic strength and a unique channel structure, which is conducive to the dissociative adsorption of propane and desorption of olefins. The Ga/Na-SSZ-39(9) catalysts showed superior olefins selectivity and catalytic stability at 600 ℃ compared to any other catalysts. This approach to quantifying support acid strength, and channel structure and applying it as a key catalytic descriptor of support effects is a useful tool to enable the rational design of next-generation CO2-assisted oxidative dehydrogenation catalysts. Full article
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18 pages, 4421 KiB  
Article
Enhanced Cyclopentanone Yield from Furfural Hydrogenation: Promotional Effect of Surface Silanols on Ni-Cu/m-Silica Catalyst
by Ravi Balaga, Putrakumar Balla, Xiaoqiang Zhang, Kishore Ramineni, Hong Du, Shrutika Lingalwar, Vijayanand Perupogu and Zongchao Conrad Zhang
Catalysts 2023, 13(3), 580; https://doi.org/10.3390/catal13030580 - 13 Mar 2023
Cited by 6 | Viewed by 1326
Abstract
A direct alkaline hydrothermal method was used to synthesize mono- and bimetallic Ni and Cu on mesoporous silica (m-SiO2) as catalysts for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). The catalysts were characterized by XRD, FTIR, H2-TPR, SEM, [...] Read more.
A direct alkaline hydrothermal method was used to synthesize mono- and bimetallic Ni and Cu on mesoporous silica (m-SiO2) as catalysts for the hydrogenation of furfural (FAL) to cyclopentanone (CPO). The catalysts were characterized by XRD, FTIR, H2-TPR, SEM, TEM, HR-TEM, XPS, ICP, BET, and CHN analysis. The results demonstrate that the addition of Cu metal improved the reducibility of Ni catalysts and revealed Ni-Cu alloy formation over m-SiO2. Furthermore, XPS and FTIR results reveal that the silanol groups on the catalyst surface play an important role in the ring rearrangement of furfuryl alcohol. Hence, the effect of silanol groups in the FOL rearrangement was studied in detail. Among the catalysts at fixed metal loading of 20 wt.%, Ni5Cu15/m-SiO2 catalyzed the formation of CPO as the main product due to the synergy of Ni-Cu alloy and surface silanol groups. Ni5Cu15 supported on a commercial mesoporous silica (Ni5Cu15/C-SiO2) showed inferior performance compared with the Ni5Cu15/m-SiO2 catalyst for the FAL hydrogenation. Reaction temperature and time were also optimized for the enhanced CPO yield over Ni5Cu15/m-SiO2. The Ni5Cu15/m-SiO2 catalyst is durable, as demonstrated by stability tests over multiple reuses. This effective and flexible NixCuy on m-SiO2 catalyst provides an effective candidate for efficient upgrading of furanics in selective hydrogenation reactions. Full article
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40 pages, 5127 KiB  
Review
Recent Advances in Coke Management for Dry Reforming of Methane over Ni-Based Catalysts
by Zhenchao Xu and Eun Duck Park
Catalysts 2024, 14(3), 176; https://doi.org/10.3390/catal14030176 - 01 Mar 2024
Viewed by 1028
Abstract
The dry reforming of methane (DRM) is a promising method for controlling greenhouse gas emissions by converting CO2 and CH4 into syngas, a mixture of CO and H2. Ni-based catalysts have been intensively investigated for their use in the [...] Read more.
The dry reforming of methane (DRM) is a promising method for controlling greenhouse gas emissions by converting CO2 and CH4 into syngas, a mixture of CO and H2. Ni-based catalysts have been intensively investigated for their use in the DRM. However, they are limited by the formation of carbonaceous materials on their surfaces. In this review, we explore carbon-induced catalyst deactivation mechanisms and summarize the recent research progress in controlling and mitigating carbon deposition by developing coke-resistant Ni-based catalysts. This review emphasizes the significance of support, alloy, and catalyst structural strategies, and the importance of comprehending the interactions between catalyst components to achieve improved catalytic performance and stability. Full article
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