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Keywords = doping carbon materials catalyst

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26 pages, 5379 KiB  
Review
A Review of Strategies to Improve the Electrocatalytic Performance of Tungsten Oxide Nanostructures for the Hydrogen Evolution Reaction
by Meng Ding, Yuan Qin, Weixiao Ji, Yafang Zhang and Gang Zhao
Nanomaterials 2025, 15(15), 1163; https://doi.org/10.3390/nano15151163 - 28 Jul 2025
Viewed by 220
Abstract
Hydrogen, as a renewable and clean energy with a high energy density, is of great significance to the realization of carbon neutrality. In recent years, extensive research has been conducted on the electrocatalytic hydrogen evolution reaction (HER) by splitting water, with a focus [...] Read more.
Hydrogen, as a renewable and clean energy with a high energy density, is of great significance to the realization of carbon neutrality. In recent years, extensive research has been conducted on the electrocatalytic hydrogen evolution reaction (HER) by splitting water, with a focus on developing efficient electrocatalysts that can perform the HER at an overpotential with minimal power consumption. Tungsten oxide (WO3), a non-noble-metal-based material, has great potential in hydrogen evolution due to its excellent redox capability, low cost, and high stability. However, it cannot meet practical needs because of its poor electrical conductivity and the limited number of active sites; thus, it is necessary to further improve HER performance. In this review, recent advances related to WO3-based electrocatalysts for the HER are introduced. Most importantly, several tactics for optimizing the electrocatalytic HER activity of WO3 are summarized, such as controlling its morphology, phase transition, defect engineering (anion vacancies, cation doping, and interstitial atoms), constructing a heterostructure, and the microenvironment effect. This review can provide insight into the development of novel catalysts with high activity for the HER and other renewable energy applications. Full article
(This article belongs to the Special Issue Advanced Nanocatalysis in Environmental Applications)
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16 pages, 8045 KiB  
Article
Modification of G-C3N4 by the Surface Alkalinization Method and Its Photocatalytic Depolymerization of Lignin
by Zhongmin Ma, Ling Zhang, Lihua Zang and Fei Yu
Materials 2025, 18(14), 3350; https://doi.org/10.3390/ma18143350 - 17 Jul 2025
Viewed by 294
Abstract
The efficient depolymerization of lignin has become a key challenge in the preparation of high-value-added chemicals. Graphitic carbon nitride (g-C3N4)-based photocatalytic system shows potential due to its mild and green characteristics over other depolymerization methods. However, its inherent defects, [...] Read more.
The efficient depolymerization of lignin has become a key challenge in the preparation of high-value-added chemicals. Graphitic carbon nitride (g-C3N4)-based photocatalytic system shows potential due to its mild and green characteristics over other depolymerization methods. However, its inherent defects, such as a wide band gap and rapid carrier recombination, severely limit its catalytic performance. In this paper, a g-C3N4 modification strategy of K⁺ doping and surface alkalinization is proposed, which is firstly applied to the photocatalytic depolymerization of the lignin β-O-4 model compound (2-phenoxy-1-phenylethanol). K⁺ doping is achieved by introducing KCl in the precursor thermal polymerization stage to weaken the edge structure strength of g-C3N4, and post-treatment with KOH solution is combined to optimize the surface basic groups. The structural/compositional evolution of the materials was analyzed by XRD, FTIR, and XPS. The morphology/element distribution was visualized by SEM-EDS, and the optoelectronic properties were evaluated by UV–vis DRS, PL, EIS, and transient photocurrent (TPC). K⁺ doping and surface alkalinization synergistically regulate the layered structure of the material, significantly increase the specific surface area, introduce nitrogen vacancies and hydroxyl functional groups, effectively narrow the band gap (optimized to 2.35 eV), and inhibit the recombination of photogenerated carriers by forming electron capture centers. Photocatalytic experiments show that the alkalinized g-C3N4 can completely depolymerize 2-phenoxy-1-phenylethanol with tunable product selectivity. By adjusting reaction time and catalyst dosage, the dominant product can be shifted from benzaldehyde (up to 77.28% selectivity) to benzoic acid, demonstrating precise control over oxidation degree. Mechanistic analysis shows that the surface alkaline sites synergistically optimize the Cβ-O bond breakage path by enhancing substrate adsorption and promoting the generation of active oxygen species (·OH, ·O2). This study provides a new idea for the efficient photocatalytic depolymerization of lignin and lays an experimental foundation for the interface engineering and band regulation strategies of g-C3N4-based catalysts. Full article
(This article belongs to the Section Catalytic Materials)
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12 pages, 2721 KiB  
Article
Conjugated Polyaniline–Phytic Acid Polymer Derived 3D N, P-Doped Porous Carbon as a Metal-Free Electrocatalyst for Zn–Air Batteries
by Wanting Xiong, Yifan Kong, Jiangrong Xiao, Tingting Wang and Xiaoli Chen
Catalysts 2025, 15(7), 683; https://doi.org/10.3390/catal15070683 - 14 Jul 2025
Viewed by 383
Abstract
The development of cost-effective and scalable air/oxygen electrode materials is crucial for the advancement of Zn–air batteries (ZABs). Porous carbon materials doped with heteroatoms have attracted considerable attention in energy and environmental fields because of their tunable nanoporosity and high electrical conductivity. In [...] Read more.
The development of cost-effective and scalable air/oxygen electrode materials is crucial for the advancement of Zn–air batteries (ZABs). Porous carbon materials doped with heteroatoms have attracted considerable attention in energy and environmental fields because of their tunable nanoporosity and high electrical conductivity. In this work, we report the synthesis of a three-dimensional (3D) N and P co-doped porous carbon (PA@pDC-1000), derived from a conjugated polyaniline–phytic acid polymer. The cross-linked, rigid conjugated polymeric framework plays a crucial role in maintaining the integrity of micro- and mesoporous structures and promoting graphitization during carbonization. As a result, the material exhibits a hierarchical pore structure, a high specific surface area (1045 m2 g−1), and a large pore volume (1.02 cm3 g−1). The 3D N, P co-doped PA@pDC-1000 catalyst delivers a half-wave potential of 0.80 V (vs. RHE) and demonstrates a higher current density compared to commercial Pt/C. A primary ZAB utilizing this material achieves an open-circuit voltage of 1.51 V and a peak power density of 217 mW cm−2. This metal-free, self-templating presents a scalable route for the generating and producing of high-performance oxygen reduction reaction catalysts for ZABs. Full article
(This article belongs to the Special Issue Electrocatalysis and Photocatalysis in Redox Flow Batteries)
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32 pages, 4753 KiB  
Review
Prospective Obstacles and Improvement Strategies of Manganese-Based Materials in Achieving High-Performance Rechargeable Zinc–Air Batteries
by Zhangli Ye, Tianjing Wu, Lanhua Yi and Mingjun Jing
Batteries 2025, 11(7), 255; https://doi.org/10.3390/batteries11070255 - 8 Jul 2025
Viewed by 622
Abstract
Zinc–air batteries (ZABs) are crucial for renewable energy conversion and storage due to their cost-effectiveness, excellent safety, and superior cycling stability. However, developing efficient and affordable bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) at the air [...] Read more.
Zinc–air batteries (ZABs) are crucial for renewable energy conversion and storage due to their cost-effectiveness, excellent safety, and superior cycling stability. However, developing efficient and affordable bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) at the air cathode remains a significant challenge. Manganese (Mn)-based materials, known for their tunable oxidation states, adaptable crystal structures, and environmental friendliness, are regarded as the most promising candidates. This review systematically summarizes recent advances in Mn-based bifunctional catalysts, concentrating on four primary categories: Mn–N–C electrocatalysts, manganese oxides, manganates, and other Mn-based compounds. By examining the intrinsic merits and limitations of each category, we provide a comprehensive discussion of optimization strategies, which include morphological modulation, structural engineering, carbon hybridization, heterointerface construction, heteroatom doping, and defect engineering, aimed at enhancing catalytic performance. Additionally, we critically address existing challenges and propose future research directions for Mn-based materials in rechargeable ZABs, offering theoretical insights and design principles to advance the development of next-generation energy storage systems. Full article
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30 pages, 5199 KiB  
Review
Modification Strategies of g-C3N4-Based Materials for Enhanced Photoelectrocatalytic Degradation of Pollutants: A Review
by Yijie Zhang, Peng Lian, Xinyu Hao, Li Zhang, Lihua Yang, Li Jiang, Kaiyou Zhang, Lei Liao and Aimiao Qin
Inorganics 2025, 13(7), 225; https://doi.org/10.3390/inorganics13070225 - 3 Jul 2025
Viewed by 452
Abstract
Graphite carbon nitride (g-C3N4) is a low band gap non-metallic polymer semiconductor that has broad application prospects and is an ideal material for absorbing visible light, as g-C3N4 materials have strong oxidation properties and are easy [...] Read more.
Graphite carbon nitride (g-C3N4) is a low band gap non-metallic polymer semiconductor that has broad application prospects and is an ideal material for absorbing visible light, as g-C3N4 materials have strong oxidation properties and are easy to modify. The structure formation of g-C3N4-based materials makes a series of photocatalytic synthesis reactions possible and improves photocatalytic reaction activity. In this paper, the development history, structures, and performance of g-C3N4 are briefly introduced, and the modification strategies of g-C3N4 are summarized to improve its photocatalytic and photoelectric catalytic properties via doping, heterojunction construction, etc. The light absorption and utilization of the catalysts are also analyzed in terms of light source conditions, and the application of g-C3N4 and its modified materials in photocatalysis and photocatalytic degradation is reviewed. Full article
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22 pages, 3709 KiB  
Review
Carbon-Based Catalysts for Electrochemical Nitrate Reduction to Ammonia: Design Strategies and Mechanistic Insights
by Qunyu Chen, Liuyang Deng, Jinrui Zhang, Ying Zhang, Lei Zhang, Shun Lu and Yanwei Wang
Materials 2025, 18(13), 3019; https://doi.org/10.3390/ma18133019 - 25 Jun 2025
Viewed by 522
Abstract
The electrochemical reduction of nitrate to ammonia offers a promising solution for both alleviating nitrate pollution in wastewater and providing a sustainable ammonia source for agriculture use. This review focuses on the role of carbon-based catalysts in electrochemical nitrate reduction to ammonia, emphasizing [...] Read more.
The electrochemical reduction of nitrate to ammonia offers a promising solution for both alleviating nitrate pollution in wastewater and providing a sustainable ammonia source for agriculture use. This review focuses on the role of carbon-based catalysts in electrochemical nitrate reduction to ammonia, emphasizing their potential in addressing environmental pollution and supporting sustainable ammonia production. Carbon materials, known for their abundance, affordability, and eco-friendly properties, are central to this process. The review highlights key strategies for enhancing catalytic performance, including heteroatom doping, the development of porous structures, and the integration of metal/metal oxide nanoparticles. Additionally, it addresses significant challenges such as weak nitrate adsorption, slow reaction kinetics, and competition with the hydrogen evolution reaction. Through the integration of advanced material design, mechanistic insights, and innovative engineering strategies, this review provides valuable guidance for the future design of carbon-based catalysts, paving the way for significant advancements in both nitrate removal and sustainable ammonia synthesis. Full article
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21 pages, 3361 KiB  
Article
Alternative Supports for Electrocatalysis of the Oxygen Evolution Reaction in Alkaline Media
by Gwénaëlle Kéranguéven, Ivan Filimonenkov, Thierry Dintzer and Matthieu Picher
Electrochem 2025, 6(3), 23; https://doi.org/10.3390/electrochem6030023 - 25 Jun 2025
Viewed by 439
Abstract
The anodic stability of tungsten carbide (WC) and iron oxide with a spinel structure (Fe3O4) were compared against similar data for nanostructured, boron-doped diamond (BDD), and the benchmark Vulcan XC72 carbon, in view of their eventual application as alternative [...] Read more.
The anodic stability of tungsten carbide (WC) and iron oxide with a spinel structure (Fe3O4) were compared against similar data for nanostructured, boron-doped diamond (BDD), and the benchmark Vulcan XC72 carbon, in view of their eventual application as alternative supports for the anion exchange membrane electrolyzer anode. To this end, metal oxide composites were prepared by the in situ autocombustion (ISAC) method, and the anodic behavior of materials (composites as well as supports alone) was investigated in 1 M NaOH electrolyte by the rotating ring–disc electrode method, which enables the separation oxygen evolution reaction and materials’ degradation currents. Among all supports, BDD has proven to be the most stable, while Vulcan XC72 is the least stable under the anodic polarization, with Fe3O4 and WC demonstrating intermediate behavior. The Co3O4-BDD, -Fe3O4, -WC, and -Vulcan composites prepared by the ISAC method were then tested as catalysts of the oxygen evolution reaction. The Co3O4-BDD and Co3O4-Fe3O4 composites appear to be competitive electrocatalysts for the OER in alkaline medium, showing activity comparable to the literature and higher support stability towards oxidation, either in cyclic voltammetry or chronoamperometry stability tests. On the contrary, WC- and Vulcan-based composites are prone to degradation. Full article
(This article belongs to the Topic Electrocatalytic Advances for Sustainable Energy)
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16 pages, 1927 KiB  
Review
Recent Advances of the Electrochemical Hydrogenation of Biofuels and Chemicals from Furfural
by Huiyi Liang, Ke Liu, Xinghua Zhang, Qi Zhang, Lungang Chen, Yubao Chen, Xiuzheng Zhuang and Longlong Ma
Energies 2025, 18(12), 3075; https://doi.org/10.3390/en18123075 - 11 Jun 2025
Viewed by 468
Abstract
With increasing energy demand and depletion of fossil fuels, the search for renewable energy sources has become imperative. Among them, biomass energy has attracted significant attention as it is clean, renewable, and abundant. This review summarizes recent advances in the electroreduction of the [...] Read more.
With increasing energy demand and depletion of fossil fuels, the search for renewable energy sources has become imperative. Among them, biomass energy has attracted significant attention as it is clean, renewable, and abundant. This review summarizes recent advances in the electroreduction of the biomass-derived platform compound furfural (FF) for producing high-value fuels and chemicals. First, the principles and mechanisms of electrocatalysis are introduced, followed by a detailed analysis of reaction pathways for electrocatalytic hydrogenation, hydrogenolysis, and dimerization. Subsequently, the review highlights the research progress on the electrochemical reduction of FF to hydrofuroin (HDF, a precursor for jet fuel), analyzing its reaction mechanisms and summarizing the effects of catalytic materials and reaction conditions on product selectivity and faradaic efficiency. Additionally, it provides an overview of catalyst selection for both hydrogenation and hydrogenolysis processes. Studies indicate that Cu-based catalysts exhibit superior performance in hydrogenation and hydrogenolysis, with the latter being more favorable under low pH. In contrast, metal-doped carbon catalysts demonstrate enhanced activity in dimerization reactions. Reaction conditions also significantly influence product distribution, with lower reduction potentials generally favoring dimerization. Finally, the challenges and future directions in FF electroreduction are discussed, including the need for deeper understanding of competing pathways, improved electrode stability, and scalable reactor design. The integration of electrocatalytic with renewable energy offers a green and sustainable approach for the efficient utilization of biomass-derived compounds, holding substantial research significance and application potential. Full article
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24 pages, 3128 KiB  
Review
Biochar-Based Materials for Catalytic CO2 Valorization
by Shahab Zomorodbakhsh, Lucas D. Dias, Mário J. F. Calvete, Andreia F. Peixoto, Rui M. B. Carrilho and Mariette M. Pereira
Catalysts 2025, 15(6), 568; https://doi.org/10.3390/catal15060568 - 8 Jun 2025
Viewed by 1490
Abstract
Biochar-based materials have gathered increasing attention as sustainable catalysts for carbon dioxide (CO2) valorization, offering a green alternative to traditional metal-based systems. Produced from renewable biomass through pyrolysis, biochar possesses key features—such as high surface area, rich porosity and tunable surface [...] Read more.
Biochar-based materials have gathered increasing attention as sustainable catalysts for carbon dioxide (CO2) valorization, offering a green alternative to traditional metal-based systems. Produced from renewable biomass through pyrolysis, biochar possesses key features—such as high surface area, rich porosity and tunable surface chemistry—that make it particularly suited for heterogeneous catalysis. This review highlights recent advances in the use of biochar-derived catalysts for key CO2 conversion reactions, focusing on cycloaddition to epoxides, dry reforming of methane and catalytic biomass upgrading. Emphasis is given to the role of biochar’s origin and preparation methods, which critically influence its structure, surface functionality and catalytic performance. Feedstocks rich in mineral content or oxygenated groups, for instance, can enhance CO2 activation and product selectivity. Furthermore, tailored modifications—such as doping with heteroatoms or supporting metal nanoparticles—further boost catalytic activity and stability by tuning acid–base behavior, while maintaining low toxicity and cost-effectiveness. Compared to conventional catalysts, biochar-based systems offer advantages in low cost, recyclability and resistance to deactivation. Challenges remain in standardizing production methods, controlling structural variability, minimizing metal leaching and scaling up. This review presents biochar as a versatile, renewable platform for CO2 utilization, highlighting the importance of rational design, feedstock selection and functionalization strategies for developing efficient, sustainable catalytic systems, in line with green chemistry and circular economy principles. Full article
(This article belongs to the Special Issue Carbon-Based Catalysts to Address Environmental Challenges)
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15 pages, 3628 KiB  
Article
Nitrogen-Doped Biochar Aerogel as Efficient Peroxymonosulfate Activator for Organic Pollutant Removal
by Lingshuai Kong, Mingshuo Zhu and Jinhua Zhan
Nanomaterials 2025, 15(11), 865; https://doi.org/10.3390/nano15110865 - 4 Jun 2025
Viewed by 471
Abstract
Rapid industrialization has escalated environmental pollution caused by organic compounds, posing critical challenges for wastewater treatment. Advanced oxidation processes based on peroxymonosulfate (PMS) suffer from metal leaching and catalyst recycling challenges. To address these limitations, this study developed a nitrogen-doped biochar aerogel (NBA) [...] Read more.
Rapid industrialization has escalated environmental pollution caused by organic compounds, posing critical challenges for wastewater treatment. Advanced oxidation processes based on peroxymonosulfate (PMS) suffer from metal leaching and catalyst recycling challenges. To address these limitations, this study developed a nitrogen-doped biochar aerogel (NBA) derived from poplar wood powder as an eco-friendly and easily recoverable PMS activator. The NBA catalyst, optimized by tuning the calcination temperature to achieve a specific surface area of 297.5 m2 g−1, achieved 97% bisphenol A (BPA) removal within 60 min with a catalyst dosage of 0.3 g/L and 1.0 mM PMS under mild conditions. The material exhibited broad pH adaptability (pH 3.5–9), recyclability (>94% efficiency after thermal treatment), and versatility in degrading seven pollutants (BPA, phenol, 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, rhodamine 6G, and levofloxacin) through synergistic radical (•OH, SO4•−, O2•−) and non-radical (1O2) pathways. X-ray photoelectron spectroscopy (XPS) analyses revealed that nitrogen doping enhanced PMS activation by optimizing electronic structures. This study highlights the potential of waste biomass-derived carbon aerogels as eco-friendly, efficient, and reusable catalysts for advanced oxidation processes in wastewater treatment. Full article
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20 pages, 1850 KiB  
Article
Constructing Novel 2D Composite Nanomaterials by Coupling Graphene or Silicene with TM3N2 MXene (TM = Nb, Ta, Mo, and W) to Achieve Highly Efficient HER Catalysts
by Xiuyi Zhang, Guangtao Yu, Wei Zhang, E Yang and Wei Chen
Molecules 2025, 30(11), 2401; https://doi.org/10.3390/molecules30112401 - 30 May 2025
Cited by 1 | Viewed by 473
Abstract
MXenes have emerged as promising candidates for energy storage and catalyst design. Through detailed density functional theory (DFT) calculations, we designed a series of new 2D composite MXene-based nanomaterials by covering excellent TM3N2 MXenes (TM = Nb, Ta, Mo, and [...] Read more.
MXenes have emerged as promising candidates for energy storage and catalyst design. Through detailed density functional theory (DFT) calculations, we designed a series of new 2D composite MXene-based nanomaterials by covering excellent TM3N2 MXenes (TM = Nb, Ta, Mo, and W) with graphene or buckled silicene. Our findings demonstrate that this coating can lead to high catalytic activity for hydrogen evolution reactions (HER) in these composite MXene-based systems, with silicene exhibiting superior performance compared to graphene. The relevant carbon and silicon atoms in the coated materials serve as active sites for HER due to complex electron transfer processes. Additionally, doping N or P atoms into graphene/silicene, which have similar atomic radii, but larger electronegativity than C/Si atoms, can further enhance the HER activity of adjacent carbon or silicon atoms, thus endowing the composite systems with higher HER catalytic performance. Coupled with their high stability and metallic conductivity, all these composite systems show great potential as electrocatalysts for HER. These remarkable findings offer new strategies and valuable insights for designing non-precious and highly efficient MXene-based HER electrocatalysts. Full article
(This article belongs to the Special Issue Synthesis and Crystal Structure Studies of Metal Complexes)
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15 pages, 1853 KiB  
Article
Degradation of Micropollutants in Wastewater Using Photocatalytic TiO2@Ag-NPs Coatings Under Visible Irradiation
by Cristian Yoel Quintero-Castañeda, Claire Tendero, Thibaut Triquet, Arturo I. Villegas-Andrade, María Margarita Sierra-Carrillo and Caroline Andriantsiferana
Water 2025, 17(11), 1632; https://doi.org/10.3390/w17111632 - 27 May 2025
Viewed by 595
Abstract
The contamination of aquatic ecosystems by the micropollutants in wastewater discharges is currently a critical issue. Therefore, the development of novel treatment processes and materials is essential to ensure the availability of safe water. The present study aims to develop a photocatalytic material [...] Read more.
The contamination of aquatic ecosystems by the micropollutants in wastewater discharges is currently a critical issue. Therefore, the development of novel treatment processes and materials is essential to ensure the availability of safe water. The present study aims to develop a photocatalytic material composed of silver nanoparticles (Ag-NPs)-doped TiO2 supported on a Pyrex® plate (TiO2@Ag-NPs) exhibiting catalytic activity under visible irradiation (λ > 400 nm). The effects of Ag-NPs doping on the TiO2 matrix, the resistance of the coating at the catalyst/substrate interface, and the photocatalytic degradation efficiency of the photocatalyst for a micropollutant (diuron) of the pesticide family were studied. The photocatalyst was characterised using X-ray diffraction, scanning electron microscopy, ultraviolet–visible spectrophotometry, and scratch tests. The solution concentrations were monitored using high-performance liquid chromatography and total organic carbon analyses. A 32% diuron removal was achieved using photocatalytic TiO2@Ag-NPs under visible irradiation, whereas undoped TiO2 showed no activity. Furthermore, the effects of the nanoparticle growth mode on the photocatalytic activity of TiO2@Ag-NPs were explored. The presence of a TiO2 sublayer ensured the adhesion of the coating and promoted the dispersion of nanoparticles within the matrix. It ensured chemical continuity (TiO2@Ag-NPs/Pyrex®), reduced the bandgap, and decreased electron–hole pair recombination. Full article
(This article belongs to the Special Issue Recent Advances in Photocatalysis in Water and Wastewater Treatment)
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15 pages, 2127 KiB  
Article
Amorphous Fe-Doped Manganese Carbonate for Efficient Activation of Peroxymonosulfate: Mechanism and Performance Toward Orange II Degradation
by Peng Cheng, Yuqing Li, Yunlong Ma, Cui Qiu, Tengfei Fu, Yajie Wang and Feng Wu
Molecules 2025, 30(11), 2325; https://doi.org/10.3390/molecules30112325 - 26 May 2025
Viewed by 399
Abstract
A novel amorphous Fe-doped manganese carbonate (a-FeMn-1) was synthesized via a facile co-precipitation method and evaluated as an efficient heterogeneous catalyst for the activation of peroxymonosulfate (PMS) in the degradation of Orange II. Among various Fe/Mn molar ratios, the 1:1 composition (a-FeMn-1) showed [...] Read more.
A novel amorphous Fe-doped manganese carbonate (a-FeMn-1) was synthesized via a facile co-precipitation method and evaluated as an efficient heterogeneous catalyst for the activation of peroxymonosulfate (PMS) in the degradation of Orange II. Among various Fe/Mn molar ratios, the 1:1 composition (a-FeMn-1) showed optimal catalytic activity, achieving 98% removal efficiency within 60 min under near-neutral pH conditions. Characterization results indicated that Fe doping effectively induced an amorphous structure and increased surface area and oxygen defects, promoting PMS activation. The system displayed broad pH applicability and resistance to Cl and natural organic matter, while degradation was inhibited by HCO3 and PO43−. EPR and quenching experiments confirmed that surface-bound sulfate radicals (SO4•−), hydroxyl radicals (OH), and singlet oxygen (1O2) were the primary reactive species. XPS analysis further revealed the redox cycling of Fe and Mn and the involvement of defect oxygen in the PMS activation process. The catalyst also demonstrated excellent reusability over five cycles without significant loss in efficiency. This work provides insights into the rational design of amorphous bimetallic materials for sulfate radical-based advanced oxidation processes. Full article
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14 pages, 2976 KiB  
Article
Chromium-Doped Biomass-Based Hydrochar-Catalyzed Synthesis of 5-Hydroxymethylfurfural from Glucose
by Huimin Gao, Wei Mao, Pize Xiao, Chutong Ling, Zhiming Wu and Jinghong Zhou
Polymers 2025, 17(10), 1413; https://doi.org/10.3390/polym17101413 - 20 May 2025
Viewed by 390
Abstract
5-Hydroxymethylfurfural (HMF) is a versatile carbohydrate-derived platform chemical that has been used for the synthesis of a number of commercially valuable compounds. In this study, several chromium (Cr)-doped, biomass-derived hydrochar catalysts were synthesized via the one-pot method using starch, eucalyptus wood, and bagasse [...] Read more.
5-Hydroxymethylfurfural (HMF) is a versatile carbohydrate-derived platform chemical that has been used for the synthesis of a number of commercially valuable compounds. In this study, several chromium (Cr)-doped, biomass-derived hydrochar catalysts were synthesized via the one-pot method using starch, eucalyptus wood, and bagasse as carbon sources. Then, the performance of these synthesized materials for the catalytic conversion of glucose into HMF was evaluated by, primarily, the yield of HMF. The synergistic interactions between the Cr salt and the different biomass components were investigated, along with their effects on the catalytic efficiency. The differences in the catalytic activity of the synthesized materials were analyzed through structural characterization, as well as assessments of the acid density and strength. Among the catalysts, Cr5BHC180 derived from bagasse presented the highest activity, achieving an HMF yield of 64.5% in an aqueous solvent system of dimethyl sulfoxide (DMSO) and saturated sodium chloride (NaCl) at 170 °C after 5 h. After four cycles, the HMF yield of Cr5BHC180 decreased to 38.7%. Characterization techniques such as N2 adsorption–desorption and Py-FTIR suggested that such a decline in the HMF yield is due to pore blockage and acid site coverage by humic by-products, as demonstrated by the fact that regeneration by calcination at 300 °C restored the HMF yield to 50.5%. Full article
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18 pages, 5259 KiB  
Article
Synergistic Cu-Pd Nanocatalysts on MOF-Derived N-Doped Carbon for Selective Hydrogenolysis of Lignin to Aromatic Monomers
by Wenjun Lei, Yan Fu, Shipeng Gu, Shuaishuai Qiu and Jie Chang
Catalysts 2025, 15(5), 455; https://doi.org/10.3390/catal15050455 - 7 May 2025
Viewed by 533
Abstract
Catalytic hydrogenolysis of lignin to produce high-value monophenols has emerged as a pivotal strategy in modern biorefineries. In this study, we synthesized spherical nitrogen-doped porous carbon (SNCB) materials by using Al/Co-BTC as a precursor, introducing melamine as a supplementary carbon and nitrogen source, [...] Read more.
Catalytic hydrogenolysis of lignin to produce high-value monophenols has emerged as a pivotal strategy in modern biorefineries. In this study, we synthesized spherical nitrogen-doped porous carbon (SNCB) materials by using Al/Co-BTC as a precursor, introducing melamine as a supplementary carbon and nitrogen source, and activating the material with NaOH solution. The SNCB framework was decorated with Cu-Pd bimetallic nanoparticles, exhibiting outstanding catalytic activity in the hydrogenolytic depolymerization of organosolv lignin. The Cu-Pd@SNCB catalyst exhibited remarkable activity, attributed to the hierarchical porous structure of SNCB that facilitated metal nanoparticle dispersion and reactant accessibility. The synergistic effect between Cu as the reactive site for reactant adsorption and Pd as the reactive site for H2 adsorption enhanced the catalytic activity of the catalyst. Systematically optimized conditions (2 MPa H2, 270 °C, 3 h) yielded 43.02 wt% phenolic monomers, with 4-(3-hydroxypropyl)-2,6-dimethoxyphenol dominating the product profile at 46.3% selectivity. The catalyst and its reaction products were analyzed using advanced characterization techniques, including XPS, XRD, TEM, SEM, BET, GC-MS, GPC, 2D HSQC NMR, and FT-IR, to elucidate the reaction mechanism. The mechanism proceeds through: (1) nucleophilic substitution of the β-O-4 hydroxyl group by MeOH, followed by (2) simultaneous hydrogenolytic cleavage of Cβ-O and Cα-O bonds mediated by Cu-Pd@SNCB under H2 atmosphere, which selectively produces 4-(3-hydroxypropyl)-2,6-dimethoxyphenol and 4-propyl-2,6-dimethoxyphenol. This study proposes a bimetallic synergistic mechanism, offering a general blueprint for developing selective lignin valorization catalysts. Full article
(This article belongs to the Special Issue Catalytic Conversion and Utilization of Biomass)
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