Carbon Catalyst Research Articles

ZIF-8/balsa wood derived N-doped porous carbon as self-supporting electro-Fenton cathode for efficient antibiotics degradation

Efficient electrochemical advanced oxidation processes (EAOPs) based on carbon catalysts are highly promising candidates for green environmental remediation technologies. Wood derived N-doped porous carbon (WNPC) was prepared the balsa wood with in-situ growth of zeolitic imidazolate framework-8 (ZIF-8) was used as precursor. WNPC acted as self-supporting electric Fenton cathode with high yield and selectivity (96 %) of in-situ H2O2 generation, which effectively avoided the use binder for powder material. Owing to abundant N-doping and oxygen functional groups, the H2O2 yield of WNPC was three times that of balsa wood derived carbon (WC) in electro-Fenton system. The graphite-N promoted the electron transfer, while the pyridinic-N could enhance the selectivity of the 2e-ORR for H2O2 generation. Furthermore, the specific surface area of WNPC was 10 times of WC, with improved hydrophilicity and accelerated electron transfer. The removal efficiency of tetracycline hydrochloride (TC) achieved 91 % within 120 min in electro-Fenton system with WNPC and Fe2+, which was much higher than that with WC (63 %). Free radical scavenging and electron paramagnetic resonance experiments confirmed that ·OH and O2–· were the main active substances for TC degradation in electro-Fenton system. In addition, WNPC has good stability, reusability, and comparable degradation performance of various organic pollutants, and also had efficient degradation performance with actual water. This research proposed a novel strategy to construct efficient electro-Fenton catalyst with wood as precursor, which provides an advancing electrocatalytic methods to achieve efficient and environmentally conscious water purification.

Zeolitic imidazolate framework derived Fe catalyst electrocatalytic-driven atomic hydrogen for efficient reduction of nitrate to N2

Excessive discharge of nitrogen-containing chemical products into the natural water environment leads to the serious environmental problem of nitrate-nitrogen pollution, threatening the ecological balance and human health. In this study, we propose an efficient denitrification electrochemical method utilizing iron-doped zeolite imidazolium framework derived defective nitrogen-doped carbon (d-FeNC) catalysts. The d-FeNC catalyst exhibited 97 % nitrate removal efficiency and 94 % total nitrogen (TN) removal, and the reaction rate constant was increased from 0.73 h−1 of the Fe-undoped electrocatalyst (d-NC) to 1.11 h−1. The successful synthesis of d-FeNC with carbon defect sites and encapsulated Fe was confirmed by in-depth characterization. In situ electron paramagnetic resonance (EPR) analysis in conjunction with cyclic voltammetry (CV) tests confirmed the carbon substrates with defect enhanced the trapping of atomic hydrogen (H*) on the catalyst surface. Density functional theory (DFT) calculations clarified the doping of Fe facilitated the adsorption of nitrate, resulting in contact of H* with nitrate on the catalyst surface. In the synergy of the defective state organic framework and metal Fe, H* and nitrate realized a collision process. The electrochemical denitrification system achieved an excellent nitrate removal capacity of 7587 mgN·g−1cat in high-concentration nitrate solution and showed excellent stability under various conditions. Overall, this study underscores the potential of defective iron-doped carbon catalysts for efficient electrocatalytic denitrification, providing a promising approach for sustainable wastewater treatment.

Preparation of High-Efficiency Fe/N-Doped Carbon Catalysts Derived from Graphite Phase Carbon Nitride for Reduction of Oxygen

Preparation of High-Efficiency Fe/N-Doped Carbon Catalysts Derived from Graphite Phase Carbon Nitride for Reduction of Oxygen

Efficient isomerization of glucose to fructose over Al-loaded functional lignin biopolymer

Al-loaded functional lignin biopolymer (Alx-Lbp) catalysts were synthesized using H2O2 oxidized alkali lignin and aluminum acetate via mechanochemical modification without post-calcination treatment. The Alx-Lbp catalysts exhibited higher hydrophilicity and lower surface energy than lignin-free Al-activated carbon catalysts. Unprecedented high yields (58.5 %) of fructose from glucose were obtained over Al1-Lbp in ethanol at 140 ºC in 30 min reaction time. Al1-Lbp catalyst had Lewis acid sites (47.2 μmol/g), Brønsted acid sites (6.9 μmol/g) and a surface energy of 39.1 mN/m that facilitated glucopyranose ring-opening and gave a glucose isomerization activation energy of 65.2 kJ/mol, which was lower than values reported for Lewis acid-catalyzed systems. Active sites of Al2O3 and Al(OH)3 formed on the Al1-Lbp catalyst in ethanol promoted the formation of an enediol intermediate as confirmed with isotope experiments to achieve efficient isomerization of glucose to fructose. The Al1-Lbp catalyst demonstrated recyclability and maintained its initial activity for eight times reuse.

Pyrrolic Nitrogen Boosted H2 Generation from an Aqueous Solution of HCHO at Room Temperature by Metal-Free Carbon Catalysts.

Hydrogen production from organic hydrides represents a promising strategy for the development of safe and sustainable technologies for H2 storage and transportation. Nonetheless, the majority of existing procedures rely on noble metal catalysts and emit greenhouse gases such as CO2/CO. Herein, we demonstrated an alternative N-doped carbon (CN) catalyst for highly efficient and robust H2 production from an aqueous solution of formaldehyde (HCHO). Importantly, this process generated formic acid as a valuable byproduct instead of CO2/CO, enabling a clean H2 generation process with 100% atom economy. Mechanism investigations revealed that the pyrrolic N in the CN catalysts played a critical role in promoting H2 generation via enhancing the transformation of O2 to generate •OO- free radicals. Consequently, the optimized CN catalysts achieved a remarkable H2 generation rate of 13.6 mmol g-1 h-1 at 30 °C. This finding is anticipated to facilitate the development of liquid H2 storage and its large-scale utilization.

Synergistic oxidation of humic acid treated by H2O2/O3 activated by CuCo/C with high efficiency and wide pH range

Combination of oxidation processes are one of the most promising humic acid treatment technologies. Single oxidant or even two oxidants in advance oxidation process can hardly achieve satisfactory removal efficiency of refractory organic matter, mainly humic acid, in the treatment process of reverse osmosis concentrates from landfill leachate. To solve this problem, this study investigated the synergistic degradation of Humic acid (HA) using a Cu and Co supported on carbon catalyst (CuCo/C) in a Hydrogen peroxide (H2O2) with ozone (O3) system. The catalyst was characterized by performing SEM, XRD, BET, XPS and FTIR technologies. UV–vis spectra, 3D Excitation Emission Matrix Spectra (3D-EEM) and gas chromatography-mass spectrometry (GC–MS) were applied for exploring degradation mechanism of HA. To further understand the oxidation mechanism, electron paramagnetic resonance (EPR) was used to evaluate the generation of hydroxyl (·OH) and superoxide radicals (O2·-). As a result, CuCo/C catalyst possessed stable catalytic performance for HA degradation with a wide pH range from 5 to 8, while T = 40 °C，catalyst dosage of 2.4 g/L，O3 intake rate of 0.15 g/min and H2O2 dosage of 1.92 mL/L, the degradation rate of total organic carbon (TOC) achieved 40–46.5 mg·L−1min−1. As affirmed by the EPR, ·OH and O2·- were effectively generated with addition of the CuCo/C catalyst. Degradation performance of UV254 proved that the catalytic activity can still be maintained above 95% with removal rate of 82% after 5 cycles reuse. GC-MS shows that the oxidation products mainly consist of amide, benzoheterocyclic ring and carboxylic acid. This work promotes an effective method for degrading HA, which has the potential for satisfactory application in landfill leachate.

How the macrocyclic precursors influence the M-N-C catalysts? Preparation and their applications on the electrochemically catalyzed hydrogen evolutions

Herein, a series of metallo-porphyrins, corroles and phthalocyanines were applied as the key precursors to confirm the influence of macrocyclic cores on the preparation of single- and dual-metal nitrogen-doped carbon (M-N-C) catalysts, and the control the M-N-C catalyst preparation towards accelerating electrocatalyzed hydrogen evolutions could be rationally modulated. Due to the synergetic effect, the dual-metal Co0.97Cu0.03TPP@rGO-900 M-N-C catalyst has the best performance on the electrochemically catalyzed hydrogen evolution with onset potentials as −166 mV and Tafel 117 mV·dec−1. More importantly, these M-N-C catalysts could also be used in a wide range of pH values, such as PBS and KOH medias.

Development of single-atom Ru and N, S-Co-doped carbon catalyst for enhanced cycling stability of lithium-oxygen batteries

Li-oxygen (Li-O2) battery is a novel energy storage equipment. However, its poor reaction reversibility relating to the insoluble lithium peroxide (Li2O2) generated during the discharge process, limits its application and development for large scale use. Therefore, the design and synthesis of effective catalysts which can efficiently catalyze the production and decomposition of Li2O2 and exclude the generation of side-products has become the primary task to develop Li-O2 batteries. Herein, a new type of electrocatalyst based on single-atom Ru and N, S-co-doped carbon materials (Ru/CNS/CNT) is introduced to reduce the overpotential of the battery reaction and accelerate the formation and decomposition of Li2O2. Galvanostatic charge-discharge tests were performed on the Li-oxygen (Li-O2) battery with Ru/CNS/CNT as the cathode catalyst material. With a limited specific capacity of 1000 mA h g−1, the battery can stably cycle for 79 cycles at a current density of 200 mA g−1. Furthermore, the existence of the single atom of Ru was demonstrated according to the characterization of HAADF-STEM. The experimental results showed that composite material Ru/CNS/CNT can accelerate the formation and decomposition of lithium peroxide (Li2O2), thereby greatly improving the cycling stability of the battery.

Bimetal organic framework derived CoM@N–C composites as bifunctional oxygen catalysts for Zn-air batteries

Metal-loaded nitrogen-doped carbon (M@N–C) catalysts have shown promise as electrocatalysts for replacing noble metal catalysts in industrial processes. To study the influence on structural and performance caused by different bimetal doping, a family of bimetals CoM@N–C (M = Cu/Ni/Fe) composites with porous surface and abundant C defects were well-designed. After bimetallic doping, more defects are introduced into the carbon frameworks, and the metal-N species are fixed. As such, efficient utilization of active sites and rapid mass transfer make the reaction kinetics process more favorable and stable. Density functional theory calculations indicate that Cu/Ni doping optimizes the electronic environment of the Co–N, resulting in the balanced adsorption and dissociation of oxygen intermediates. While the synergy of FeCo activates the O=O, which promotes the sharp decrease in free energy of ∗OOH to ∗O, shifting the rate-determining step for oxygen reduction reaction. This indicates the adsorption site transfer of CoFe0.05@N–C in oxygen reduction and evolution reactions. The CoFe0.05@N–C catalyst exhibits superior bifunctional catalytic activity (with a potential gap of 0.80 V) than that of Pt catalysts. This work presents a simple strategy to fabricate well-defined bimetals doping in bifunctional oxygen electrocatalysts and it is expected to inspire future work on the role of electronic structure modulation and interface engineering.

Green preparation of fiberboard waste derived N–doped carbon catalysts with tailored properties for efficient hydrogenation reduction of nitroaromatics

Biomass–derived carbon materials doped with diverse heteroatoms have demonstrated huge potentials for environment and energy applications, thanks to the availability, preferable porous and channel structures, and excellent conductivity and stability. In this work, fiberboard waste containing resin–based adhesive was selected for the green fabrication of N–doped carbon catalysts without using extra N–sources. A facile two–step calcination strategy with sequential carbonization and activation was proposed for generation and exposure of indispensable active sites, realizing the controllable regulation of textural and morphological characteristics. The resulting N–doped fiberboard derived carbon (NFC) samples possessed unique hierarchically porous structures with a significantly enlarged surface area, plentiful activity–dependent N species (e.g., graphitic N and pyridinic N), as well as suitable graphitization degree and surface hydrophilicity. As a result, a favorable adsorption procedure and an enhanced accessibility of active sites synergistically boosted the catalytic performance towards hydrogenation reduction of nitroaromatics. Taking the NFC–hh sample as paradigm, an excellent performance was demonstrated for 4–nitrophenol (4–NP) reduction, achieving a high apparent rate constant of 0.40 min−1 and an impressive turnover frequency of ∼0.20 mmol g−1 min−1. Besides, the continuous–flowing catalytic test exhibited an excellent conversion efficiency > 99.50% with a long–term stability over 100 h, showing an attractive prospect for industrial application. This work presents a new approach for high value–added utilization of biomass waste, and provides a low–cost and high–active catalyst for environmental remediation.

Carbon derived from orange peel waste for preparation of benign bimetallic catalyst in organic reactions

In this work, a convenient approach has been applied to discover the potential valorization of biomass waste such as orange peel in which PdCu-based nanostructured systems were synthesized via a one-step in-situ dry-milling approach to obtain the benign bimetallic catalysts with different palladium(Pd) and Copper(Cu) loadings on the orange peel support (Pd1%Cu1%, Pd0.3%Cu0.7%, Pd0.5%Cu0.5%, Pd0.5%Cu1%). Catalytic applications of these new composites were investigated in the Sonogashira-Hagihara coupling reaction as well as the Sonogashira–click reaction sequence to the preparation of substituted 4-aryl-1,2,3-triazoles and reduction of nitroaromatics under mild reaction conditions. Catalytic tests with the four activated carbons catalysts showed that the C@Pd1%Cu1% catalyst was the most active in the Sonogashira-Hagihara coupling reaction compared to the other catalysts. Also, the C@Pd0.5%Cu0.5% catalyst showed the highest catalytic activity in the reduction of 1-chloro-4-nitrobenzene and 4-nitrophenol in comparison with other prepared carbon catalysts.

Efficient isomerization of glucose into fructose by MgO-doped lignin-derived ordered mesoporous carbon

The conversion of glucose into fructose can transform cellulose into high-value chemicals. This study introduces an innovative synthesis method for creating an MgO-based ordered mesoporous carbon (MgO@OMC) catalyst, aimed at the efficient isomerization of glucose into fructose. Throughout the synthesis process, lignin serves as the exclusive carbon precursor, while Mg2+ functions as both a crosslinking agent and a metallic active center. This enables a one-step synthesis of MgO@OMC via a solvent-induced evaporation self-assembly (EISA) method. The synthesized MgO@OMCs exhibit an impeccable 2D hexagonal ordered mesoporous structure, in addition to a substantial specific surface area (378.2 m2/g) and small MgO nanoparticles (1.52 nm). Furthermore, this catalyst was shown active, selective, and reusable in the isomerization of glucose to fructose. It yields 41 % fructose with a selectivity of up to 89.3 % at a significant glucose loading of 7 wt% in aqueous solution over MgO0.5@OMC-600. This performance closely rivals the current maximum glucose isomerization yield achieved with solid base catalysts. Additionally, the catalyst retains a fructose selectivity above 60 % even after 4 cycles, a feature attributable to its extended ordered mesoporous structure and the spatial confinement effect of the OMCs, bestowing it with high catalytic efficiency.

Catalytically Active Carbon for Oxygen Reduction Reaction in Energy Conversion: Recent Advances and Future Perspectives.

The shortage and unevenness of fossil energy sources are affecting the development and progress of human civilization. The technology of efficiently converting material resources into energy for utilization and storage is attracting the attention of researchers. Environmentally friendly biomass materials are a treasure to drive the development of new-generation energy sources. Electrochemical theory is used to efficiently convert the chemical energy of chemical substances into electrical energy. In recent years, significant progress has been made in the development of green and economical electrocatalysts for oxygen reduction reaction (ORR). Although many reviews have been reported around the application of biomass-derived catalytically active carbon (CAC) catalysts in ORR, these reviews have only selected a single/partial topic (including synthesis and preparation of catalysts from different sources, structural optimization, or performance enhancement methods based on CAC catalysts, and application of biomass-derived CACs) for discussion. There is no review that systematically addresses the latest progress in the synthesis, performance enhancement, and applications related to biomass-derived CAC-based oxygen reduction electrocatalysts synchronously. This review fills the gap by providing a timely and comprehensive review and summary from the following sections: the exposition of the basic catalytic principles of ORR, the summary of the chemical composition and structural properties of various types of biomass, the analysis of traditional and the latest popular biomass-derived CAC synthesis methods and optimization strategies, and the summary of the practical applications of biomass-derived CAC-based oxidative reduction electrocatalysts. This review provides a comprehensive summary of the latest advances to provide research directions and design ideas for the development of catalyst synthesis/optimization and contributes to the industrialization of biomass-derived CAC electrocatalysis and electric energy storage.

Biobased Vanillin Production by Oxidative Depolymerization of Kraft Lignin on a Nitrogen- and Phosphorus-Functionalized Activated Carbon Catalyst

Biobased Vanillin Production by Oxidative Depolymerization of Kraft Lignin on a Nitrogen- and Phosphorus-Functionalized Activated Carbon Catalyst

Local oxygen transport resistance in polymer electrolyte fuel cells: origin, dependencies and mitigation

Next-generation polymer electrolyte fuel cells (PEFCs) require an integral design of the porous structure of electrodes at different scales to improve performance and enlarge durability while reducing cost. One of today’s biggest challenges is the stable, high-performance operation at low Pt loading due to the detrimental effect of the local oxygen transport resistance caused by ionomer around catalyst sites. Hindered local oxygen transport arises from sluggish kinetics at the local reaction environment, that comprises adsorption at (wet) ionomer and Pt interfaces, and diffusivity of gas species in ionomer and water. Diverse factors affect oxygen transport, including operating conditions (relative humidity, temperature, and pressure), ionomer content and morphology, ionomer heterogeneity, porosity of carbon support, catalyst dispersity, and flooding. To attain performance and durability targets, it is essential to maximize the oxygen utilization of the catalyst layer by implementing enhanced membrane electrode assembly architectures. This involves employing advanced catalyst layer preparation techniques, including electrospraying, to generate optimized highly porous morphologies. Furthermore, achieving these targets necessitates the development of new materials with tailored properties, such as high permeability and porous ionomers, among other innovative strategies.

Synthesis of high-performance low-Pt (1 1 1)-loading catalysts for ORR by interaction between solution and nonthermal plasma

One important approach to address the cost issue of fuel cells is to maximize the utilization of Pt by reducing its loading and enhancing the performance for the oxygen reduction reaction (ORR) as well as durability of catalysts. In this work, a one-step synthesis of highly dispersed low-Pt (111) electrocatalysts (p-Pt/KBs) supported by Ketjenblack is conducted using interaction between solution and nonthermal plasma (SNP). The results show that the plasma-treated platinum precursor dispersion efficiently avoids particle agglomeration and increases more defects of the support surface, which are conducive to the trapping and anchoring of platinum nanoparticles (Pt NPs). The catalyst (p-Pt/KB-NaOH) with a platinum load of 10.8 wt% is obtained by adding sodium hydroxide to the platinum precursor dispersion solution, showing better ORR performance (E1/2 = 0.88 V) and stability compared to the commercial platinum on carbon (Pt/C) catalyst (20 wt%, E1/2 = 0.86 V). This improvement is attributed to the fact that neutralizing chloroplatinic acid slows down the reduction rate of the platinum precursor, effectively controlling the rapid nucleation and slow crystal growth of platinum. As the cathode catalyst for PEMFCs, p-Pt/KB-NaOH exhibits remarkable mass-transfer performance in the high-current density domain (HCD), with maximum power density (Pmax) of 1131 mW cm−2 at 2500 mA cm−2, which is 9.1 % higher than commercial Pt/C. Moreover, the single-cell operates stably for at least 100 h at 1000 mA cm−2 with a negligible decay (1.9 %) of the working voltage, ensuring long-term durability.

A universal method for preparing biomass derived topologically defective carbons with superior catalytic performance in cationic radical polymerization

This study aims to develop a universal preparation method for biomass-derived topologically defective carbons and reveal the catalytic mechanism of such carbons for cationic radical polymerization. Firstly, bamboo fiber-derived topologically defective carbon (BFTC) is prepared by an ammonia-assisted heat treatment method. BFTC can significantly promote the chemical oxidative polymerization of 3-aminophenylboronic acid (a typical cationic radical polymerization process) and obtain high molecular weight products, which is mainly attributed to the rich topological defect structure of BFTC. Secondly, the ammonia-assisted heat treatment method is applied to two other biomasses, and the derived carbons have similar microstructure and chemical composition to BFTC, indicating the universality of this method at the material preparation level; meanwhile, these derived carbons also exhibit excellent catalytic properties when they promote 3-aminophenylboronic acid (ABA) polymerization, which further confirms the universality of this method from the perspective of material properties. Finally, research on the catalytic mechanism shows that there is an interaction based on partial electron transfer between the topological defects of the carbon catalyst and ABA or ABA-derived radical. This effect promotes the rapid derivatization of ABA into cationic radical, and also improves the stability of the radical, thereby achieving efficient polymerization of ABA around the topological defect active center. Therefore, this study confirms the universality of the ammonia-assisted heat treatment method to prepare biomass-derived topologically defective carbon, and such defective carbons are likely to serve as catalysts for cationic radical polymerization.

A novel magnetic Fe, N co-doped Ce-MOFs derived carbon as a peroxymonosulfate activator for the degradation of tetracycline hydrochloride: Performance and activation mechanism

The activation of peroxymonosulfate (PMS) using metal-organic frameworks (MOFs) has garnered significant interest in the field of wastewater treatment. However, the environmental challenges associated with traditional methods for synthesizing MOFs precursors, such as the requirement for high temperatures and pressures, remain. Furthermore, the catalytic performance and stability of mono-metallic materials are areas needing enhancement. This work successfully synthesized a novel magnetic Fe-Ce bimetallic N-doped porous MOF material (Fe/Ce@5MNC). The optimized Fe/Ce@5MNC exhibited a higher specific surface area and a more extensive pore structure, as verified by various characterization techniques. Moreover, the synthesis process of the precursor is simpler, energy-saving, and relatively environmentally friendly. Notably, the synergistic effect between Fe and Ce, coupled with the presence of multiple active sites such as FeNx and graphite N, enabled Fe/Ce@5MNC to decompose 86.4 % of TCH within 30 min, marking a 31.4 % increase over Ce@NC. After four cycles, the catalyst maintained good surface stability, with the degradation efficiency remaining at 67.7 %. Quenching and electron paramagnetic resonance (EPR) experiments confirmed that the main degradation mechanisms are singlet oxygen (1O2) generation and electron transfer. This study presents a new method for synthesizing efficient Fe, N co-doped magnetic bimetallic PMS activators and designing carbon catalysts for deep oxidation.

Understanding amorphous PrOx-based N-doped carbon catalyst as an efficient electrocatalyst for oxygen reduction reaction

Understanding amorphous PrOx-based N-doped carbon catalyst as an efficient electrocatalyst for oxygen reduction reaction

Improving the anti-coking ability in the Ni-M(M = Ce, Zr, Co)@SiO2 yolk-shell catalysts for dry reforming of methane

Dry methane reforming (DRM) represents a highly promising approach to greenhouse gas conversion (CO2 and CH4) to valuable byproducts. However, severe carbon deposition and catalyst deactivation inhibit large-scale applications. The work designed new catalysts with a yolk-shell structure using the water-in-oil microemulsion method. The catalysts were composed of a yolk-shell structure, with Ni-M as the active point and silica as the shell. The catalytic performance evaluation indicates that the Ni-M @SiO2 catalysts show higher CH4 and CO2 conversion compared with the Ni@SiO2 and conventional catalysts at 750 ℃, suggesting the yolk-shell structure and added M species enhance the DRM activity. The XRD, HRTEM, XPS, BET, H2-TPR, and CO2-TPD analysis confirmed the existence of yolk-shell configuration and evident electronic effect among Ni, M species, and SiO2. The long term measurements indicate that the added M species also bring higher carbon deposition tolerance for DRM, where Ni-Ce@SiO2 and Ni-Zr@SiO2 exhibit good structural and catalytic stability for DRM over 100 h. Through XRD, TEM, and TGA characterizations of the exhausted catalysts, it is determined that the coke deposition resistance of the catalyst is improved as a result of increased oxygen mobility and enhanced Ni dispersion on the catalytic surface, both of which are enhanced by the added Ce species. The structural analysis of the spent catalysts indicates that the tolerance of carbon deposition is improved by the yolk-shell samples. This study can offer valuable insights for the development of Ni-based catalysts with exceptional carbon deposition capability for DRM.