Preparation Of Catalysts Research Articles

Construction of an Axial Charge Transfer Channel Between Single-Atom Fe Sites and Nitrogen-Doped Carbon Supports for Boosting Oxygen Reduction.

The introduction of axial-coordinated heteroatoms in Fe─N─C single-atom catalysts enables the significant enhancement of their oxygen reduction reaction (ORR) performance. However, the interaction relationship between the axial-coordinated heteroatoms and their carbon supports is still unclear. In this work, a gas phase surface treatment method is proposed to prepare a series of X─Fe─N─C (X = O, P, and S) single-atom catalysts with axial X-coordination on graphitic-N-rich carbon supports. Synchrotron-based X-ray absorption near-edge structure spectra and X-ray photoelectron spectroscopy indicate the formation of an axial charge transfer channel between the graphitic-N-rich carbon supports and single-atom Fe sites by axial O atoms in O─Fe─N─C. As a result, the O─Fe─N─C exhibits excellent ORR performance with a half-wave potential of 0.905V versus RHE and a high specific capacity of 884 mAh g-1 for zinc-air battery, which is superior to other X─Fe─N─C catalysts without axial charge transfer and the commercial Pt/C catalyst. This work not only demonstrates a general synthesis strategy for the preparation of single-atom catalysts with axial-coordinated heteroatoms, but also presents insights into the interaction between single-atom active sites and doped carbon supports.

Non-oxidative ethane dehydrogenation reaction over molybdenum and chromium incorporated MgO encapsulated carbon-core catalysts in microwave reactor

AbstractChromium and molybdenum incorporated MgO and MgO–C catalysts were synthesized for hydrogen production from a non-oxidative ethane dehydration reaction. Hydrogen production studies were carried out using a microwave-heated reactor system. The study investigated the effects of reaction temperature, type of active metal, and catalyst preparation method (physical mixture or core–shell structure) on hydrogen selectivity and ethane conversion during dehydrogenation reactions. The results showed that the optimal reaction temperature for the non-oxidative ethane dehydration reaction was 450 °C. Above this temperature, the selectivity of undesired byproducts increased. Catalysts containing molybdenum exhibited higher ethane conversion. Moreover, a comparison of MgO–C-supported catalysts with MgO-supported catalysts revealed that the core–shell catalysts exhibited superior ethane conversion. Notably, the 5Mo@MgO–C catalyst demonstrated exceptional catalytic activity, achieving a high ethane conversion rate of 72% along with excellent stability.

Preparation and Application of Latent Microcapsule Catalysts in One-Component Silicone Rubber Curing

Preparation and Application of Latent Microcapsule Catalysts in One-Component Silicone Rubber Curing

One-Step Synthesis of High-Efficiency Oxygen Evolution Reaction Catalyst FeSx(Y/MB) with High Temperature Resistance and Strong Alkali

Given the energy crisis and escalating environmental pollution, the imperative for developing clean new energy is evident. Hydrogen has garnered significant attention owing to its clean properties, high energy density, and ease of storage and transportation. This study synthesized four types of catalysts—FeS(DI/MB), FeS(ET/MB), Fe(DI/MB), and Fe(ET/MB)—using two distinct solution systems: DI/MB and ET/MB. The FeS(DI/MB) catalyst, synthesized using the layered solution system (DI/MB), demonstrates a uniformly distributed and dense nanosheet structure, exhibiting excellent resistance to strong bases and superior catalytic properties. The FeS(DI/MB) electrode showed OER overpotentials of 460 mV and 318 mV in 1 M and 6 M, respectively, at current densities of up to 500 mA cm−2. Under industrial electrolysis test conditions, the FeS(DI/MB) electrode required only 262 mV to achieve a current density of 500 mA cm−2, operating in a high-temperature, strong alkaline environment of 6 M at 60 °C. Furthermore, the FeS(DI/MB) electrode exhibited excellent OER catalytic activity and stability, as evidenced by a 60 h stability test These findings provide valuable insights into the preparation of iron nickel sulfide-based catalysts, and further in-depth and comprehensive exploration is anticipated to yield the excellent catalytic performance of these catalysts in the realm of electrolytic water hydrogen production.

Facile Synthesis of WS2/WO3 Materials in a Batch Reactor for the Hydrogen Evolution Reaction

In this study, a new and facile process was developed for the preparation of composite catalysts based on tungsten oxide (WO3) by batch reactor routes. The structures, morphologies, compositions, and characteristics of synthesized materials were investigated and confirmed. Using batch reactor processes, WO3 nanorods (WO3 NR), heterostructures of WS2/WO3 nanobricks (WS2/WO3 NB), and WS2/WO3 nanorods (WS2/WO3 NR) were successfully prepared. The prepared materials were then employed for hydrogen evolution reaction (HER) to investigate their catalytic performance. The results indicated that the electrocatalytic activities of WS2/WO3 NR are significantly improved compared to those of WO3 NR and WS2/WO3 NB. This improvement could be attributed to the formation of heterostructure between WS2 and WO3 elements in highly uniform materials, which could create the synergistic effect and further improve the catalytic activities of the catalyst. The data shows that the Tafel slope of WS2/WO3 NR (82.7 mV dec−1) is significantly lower than that of WO3 NR (112.5 mV dec−1) and WS2/WO3 NB (195.5 mV dec−1). Furthermore, the resistance of WS2/WO3 NR (397.7 Ω) is markedly decreased compared to those of WO3 NR (1816 Ω) and WS2/WO3 NB (3597 Ω). The results indicate that WS2/WO3 NR could be a great catalyst for electrochemical applications.

Preparation and Evaluation of FeMnTi Monolithic Catalysts for High‐Efficiency CO Oxidation

AbstractA comprehensive study was conducted on the synthesis of FeMnTi monolithic catalysts using plasma electrolytic oxidation (PEO) process combined with hydrothermal method followed by depositing active nanostructures. As synthesized catalysts were characterized using a series of techniques for morphology, structure and surface chemical state investigations. Meanwhile, the CO light‐off curves demonstrate that they possess excellent low‐temperature catalytic performance compared with TiO2 based single transition oxides. Specifically, FeMnTi(0.10, 4) can achieve 100 % conversion at 201 °C, which is due to the homogeneous elements distribution, large surface area and high surface activity. The supersaturation of the deposited solution and deposition time determine the growth of MnOx and the FeMnTi(0.10, 4) has the most suitable Fe/Mn atom ratio of 2.5. Furthermore, the electron transfer between Fe (Fe2+ and Fe3+) and Mn (Mn2+, Mn3+ and Mn4+) ensures the excellent redox properties. The synthetic strategy proposed in this work has general applicability for synthesizing multiple transition oxides monolithic catalysts not only for CO oxidation.

Enhanced activity of Ru-based catalysts for ammonia decomposition through nitrogen doping of hierarchical porous carbon carriers

Activated carbon (AC) materials, renowned for their high specific surface area, excellent conductivity, and customizable functional groups, are widely employed as catalyst carriers. However, enhancing the activity of Ru-based catalysts supported on AC (Ru/AC) for ammonia decomposition remains a challenge. In this study, commercial AC was utilized as a substrate, with glucose and urea employed as modifiers. Specifically, the surface of the AC was modified via a hydrothermal pyrolysis method, resulting in the successful post-treatment in situ co-doping of nitrogen (AC-GN). Experimental results revealed that Ru/AC-GN exhibited a hydrogen production rate 46% higher than that of Ru/AC at 475 °C, indicating improved activity and stability. The characterization of AC-GN demonstrated that nitrogen doping primarily occurred on the external surface and macropores of the AC, increasing the nitrogen content in the carrier, particularly pyrrolic nitrogen content, while preserving the original structural and morphological integrity of the AC. The enhanced dispersion of Ru, combined with the improved electronic transmission capabilities and strengthened interactions between the metal and the modified carrier, were identified as pivotal factors contributing to the enhanced low-temperature efficacy of Ru/AC-GN. This paper presents a novel direction for the large-scale preparation of efficient catalysts for ammonia decomposition.

4‐Methyltetrahydropyran: a Versatile Alternative Solvent for the Preparation of Chiral BINOL Catalysts and the Asymmetric Alkylation of Aldehydes

We herein report that the highly hydrophobic ether 4‐MeTHP constitutes a promising resource for the development of sustainable synthetic methodologies grounded on the use of organometallic reagents. The beneficial effects of 4‐MeTHP as reaction media are illustrated in the organolithium‐promoted anionic ortho‐Fries rearrangement of 1,1’‐bi‐2‐naphthol (BINOL)‐based carbamates under bench‐type conditions. The use of 4‐MeTHP induces a remarkable and unexpected stability of the organolithiums species, enabling the efficient preparation of chiral (bis)carboxamide catalysts. Furthermore, superior performances of 4‐MeTHP than other environmentally responsible solvents are observed using the synthesized BINOL catalysts in the asymmetric addition of organozinc reagents to aldehydes. Spectroscopic studies in solution suggest that 4‐MeTHP plays a key role in these reactions by inducing the preferential formation of a reactive monomeric dinuclear complex. This methodology allows for the asymmetric assembly of enantioenriched secondary alcohols in good yields and high stereoselectivity, working at 0 °C and under air.

Preparation of palladium-based catalyst by plasma-assisted atomic layer deposition and its applications in CO2 hydrogenation reduction

Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO2 hydrogenation. A fluidized-bed plasma assisted atomic layer deposition (FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al2O3 or Fe2O3/γ-Al2O3 support, using palladium hexafluoroacetylacetonate as the Pd precursor and H2 plasma as counter-reactant. Scanning transmission electron microscopy exhibits that high-density Pd nanoparticles are uniformly dispersed over Fe2O3/γ-Al2O3 support with an average diameter of 4.4 nm. The deposited Pd-Fe2O3/γ-Al2O3 shows excellent catalytic performance for CO2 hydrogenation in a dielectric barrier discharge reactor. Under a typical condition of H2 to CO2 ratio of 4 in the feed gas, the discharge power of 19.6 W, and gas hourly space velocity of 10000 h−1, the conversion of CO2 is as high as 16.3% with CH3OH and CH4 selectivities of 26.5% and 3.9%, respectively.

Homogenous Oxidizing Oligomerization Coupled with Coagulation for Water Purification

Natural manganese oxides could induce the intermolecular coupling reactions among small-molecule organics in aqueous environments, which is one of the fundamental processes contributing to natural humification. These processes could be simulated to design novel advanced oxidation technology for water purification. In this study, periodate (PI) was selected as the supplementary electron-acceptor for colloidal manganese oxides (Mn(IV)aq) to remove phenolic contaminants from water. By introducing polyferric sulfate (PFS) into the Mn(IV)aq/PI system and exploiting the flocculation potential of Mn(IV)aq, a post-coagulation process was triggered to eliminate soluble manganese after oxidation. Under acidic conditions, periodate exists in the H4IO6− form as an octahedral oxyacid capable of coordinating with Mn(IV)aq to form bidentate complexes or oligomers (Mn(IV)-PI*) as reactive oxidants. The Mn(IV)-PI* complex could induce cross-coupling process between phenolic contaminants, resulting in the formation of oligomerized products ranging from dimers to hexamers. These oligomerized products participate in the coagulation process and become stored within the nascent floc due to their catenulate nature and strong hydrophobicity. Through coordination between Mn(IV)aq and H4IO6−, residual periodate is firmly connected with manganese oxides in the floc after coagulation and could be simultaneously separated from the aqueous phase. This study achieves oxidizing oligomerization through a homogeneous process under mild conditions without additional energy input or heterogeneous catalyst preparation. Compared to traditional mineralization-driven oxidation techniques, the proposed novel cascade processes realize transformation, convergence, and separation of phenolic contaminants with high oxidant utilization efficiency for low-carbon purification.

Ferric sludge derived pyrolyzed-hydrochar supported iron catalysts for catalytic cracking of toluene

Effective treatment of ferric sludge in an eco-friendly method is key to the feasibility of Fenton technology in pollution treatment, contributing to the realization of the “dual-carbon” strategic objectives. In this study, Fe-loaded pyrolyzed-hydrochar catalysts were prepared using simple one-pot hydrothermal carbonization (HTC) method with ferric sludge as the precursor, which greatly reduced the energy and time consumption on the preparation of the sludge derived catalyst. At 800 °C with a reaction time of 20 min, all catalysts showed high toluene removal performance (>60 %) and produced H2-rich syngas (H2 > 90 %). In particular, the catalyst prepared by HNO3-assisted HTC (HNC) presented the highest toluene removal efficiency and H2 yield, 77.52 ± 3.36 % and 11.12 ± 0.66 mol%, respectively. Additionally, the sources of carbon deposits and the interaction between the active site and carbon deposits were analyzed in detail by DFT to reveal the catalytic activity and deactivation mechanism of catalyst. The results showed that the adsorption energy of C generated from methyl on different Fe phases was lowest (the adsorption energy of C was −8.79 eV for Fe, −5.28 eV for Fe2O3, and −4.70 eV for Fe3O4), suggesting that the adsorption of C on catalyst was the main reason for the formation of carbon deposits. The lowest adsorption energy of the metallic Fe phase for C indicated that Fe0 was coated by carbon deposits during toluene catalytic cracking, which hampered catalytic activity. These results are of great significance for optimizing the preparation of Fe-loaded carbonaceous catalysts and the regulation of Fe active phase.

Magnetic FNS/MILs nanofibers for highly efficient removal of norfloxacin via adsorption and Fenton-like reaction

Iron-containing MOFs have attracted extensive interest as promising Fenton-like catalysts. In this work, magnetic Fe3O4 nanofiber (FNS)/MOFs composites with stable structure, included FNS/MIL-88B, FNS/MIL-88A and FNS/MIL-100, were prepared via the in-situ solvothermal method. The surface of the obtained fibers was covered by a dense and continuous MOFs layer, which could effectively solve the agglomeration problem of MOFs powder and improved the catalytic performance. The adsorption and catalytic properties of FNS/MOFs composites were evaluated by removal of norfloxacin. FNS/MIL-88B showed the best performance with a maximum adsorption capacity up to 214.09 mg/g, and could degrade 99% of NRF in 60 min. Meanwhile, FNS/MIL-88B had a saturation magnetization of 20 emu/g, and could be rapidly separated by an applied magnetic field. The self-supported nanofibers allowed the adequate contact between MOFs and pollutants, and promoted the catalytic activity and high stability. We believe that this work provided a new idea for the design and preparation of Fenton-like catalysts especially MOFs composites.

Reverse loading of inert Al2O3 onto active iron oxide for improved H2O2 activation and pollutant degradation

Developing heterogeneous iron-based catalysts with superior reactivity and stability is a long-term goal for hydrogen peroxide (H2O2) activation in Fenton-like technique for water remediation. Supported iron-based nanocomposites are of great interest due to their earth abundance, environmental friendliness, and tunable structure. However, existing iron-based Fenton catalysts are normally designed via the loading of iron-derived nanoparticles onto various inert substrates, where the surface reactive sites are hardly affected by the substrate. Here, we report the first example of reversely loaded FeOx-Al2O3 nanocomposite via overturning the loading direction, i.e., loading inert Al2O3 support onto reactive FeOx nanoparticles. The resultant FeOx@Al2O3-R catalyst demonstrated much improved reactivity for H2O2 activation and bisphenol A removal (by 14 times in terms of first-order rate constant) than its analog FeOx/Al2O3-T, which was prepared via the loading of FeOx nanoparticles onto inert Al2O3 support. Moreover, FeOx@Al2O3-R exhibited excellent stability with Fe leaching only one sixth of FeOx/Al2O3-T. Systematic characterization results revealed that the inert Al ions modify the electronic environment and properties of the surface Fe reactive sites. This work provides an alternative reverse loading strategy to traditional loading method for the preparation of iron-based nanocomposite catalyst that is highly efficient for H2O2 activation and pollutant removal.

Deposition of Pd, Pt, and PdPt Nanoparticles on TiO2 Powder Using Supercritical Fluid Reactive Deposition: Application in the Direct Synthesis of H2O2.

In this study, we investigated the catalytic properties of mono- and bimetallic palladium (Pd) and platinum (Pt) nanoparticles deposited via supercritical fluid reactive deposition (SFRD) on titanium dioxide (TiO2) powder. Transmission electron microscopy analyses verified that SFRD experiments performed at 353 K and 15.6 MPa enabled the deposition of uniform mono- and bimetallic nanoparticles smaller than 3 nm on TiO2. Electron-dispersive X-ray spectroscopy demonstrated the formation of alloy-type structures for the bimetallic PdPt nanoparticles. H2O2 is an excellent oxidizing reagent for the production of fine and bulk chemicals. However, until today, the design and preparation of catalysts with high H2O2 selectivity and productivity remain a great challenge. The focus of this study was on answering the questions of (a) whether the catalysts produced are suitable for the direct synthesis of hydrogen peroxide (H2O2) in the liquid phase and (b) how the metal type affects the catalytic properties. It was found that the metal type (Pd or Pt) influenced the catalytic performance strongly; the mean productivity of the mono- and bimetallic catalysts decreased in the following order: Pd > PdPt > Pt. Furthermore, all catalysts prepared by SFRD showed a significantly higher mean productivity compared to the catalyst prepared by incipient wetness impregnation.

Preparation and Evaluation of Resistance Coke Formation Catalysts in Combined Reforming of Methane Using Steam and Oxygen for the Production of Synthesis Gas

Preparation and Evaluation of Resistance Coke Formation Catalysts in Combined Reforming of Methane Using Steam and Oxygen for the Production of Synthesis Gas

In-situ integration of potassium carbonate/Kraft lignin catalyst preparation and biodiesel production via ball-milling process

In this paper, an in-situ integration process of catalyst preparation and biodiesel production via ball-milling process was first proposed. The yield of biodiesel can reach 100 % in a short preparation time of 10 min and a reaction time of 20 min. According to the temperature tracking data during the reaction, there is a synergistic catalytic effect of mechanical energy and thermal energy in the reaction process. The characterization results showed the catalyst prepared by ball-milling process has excellent catalytic activity and potassium (K) is uniformly dispersed on ball-milling-K2CO3/Kraft lignin (BM-K2CO3/KL) catalysts. Based on socio-economic and techno-economic evaluation, biochar-derived catalyst for biodiesel production has created a good market value, and the mechanochemical processes are more cost-effective than traditional thermal catalytic process. This process uses ball-milling technology to integrate catalyst preparation and biodiesel production, which has the advantage of simple operation, strong controllability, and is conducive to improving the FAME yield.

Universal, minute-scale synthesis of transition metal compound nanocatalysts via graphene-microwave system for enhancing sulfur kinetics in lithium-sulfur batteries

The application of Li-S batteries on large scale is held back by the sluggish sulfur kinetics and low synthesis efficiency of sulfur host. In addition, the preparation of catalysts that promote polysulfide redox kinetics is complex and time-consuming, reducing the cost of raw materials in Li-S. Here, a universal synthetic strategy for rapid fabrication of sulfur cathode and metal compounds nanocatalysts is reported based on microwave heating of graphene. Heat-sensitive materials can achieve rapid heating due to graphene reaching 500 ℃ within 4 s via microwave irradiation. The MoP-MoS2/rGO catalyst demonstrated in this work was synthesized within 60 s. When used for catalysts for Li-S batteries whose graphene/sulfur cathodes were also synthesized by microwave heating, enhanced catalytic effect for sulfur redox reaction was verified via experimental and DFT theoretical results. Benefiting from fast redox reaction (MoP), smooth Li+ diffusion pathways (MoS2), and large conductive network (rGO), the assembled Li-S battery with MoP-MoS2/rGO-Add@CS displays a remarkable initial specific capacity, stable lithium anode and good cycle stability (in pouch cells) using this two-pronged strategy. The work provides a practical strategy for advanced Li-S batteries toward a wide range of applications.

Iron catalysts enhanced by ultrasound for methane decomposition and hydrogen generation

Clean hydrogen production offers a viable alternative in the transition to a greener and more sustainable energy future. This study introduces a novel method for enhancing Fe/Al2O3 catalysts using La2O3 and CeO2 doping, aimed at improving hydrogen production via methane decomposition. It addresses the critical challenge of modulating metal-support interaction. Employing ultrasonication in the catalyst preparation, we observed through XRD, H2-TPR, H2 chemisorption, Raman spectroscopy, TGA, and TPO analyses that La2O3 addition prevents FeAl2O4 formation and increases Fe reduction and active sites. Catalysts assisted by ultrasound outperform traditional methods, exhibiting a consistent and significant increase in conversion and yield efficiencies. The La2O3-modified catalysts outperformed the standard Fe/Al2O3 catalyst in methane decomposition. At 800 °C, they demonstrated enhanced activity and stability under demanding conditions, achieving a methane conversion of 93% and hydrogen yield of 84%. This approach boosts hydrogen production and contributes to the development of sustainable and efficient energy solutions.

Deactivation of nickel/biochar catalyst through metal-volatiles interaction in pyrolysis of poplar sawdust loaded with nickel salt

Metal/biochar is an important category of catalyst that can be prepared via direct impregnation of metal salt to a biomass feedstock. However, during pyrolysis of metal salt@biomass for catalyst preparation, metal-volatiles interaction might affect exposure or dispersion of metal species. To verify this, loading of nickel acetate to poplar sawdust directly and to the sawdust-derived biochar was conducted to prepare Ni/biochar and biochar/Ni at 500 or 750 °C, aiming to understand the effect of metal-volatiles interaction on exposure of nickel species in resulting Ni/biochar. The results indicated Ni species catalyzed cracking, dehydrogenation, and reforming reactions in sawdust pyrolysis, producing more bio-oil/gases at the expense of biochar and also making biochar of higher aromatic degree with improved thermal stability. The in-situ IR characterizations also evidenced high activity of Ni towards dehydration and cracking of carbonyls for enhancing aromatization of biochar. In biochar/Ni catalysts prepared via loading nickel to biochar, little metal-volatiles interaction existed and nickel species weakly interacted with the biochar, resulting in remarkable migration and agglomeration of nickel, forming nickel size of 2–3 times larger than that in Ni/biochar. However, biochar/Ni possessed higher capability for adsorption/activation of H2, thus exhibiting superior catalytic activity than Ni/biochar for hydrogenation of phenolics.

Efficient Life-Cycle Management: Recyclable self-support MnCuOxS1-x wastewater treatment catalyst for electrosynthesis of benzoic acid to accelerate hydrogen production

Integrating recyclability and reusability into catalyst design can effectively mitigate environmental impact. In this investigation, a three-dimensional Mn-doped Cu2OxS1-x catalyst was incorporated into Cu foam. Following its application in wastewater treatment, the reclaimed catalyst demonstrates robust electrocatalytic prowess in benzyl alcohol oxidation. It efficiently degrades 93.5 % of tetracycline within a 30-minute timeframe in neutral wastewater conditions. Notably, alterations in its morphology and valence state have bolstered its electrocatalytic performance. During the electrosynthesis of benzoic acid, it showcases a diminished starting voltage (1.27 V) while retaining an impressive Faraday efficiency of 97.4 % even at a high voltage of 1.70 V. Density Functional Theory (DFT) analyses shed light on the integration of the catalyst onto Cu foam, facilitating electron transfer from the Cu substrate to the surface catalyst. Furthermore, it is readily recoverable and enhances the adsorption of electrophilic H2O2, thereby augmenting wastewater treatment efficacy. In the context of benzoic acid electrosynthesis, DFT investigations demonstrate that Mn doping significantly enhances the adsorption of OH* and benzyl alcohol in electrocatalysis, thereby enhancing their conversion to benzoic acid. This method of catalyst design, integrating recycling and reuse strategies, has reduced material and energy consumption during catalyst preparation and provided a pathway for the development of advanced catalysts with a focus on sustainability.