Excellent Catalytic Activity Research Articles

Sulfur Modified Carbon-Based Single-Atom Catalysts for Electrocatalytic Reactions.

Efficient and sustainable energy development is a powerful tool for addressing the energy and environmental crises. Single-atom catalysts (SACs) have received high attention for their extremely high atom utilization efficiency and excellent catalytic activity, and have broad application prospects in energy development and chemical production. M-N4 is an active center model with clear catalytic activity, but its catalytic properties such as catalytic activity, selectivity, and durability need to be further improved. Adjustment of the coordination environment of the central metal by incorporating heteroatoms (e.g., sulfur) is an effective and feasible modification method. This paper describes the precise synthetic methods for introducing sulfur atoms into M-N4 and controlling whether they are directly coordinated with the central metal to form a specific coordination configuration, the application of sulfur-doped carbon-based single-atom catalysts in electrocatalytic reactions such as ORR, CO2RR, HER, OER, and other electrocatalytic reaction are systematically reviewed. Meanwhile, the effect of the tuning of the electronic structure and ligand configuration parameters of the active center due to doped sulfur atoms with the improvement of catalytic performance is introduced by combining different characterization and testing methods. Finally, several opinions on development of sulfur-doped carbon-based SACs are put forward.

Quasi-solid electrochemiluminescence immunosensor constructed with gel electrolyte for the detection of CEA

In this paper, we report a novel quasi-solid electrochemiluminescence (ECL) immunosensor platform for the detection of tumor marker carcinoembryonic antigen (CEA). Referring to the conventional three-electrode system of electrochemistry, a gel alternative solution was introduced, and a quasi-solid solvent-free scheme was designed. The use of gels brings several advantages. Firstly, the introduction of gels also provides a new platform for the specific recognition of antigens and antibodies. Secondly, gels can be mass-manufactured like ELISA plate, which reduces the cost of testing and thus provides a reference scheme for large-scale sensor applications. Thirdly, a new device was designed to accommodate the improved sensors. In addition, a simple one-step hydrothermal method was used to synthesize AuNPs/MnO2/TiO2 materials. Utilizing its excellent catalytic activity for CO-reaction reagents H₂C₂O₄, it promotes the production of CO2–• and thus enhances the ECL of Ru(bpy)32+. Thus, this biosensor provides a novel and efficient strategy for CEA detection. The gel system sensor also provides a general model for the detection of other biomarkers and provides new applications for biochemical analysis and clinical diagnosis.

Multi-omics analysis of Au@Pt nanozyme for the modulation of glucose and lipid metabolism

Au@Pt nanozyme, a bimetallic core–shell structure Au and Pt nanoparticle, has attracted significant attention due to its excellent catalytic activity and stability. Here, we propose that Au@Pt improves glucose tolerance and reduces TG after four weeks administration. The transcriptomic analysis of mouse liver tissues treated with Au@Pt nanozyme showed changes in genes related to glucose and lipid metabolism signaling pathways, including glycolysis/gluconeogenesis, pyruvate metabolism, PPAR signaling, and insulin signaling. Moreover, analysis of fecal samples from mice treated with Au@Pt nanozyme showed significant changes in the abundance of beneficial gut microbiota such as Dubosiella, Parvibacter, Enterorhabdus, Monoglobus, Lachnospiraceae_UCG-008, Lachnospiraceae_UCG-006, Lachnospiraceae_UCG-001, and Christensenellaceae_R-7_group. Combined multi-omics correlation analyses revealed that the modulation of glucose and lipid metabolism by Au@Pt was strongly correlated with changes in hepatic gene expression profiles as well as changes in gut microbial profiles. Overall, our integrated multi-omics analysis demonstrated that Au@Pt nanozyme could modulate glucose and lipid metabolism by regulating the expression of key genes in the liver and altering the composition of gut microbiota, providing new insights into the potential applications of Au@Pt nanozyme in the treatment of metabolic disorder.Graphical

Oxygen vacancies boosted Bi2WO6 for photoelectrochemical water oxidation

In this work, bismuth tungstate (Bi2WO6) films enriched with oxygen vacancies were fabricated via the hydrogen treatment with an excellent catalytic activity. The photocurrent density of Bi2WO6 H-15 is 0.18 mA/cm2 at 1.23 V (vs. RHE), which is 11.25 times higher than that of pure Bi2WO6. The introduction of oxygen vacancy not only increases the charge concentration, facilitates the charge transport, promotes the water absorption ability, but also extends the light absorption of Bi2WO6. The density of states (DOS) calculated by the density functional theory (DFT) showed that a new defect level was formed and increased DOS at the valance band maximum (VBM). This work manifests the effective use of oxygen vacancies in regulating carriers transport, which is of great significance for the PEC oxygen evolution reaction.

Insights into the multiple active sites in Bi-Co bimetallic oxide for a deeper understanding of nitrate electroreduction to ammonia

The electrochemical nitrate reduction reaction (NO3RR) is a promising approach for nitrate removal and NH3 production at ambient conditions. The development of various types of efficient electrocatalysts, especially bimetallic oxides with the advantages of superior durability and excellent catalytic activity, have become a research focus. However, the analysis of active sites for bimetallic oxide catalysts either emphasizes the role of bimetallic interactions or focuses on the role of oxygen vacancies (OVs), resulting in a lack of thoroughness. Herein, a Bi-Co bimetallic oxide (BCO) was constructed for NO3RR, illustrating 1.5∼7.8 folds higher NH3 yield rate than those of commercial single metal oxide (Bi2O3, Co3O4). The NO3RR pathway by BCO was explored according to H* capture test, DEMS, and isotope labeling experiment. An in-situ Raman test showed the structure evolution of BCO during NO3RR, and therefore the catalytic sites of BCO were further identified according to physical characteristics before and after NO3RR. Results suggest that Bi0, OVs and amorphous Co oxide as the real active sites play a vital role in nitrate electroreduction. Furthermore, research on 25 articles also indicates the presence of multiple catalytic sites in bimetallic oxides for NO3RR. This study provides a new and comprehensive insight into the active sites identification for the type of bimetallic oxide NO3RR electrocatalysts.

Highly enhanced photoelectrocatalytic activity of NiFe/Ni/BiVO4 photoanode by a facile photoelectron-activation process in neutral solution

Photoelectrocatalytic water splitting is a promising approach to convert solar energy to hydorgen energy. Delicate design of photoanode is crucial for the excellent catalytic activity. Here, a NiFe-LDH/Ni/BiVO4 composite photoanode was prepared by magnetron sputtering of Ni followed by electrochemical deposition of NiFe-LDH on BiVO4 photoelectrode. Interestingly, after a concise photoelectron-activation process, a photocurrent of 4.9 mA/cm2 (1.23 V vs. RHE) was obtained in neutral solution, which is 4 times of the pristine BiVO4 photoanode. The photoelectro-activation process not only enhances the photocurrent, but also significantly supresses the positive spiking phenomenon of the photocurrent. A series of characterizaitons including XRD, SEM, EDX, HRTEM, and XPS ect. were performed, which revealed that the photoelectron-activation process led to the reconstruction of the surface structure of NiFe-LDH/Ni/BiVO4. The dynamic characterizaitons including stepped potential chronoamperometry, steady-state photoluminescence (PL) spectra, open-circuit potential diagrams, and electrochemical impedance spectroscopy (EIS) ect. were performed. It indicates that the activated samples can provide an enhanced internal electric field and enable the charge carriers being efficiently injected into the electrode/electrolyte interface to promote the water oxidation reaction. This investigation provided a facile activation method for BiVO4-based composite photoanode, and highly increase the PEC performance in neutral condition.

Sorption-enhanced ethanol steam reforming coupled with in-situ CO2 capture and conversion

The impacts of climate change and the issue of greenhouse gas emissions have sparked research into renewable energy alternatives to fossil fuels. Hydrogen has gained attention as a clean, renewable and environmentally friendly energy source. Enhanced-ethanol steam reforming has been proposed as a promising method for blue hydrogen production, addressing greenhouse gas emission issues. The use of catalysts enhances the adsorption of ethanol and water molecules on the surface, promoting the reaction rate. This study systematically explored the effects of different Fe loading and CaO addition ratios on the ethanol steam reforming and CO2 conversion processes to optimize catalyst performance. The experimental results showed that Fe/SiC catalysts effectively promoted the conversion of ethanol and generated high-purity hydrogen, exhibiting excellent catalytic activity. Specifically, a catalyst with 10 % Fe loading and mixed with 0.3g CaO significantly increased the hydrogen yield to 64.4 mmol/g, which was 2.88 times higher than that without the catalyst.

Ag-MOF Nanocatalyst for the Asymmetric Hantzsch Synthesis of Polyhydroquinolines Under Green Conditions

A highly efficient and stable heterogeneous coordination polymer (CP) catalyst was successfully prepared by hydrothermal reaction of silver and 4,6-Diamino-2-pyrimidinethiol, using amine, thiol and pyrimidine functional groups. Besides, silver ions were coordinated to the ligand functional groups in order to give a novel Ag-CPs catalyst. Besides, it was characterized using FT-IR, XRD, TGA, SEM, EDX, X-ray mapping and BET analysis. The prepared Ag-CPs exhibit excellent catalytic activity for multicomponent Hantzsch synthesis of polyhydroquinolines under mild reaction condition in relatively short reaction times. The heterogeneity of the catalyst was confirmed by the hot filtration test and, then, the catalyst was reused for at least four times under the optimized conditions without any significant loss of its activity.

Super-exchange interaction enables Fe2−xMnxO3 perovskite with excellent catalytic oxidation activity toward hexabromocyclododecane under humidity

Although enhancing the catalytic oxidation activity is a hotspot in thermal-driven catalytic disposal of persistent organic pollutants, few studies have managed to improve catalysts' water-resistance properties. Herein, we developed Fe2−xMnxO3 perovskite to boost the catalytic oxidation of hexabromocyclododecane under humidity by modulating its super-exchange interaction (SEI, Fe3+ + Mn3+ → Fe2+ + Mn4+). Fe0.4Mn1.6O3, with the strongest SEI, exhibits the biggest oxidation rate-constant, which is 3 times higher than that of commonly used Fe2O3 without SEI. Notably, unlike Fe2O3 which deactivates at a relative humidity of 5 %. Fe0.4Mn1.6O3 maintains its activity and is even boosted by 22 % compared to dry conditions. Mechanistic insights reveal that SEI between Fe and Mn enhances the reactivity of Mn4+- linked Olatt by lowering the reductive temperature from Mn4+ to Mn3+. Meanwhile, SEI promotes the adsorption of the associatively adsorbed H2O (HOH-type water) by reducing adsorption energy, thereby facilitating the formation of hydroxyl species, which are crucial for the oxidation process under humidity.

Construction of Ru-doped Co nanoparticles loaded on carbon nanosheets in-situ grown on carbon nanofibers as self-supported catalysts for efficient hydrogen evolution reaction

Exploring efficient and economical electrocatalysts to replace noble metal electrocatalysts has become a major research focus nowadays. In this paper, Ru-doped Co nanoparticles loaded on carbon nanosheet (CNS) in-situ grown on carbon nanofibers (Ru–Co@CNS/CNFs) were constructed as a self-supporting working electrode for high-efficiency hydrogen evolution. The prepared Ru–Co@CNS/CNFs possessed excellent catalytic activity with only 78 mV overpotential at 10 mA cm−2 current density and good stability with only 102 mV voltage attenuation at 100 mA cm−2 current density for 100 h continuous operation. The excellent catalytic performance could be attributed to the unique microstructure of the nanosheets in-situ grown on the nanofibers, it resulted in a higher Co surface density of 1.28 mg cm−2, indicating more loading of metal to improve catalytic activity of HER, and the formed Ru-doped Co nanoparticles could be evenly distributed on the carbon nanosheets to prevent the aggregation of nanoparticles, which could expose more active sites. Additionally, the density functional theory (DFT) calculations revealed Ru doping could accelerate the dissociation of water, optimize the adsorption energy of hydrogen intermediates and improve the kinetics of the HER reaction. This work provides a new approach to reduce the use of noble metals while improving the catalytic performance of catalysts.

Copper supported Dowex50WX8 resin utilized for the elimination of ammonia and its sustainable application for the degradation of dyes in wastewater

To obtain high efficient elimination of ammonia (NH4+) from wastewater, Cu(II), Ni(II), and Co(II)) were loaded on Dowex-50WX8 resin (D-H) and studied their removal efficiency towards NH4+ from aqueous solutions. The adsorption capacity of Cu(II)-loaded on D-H (D-Cu2+) towards NH4+ (qe = 95.58 mg/g) was the highest one compared with that of D-Ni2+ (qe = 57.29 mg/g) and D-Co2+ (qe = 43.43 mg/g). Detailed studies focused on the removal of NH4+ utilizing D-Cu2+ were accomplished under various experimental conditions. The pseudo-second-order kinetic model fitted well the adsorption data of NH4+ on D-Cu2+. The non-linear Langmuir model was the best model for the adsorption process, producing a maximum equilibrium adsorption capacity (qmax = 280.9 mg/g) at pH = 8.4, and 303 K in less than 20 min. The adsorption of NH4+ onto D-Cu2+ was an exothermic and spontaneous process. In a sustainable step, the resulting D-Cu(II)-ammine composite from the NH4+ adsorption process displayed excellent catalytic activity for the degradation of aniline blue (AB) and methyl violet 2B (MV 2B) dyes utilizing H2O2 as an eco-friendly oxidant.

Electrocatalytic ammonia synthesis on bimetallic AuPd porous structures

In industry, production of ammonia mainly relies on the intensive Haber-Bosch process, but it consumes high energy with low efficiency and generates a large number of green-house gases. Electrocatalytic nitrogen reduction reaction (ENRR), as an alternative method for fixing N2 under ambient conditions, provides a feasible strategy for sustainable development of N2 cycle storage and utilization of renewable energy. However, traditional nanocatalysts exhibit extremely poor ENRR performance due to low activity of the solid structure and intense hydrogen evolution reactions of single component. Herein, we design and prepare porous gold–palladium nanoalloys (pAuPdNs), which effectively enhance ENRR by the excellent catalytic activity of Au and the significant N2 fixation ability of Pd, as well as the nanoporous structure and synergistic effect between alloy components. The electrochemical results show the NH3 yield of the catalyst is as high as 43.6 μg·h−1·cm−2, and Faradaic efficiency reaches 43.8%, which are superior to the performances of most reported water-based ENRR electrocatalysts. Besides, the selectivity of 95% and stability also exhibit enhancement than numerous reported researches. As compared with solid alloy and porous Au or Pd structures, the superiority of pAuPdNs states the influence of alloying and porous structure. Hence pAuPdNs are proved to be the efficient, stable, and promising electrocatalysts for N2 reduction reaction at ambient temperature and atmospheric pressure.

Borate ester hybrid photothermal nanofluid derived from C3N4/MoS2 catalyzed esterification for efficient organic-inorganic synergistic lubrication

The inferior dispersion stability and simple functionality of MoS2-based nanofluids restrict their efficient application in lubrication. Herein, a novel nanofluid composed of C3N4/MoS2, 3-isocyanatopropyltrimethoxysilane, and C3N4/MoS2-catalyzed product (polyethylene glycol-borate ester, PEG-BA) was proposed. C3N4 nanosheets could induce the formation of regular MoS2 nanospheres. The resulting C3N4/MoS2 showed excellent catalytic activity for the esterification of PEG-BA. The C3N4/MoS2 @PEG-BA nanofluid exhibited favorable dispersion stability in PEG600 with no stratification for ≥ 82 days. The addition of 3.0 wt% C3N4/MoS2 @PEG-BA nanofluid could significantly reduce friction coefficient (30.7 %) and wear scar diameter (28.9 %). The excellent lubrication properties of the nanofluid are attributed to the synergistic lubrication effect of C3N4/MoS2 and PEG-BA. Furthermore, the nanofluid exhibits remarkable photothermal conversion performance in both oil and air mediums.

Solar-driven photocatalytic nitrogen fixation on transition metal-doped covalent organic frameworks: First-principles study

Designing highly efficient single-atom catalysts for converting nitrogen into ammonia under ambient temperature conditions holds significant importance. Current research predominantly focuses on electrocatalytic nitrogen fixation, but compared to that, photocatalytic nitrogen fixation requires only sunlight as an energy source, making it more environmentally friendly and cost-effective. Developing efficient nitrogen reduction reaction (NRR) photocatalysts presents a promising yet highly challenging task. Two-dimensional (2D) covalent organic frameworks (COFs) have garnered interest because of their elevated surface area and regular pore structure. This study employs density functional theory calculations to investigate the potential of NRR photocatalysts using the 2D COF TMT-TFPT-COF (TT-COF) supported with 18 different transition metal atoms (TM = Rh, Nb, Os, Mo, Ru, Pt, Ni, Co, V, Cu, Fe, Re, W, Cr, Ta, Mn, Pd, Ti). Through a four-step selection process, the most promising photocatalyst is identified. The results indicate that a single Re atom loaded onto TT-COF (Re@TT-COF) displays the optimal nitrogen fixation performance, demonstrating excellent catalytic activity and selectivity with a limiting potential of only −0.30 V. Furthermore, its good light absorption efficiency, suitable band edge position, and significant photo-generated electron potential enable spontaneous nitrogen fixation. Our study provides useful guidance for the rational design of COF-based NRR photocatalysts with high activity, stability, and selectivity.

Study on the performance of Co–Ni sulfide electrocatalysts supported by different fibroin-based carbon precursors

Research on sustainable energy sources is crucial for alleviating environmental issues and addressing energy security concerns. This study investigates the utilization of various silk precursors in the hydrogen evolution reaction. Waste silk fabric, regenerated silk fibroin film, porous silk fibroin, silk cocoon and degummed silk fibroin were used as precursors to prepare HER electrocatalysts. To investigate the influence of precursor form on catalytic perform9ance, a comparative analysis of the morphology, structure and composition of different materials was conducted. Among various catalysts, waste silk fabric based catalysts exhibit the most excellent catalytic activity, with an overpotential of 113 mV at 10 mA cm−2 and a Tafel slope of 30.9 mV/dec. Even After 1000 cycles of testing, it still maintains excellent catalytic activity. This study provides insights into the influence of precursor forms on the electrochemical performance of biomass carbon-based catalysts, aiming to inspire further research in this field.

A magnetic nanocatalyst based on Bronsted acid and Lewis acid centers for the efficient synthesis of polycyclic melting 1,5-benzodiazepines

In this study, 3-(Triethoxysilyl)propyl chloride (CPTES) was used to modify the surface of magnetic nanoparticles Fe3O4@SiO2, and aminomethylphosphonic acid (AMPA) was further anchored on the surface. Then, Ce (III) was used as the ligand to immobilize the surface of the modified material with N/O as the donor. Magnetic nanocatalysts (Fe3O4@SiO2@CPTES@AMPA@CeCl3) were successfully prepared. The prepared catalysts were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen absorption-desorption experiment (BET), vibrating sample magnetometer (VSM), energy dispersive spectroscopy (EDS) and inductively coupled plasma atomic emission spectrometry (ICP-AES). A synergetic effect of Brønsted and Lewis acid (AMPA and CeCl3) of the magnetic nanocatalyst was examined to active carbonyl, imine or enamine bonds for the synthesis of polycyclic fused 1,5-benzodiazepine with quaternary carbon centers or quinoxaline ring in a one-pot method. It was found that this catalyst exhibited excellent catalytic activities (TON up to 111368, TOF up to 110232 h−1) and high selectivities in the synthesis of fused 1,5-benzodiazepine compounds (22 examples, 85–96 % yields). The mechanism for the synthesis of polycyclic fused 1,5-benzodiazepine catalyzed by Fe3O4@SiO2@CPTES@AMPA@CeCl3 was proposed. The nanocatalyst was readily recovered by simple magnetic decantation and can be recyclable without obviously reducing catalytic activity up to seven times.

Sponge-like tungsten phosphide-ruthenium constructed by ultrafast quasi-solid state microwave for wide pH hydrogen generation

Transition metal phosphides (TMPs) are typical of emerging hydrogen evolution reaction (HER) catalysts, but tedious synthesis approach limits its practical applications. Herein, sponge-like tungsten phosphide with ruthenium (Ru/WP) is synthesized by a simple and rapid (20 s) quasi-solid state microwave approach. The synthesized Ru/WP possesses porous morphology with rich interconnected channels to accelerate the energy transport and expose ample active sites. In addition, the strong electronic interactions promote the reaction kinetics between Ru and WP. Thus, the prepared Ru/WP owns excellent catalytic activity in alkaline freshwater/seawater, acid and neutral electrolyters, with low overpotentials of 36/24, 48, and 69 mV to provide 10 mA cm−2 for HER. In alkaline electrolyte, the overall water decomposition requires only 1.57 V to reach 10 mA cm−2 with satisfactory stability. The rapid microwave quasi-solid state synthesis strategy provides a novel direction for developing metal phosphides in the energy sector.

Regulating the microstructure and catalytic activity of metal selenides via calcination strategy for lithium-sulfur battery

Metal selenides obtain a series of advantages such as high electronic conductivity, excellent catalytic activity and facile fabrication approach, which are considered as promising catalysts in lithium sulfur (Li-S) battery. Traditional research based on metal selenides focuses on designing novel/complex microstructures or composites, however, the catalytic ability can be greatly affected by internal properties such as defect or vacancy. In this work, hollow nickel-cobalt layered double hydroxide (NiCo-LDH) is first fabricated and applied as a precursor to fabricate NiCoSe, and Se vacancy accompanied with crystal phase, microstructure and catalytic activity can be regulated by simply adjusting selenization atmosphere and temperature. Involving the application of NiCoSe in Li-S battery, the optimum fabrication parameter is perform the selenization at 600 °C under argon/5 % hydrogen, and the battery can exhibit a high discharge specific capacity of 1042.8 mAh g−1, excellent cycling performance of 500 cycles with a decay rate of 0.083 % at 1 C. This work highlights the importance of calcination process and also provides reference for further modifying the microstructure and performance of metal selenides in Li-S battery.

Construction of 2D porous g-C3N4 by steam reforming with the introduction of Fe clusters forming Fe-Nx to enhance photo-Fenton catalytic activity

In this study, the Fe clusters were anchored onto 2D porous g-C3N4 nanosheets to synthesize Photo-Fenton catalysts Fe-CNS with highly and uniformly dispersed Fe-Nx active sites via a supramolecular thermal polymerization and subsequent impregnation strategy. The obtained Fe-CNS composites exhibited excellent Photo-Fenton catalytic activity and stability even under high pH and anion conditions, suggesting Fe clusters doping into 2D porous g-C3N4 nanosheets host through Fe-Nx coordination structures enhanced the separation efficiency of light-generated charge carriers, promoted Fe3+/Fe2+ redox cycle, accelerated the activation of H2O2 and improved the stability of Fe species and leading to a remarkable Photo-Fenton synergistic effect. Among these Fe-CNS composites, Fe-CNS with doping amount of 7 % Fe species shows superior Photo-Fenton activity for the elimination of Tetracycline (TC), and the corresponding k value is 0.04729 min−1, which is 25.4 times superior to that of photocatalytic oxidation TC of bulk g-C3N4, indicating that the strategy on changing Fe doping amount yielded opportunity to optimize Photo-Fenton combined action between Fe clusters and g-C3N4 nanosheets host. The degradation mechanism of TC using Fe-CNS composites in the Photo-Fenton system has been further elucidated by considering that the embedded Fe clusters in the N-rich 2D g-C3N4 nanosheets form abundant Fe-Nx active sites.

Formulation and Characterization of Moringa Oleifera Nano Particles

The synthesis of copper oxide nano particles (CuO NPs) using moringa oleifera leaves extract as a green reducing agent has gained significant interest due to its eco-friendly and cost-effective nature. Moringa oleifera leaves extract acts as a reducing agent and capping agent simultaneously, making it a promising alternative to traditional methods. The size, shape, and optical properties of the synthesized CuO NPs can be controlled by varying the concentration of moringa oleifera leaves extract and reaction time. The synthesized CuO NPs exhibit excellent antimicrobial, antioxidant, antiviral, anti-inflammatory and catalytic activities, making them suitable for various applications in bio medicine, wastewater treatment, and energy storage. Overall, the green synthesis of CuO NPs using moringa oleifera leaves extract holds great potential for sustainable and green nanotechnology. FTIR and UV Studies carried out in which it showed that drug-drug and drug-excipients are compatible.