Latest ArticlesBimetallic catalysts usually exhibit better performance than monometallic catalysts due to synergistic effect. However, there is a lack of exploring the synergistic effect on catalytic performance caused by the introduction of inactive metal ion. In this work, we design a molecular model system that can precisely regulate the metal site number and catalytic property. When these molecular metal compounds are used as homogeneous catalysts for photocatalytic CO2 reduction, the dinuclear heterometallic CuNi-L2 shows the highest CO2-to-CO conversion, which is 2.1 and 3.0 times higher than that of dinuclear homometallic Ni2-L2 and mononuclear Ni-L1. Density functional theory calculations demonstrate that, in CuNi-L2, the introduction of inactive CuII is easier to promote the photo-generated electrons transferring to the coupled active NiII site to achieve the highest activity. In addition, this work also provides insights to design and construct more efficient bimetallic catalysts in future.
Application of Li-oxygen (Li-O2) battery is in urgent need of bifunctional ORR/OER electrocatalyst. A surface-functionalization CoP/Ti3C2Tx composite was fabricated theoretically, with the optimized electronic structure and more active electron, which is beneficial to the electrochemical reaction. The accordion shaped Ti3C2Tx is featured with large specific surface area and outstanding electronic conductivity, which is beneficial for the adequate exposure of active sites and the deposition of Li2O2. Transition metal phosphides provide more electrocatalytic active sites and present good electrocatalytic effect. The CoP/Ti3C2Tx composite served as the electrocatalyst of Li-O2 battery reaches a high specific discharge capacity of 17, 413 mAh/g at 100 mA/g and the lower overpotential of 1.25 V, superior to those of the CoP and Ti3C2Tx individually. The composite of transition metal phosphides and MXene are applied in Li-O2 battery, not only demonstrating higher cycling stability of the prepared CoP/Ti3C2Tx composite, but pointing out the direction for their electrochemical performance improvement.
Heavy metals usually exist stably as the species of organic complexes in high-salinity wastewater. Therefore, their effective removal is challenging, especially when the initial pH is neutral. Herein, a novel nitrogen doped biomass-based composite (N-CMCS) was synthesized to remove the complexed heavy metal of Cr(Ⅲ)-carboxyl. The maximum adsorption capacity of Cr(Ⅲ)-Citrate (Cr-Cit) by N-CMCS under neutral pH (7.0) and high-salinity (200 mmol/L NaCl) condition was up to 2.50 mmol/g. And the removal performance remained stable after 6 times of regeneration. Combined with species and characterizations analysis, electrostatic attraction and hydrogen bonding were the main mechanisms for N-CMCS to remove Cr(Ⅲ)-carboxyl complexes. Dynamic adsorption indicated N-CMCS column could treat about 1300 BV simulated wastewater and 350 BV actual wastewater with the concentration of effluent lower than 1.0 mg/L. Furthermore, N-CMCS could remove a variety of complexed heavy metal ions under neutral pH, indicating the great potential in practical application.
6-Thioguanine (6TG) is a widely used chemotherapeutic agent for the treatment of a variety of human diseases including acute lymphoblastic leukemia. After entry into cells, 6TG is metabolically converted into 6-thioguanosine (SG) nucleotide that can be incorporated into the genome during DNA replication. SG in genomic DNA could induce cell death by triggering the post-replicative mismatch repair (MMR) pathway. Meanwhile, incorporation of 6TG into the CpG sites could perturb the global DNA methylation and gene regulation. However, the effect of 6TG on RNA modifications is still unknown. Adenosine-to-inosine (A-to-I) editing in RNA is one of the most common post-transcriptional modifications in mammals and there is growing evidence showing the significant alteration of A-to-I RNA editing in tumor tissues compared to normal tissues. In the current study, we examined the incorporation of 6TG into RNA and investigated its effect on A-to-I editing of bladder cancer-associated protein (BLCAP) transcript in acute lymphoblastic leukemia cells. The results demonstrated that SG could be incorporated into various RNA species, with mRNA having the most abundant SG. In addition, the results showed 6TG treatment elevated A-to-I editing in BLCAP transcript through upregulating adenosine deaminase 2 acting on RNA (ADAR2), which eventually contributes to the decreased cell viability. This study highlights a new mechanism of the cytotoxicity of 6TG in inducing cell death.
Derivative-extremum analysis (DEA) of j-E curves is a newly proposed method of half wave potential (E1/2) and activation feature extraction from steady-state voltammetry. Here, the DEA is demonstrated to be valid in the full range of reversibility using numerical simulations with a derived universal electrode equation, providing a novel perspective of electrochemical kinetics in the reversibility domain. The results reveal that E1/2 is a better choice of the reference potential instead of equilibrium potential (Eeq) in electrode equations, especially since Eeq is meaningless in an irreversible case. The equations referenced with standard potential, E1/2 and Eeq, are summarized in three tables, and their applications in parameter determinations are specified. Finally, reversibility is proved to be a relative measure between kinetic slowness and mass transport of electroactive species, and the reversibility classifications are proposed according to the DEA feature in the reversibility domain. This work, based on the DEA principle, refines the electrode equation forms and generalizes their applicability in the full range of reversibility.
Manganese dioxide (MnO2), a commonly find oxidant in both natural environment and industrial application, plays a crucial role for various organic compound degradation. Tuning the MnO2 crystal structure is a cost-effective strategy to boost the oxidation reactions, where the challenge remains due to lacking in-depth investigation of the crystal properties. Herein, MnO2 with different crystalline structures (x-MnO2) including α-, β- and δ- was prepared through the hydrothermal synthesis for a typical organic pollutant removal. The structural and degradation analysis indicated that the oxidation capacity was originated from Mn3+ and oxygen vacancies (OVs). The intrinsic relationships between oxidation performance and other physiochemical properties such as morphology and electrochemistry were thoroughly discussed, and positive correlations between oxidation capacity and electrochemical properties were found which eventually led to excellent oxidation performance via modulating the above-mentioned properties. Moreover, the K+ content was determined to be the most crucial role in manipulating the structure properties. This work offers a crystal-level insight into the relationship between the crystal structure and oxidative property, promoting rational design of highly efficient oxidant.
The cycloaddition reactions of methane and ethylene mediated by Ir+ have been designed and studied by the techniques of mass spectrometry in conjunction with theoretical calculations. Studies have shown that Ir+ can mediate the cycloaddition reaction of CH4 and two C2H4 to generate a half-sandwich structure IrHCp+ (Cp = η5-C5H5) including pentamethylcyclopentadienyl ligand by continuous dehydrogenation reaction with the forming of three C-C bonds and seven C-H bonds. The orbital analysis indicates the mechanism of the cyclization reaction to generation of pentamethylcyclopentadienyl ligand with odd number carbon atom depends on the overlap of π orbitals in -C2H2 and carbene, which is more difficult than the forming of cyclobutadiene ligand and benzene. This study may help to understand the reaction mechanism in the cycloaddition reactions of organic compounds, which will be useful to guide the rational design of new catalysts with tailored selectivity and increased efficiency.
The defect engineering in graphene plays a significant role for the application of gas sensors. In this work, we proposed an efficient method to prepare ultrasensitive gas sensors based on the porous reduced graphene oxide (PRGO). Photo-Fenton etching was carried out on GO nanosheets in a controlled manner to enrich their vacancy defects. The resulting porous graphene oxide (PGO) was then drop-coated on interdigital electrodes and hydrothermal reduced at 180 ℃. Controllable reduction was achieved by varying the water amount. The gas sensor based on PRGO-5 min-6 h exhibited superior sensing and selective performance toward nitrogen dioxide (NO2), with an exceptional high sensitivity up to 12 ppm−1. The theoretical limit of detection is down to 0.66 ppb. The excellent performance could be mainly attributed to the typical vacancy defects of PRGO. Some residue carboxylic groups on the edges could also facilitate the adsorption of polar molecules. The process has a great potential for scalable fabrication of high-performance NO2 gas sensors.
Supercapacitors (SCs) are rated as the foremost efficient devices bridging the production and consumption of renewable energy. To address the ever-increasing energy requirements, it is indispensable to further develop high-performance SCs with merits of high energy-density, acceptable price and long-term stability. This review highlights the recent advances on halogen-based functionalized chemistry engineering in the state-of-the-art electrode system for high-performance SCs, primarily referring to the doping and decoration strategies of F, Cl, Br and I elements. Due to the discrepancy of electronegativity and atomic radius, the functionalization of each halogen element endows the substrate materials with different physicochemical properties, including energy bandgap structure, porosity distribution and surface affinity. The principle of halogen embedment into host materials by precisely controlling ionic adsorption and electronic structure is presented. And, the vital perspectives on the future challenges of halogen functionalization are also discussed. This work aims to deepen the understanding of halogen-based functionalized strategies to motivate further research for the development of high-performance SCs, and it also provides a prospect for exploring new material modification methods for electrochemical energy storage.
Although converting the greenhouse gasses carbon dioxide (CO2) into solar fuels is regarded as a convenient means of solar energy storage, the intrinsic mechanism on how the high chemical inertness linear CO2 molecules is activated and converted on a semiconductor oxide is still elusive. Herein, by creating the oxygen vacancies on the typical hexagonal tungsten oxide (WO3), we realize the continuous photo-induced CO2 reduction to selectively produce CO under light irradiation, which was verified by isotope labeling experiment. Detailed oxygen vacancies evolution investigation indicates that light irradiation can simultaneously induce the in-situ formation of oxygen vacancies on hexagonal WO3, and the oxygen vacancies promote the adsorption and activation of CO2 molecules, leading to the CO2 reduction to CO on the hexagonal WO3 via an oxygen vacancies-involved process. Besides, the existence of water further promotes the formation of CO2 reduction intermediate, further promote the CO2 photoreduction. Our work provides insight on the mechanism for converting CO2 into CO under light irradiation.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62662699(Operation and Technical Support)
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
