新工科背景下的应用化学综合实验改革——以可见光催化分解水制氢综合实验为例

将科研课题“ZrO_(2)@TiO_(2)异质结的制备及可见光催化分解水制氢研究”设计成应用化学专业综合实验,使科研课题的创新性和教学的可行性有机结合,推进创新人才培养。实验内容是多学科的交叉融合,涉及ZrO_(2)@TiO_(2)异质结的制备、结构表征、催化剂的活性评价等多项内容,并且将新材料的制备与材料的性能、应用关联起来,加强了学生应用能力的拓展,强调了理科向工科的渗透。通过此实验,学生经历了催化学科科学前沿研究的全过程,可激发学生的学习兴趣,提高学生的科研素养,培养学生的创新思维、独立思考和分析解决问题的能力。

纳米酶在抗肿瘤治疗中的应用

纳米酶是一类具有天然酶活性的纳米材料。相对于天然酶,纳米酶有着制备简单,成本低,稳定性高,易于保存等优点。自从2007年,我国科学家阎锡蕴院士首次发现Fe_(3)O_(4)纳米颗粒具有类过氧化物酶活性以来,对纳米酶的研究迅速崛起。纳米酶能够通过模拟天然酶,在生理环境或体内实现催化反应,改善肿瘤微环境,并通过产生活性氧实现肿瘤治疗。

Recent progress in porous organic polymers and their application for CO_(2) capture

Carbon capture,storage,and utilization(CCSU)is recognized as an effective method to reduce the excessive emission of CO_(2).Absorption by amine aqueous solutions is considered highly efficient for CO_(2) capture from the flue gas because of the large CO_(2) capture capacity and high selectivity.However,it is often limited by the equipment corrosion and the high desorption energy consumption,and adsorption of CO_(2) using solid adsorbents has been receiving more attention in recent years due to its simplicity and high efficiency.More recently,a great number of porous organic polymers(POPs)have been designed and constructed for CO_(2) capture,and they are proven promising solid adsorbents for CO_(2) capture due to their high Brunauer-Emmett-Teller(BET)surface area(SBET),adjustable pore size and easy functionalization.In particular,they usually have rigid skeleton,permanent porosity,and good physiochemical stability.In this review,we have a detailed review for the different POPs developed in recent years,not only the design strategy,but also the special structure for CO_(2) capture.The outlook of the opportunities and challenges of the POPs is also proposed.

Cryogenic Exfoliation of 2D Stanene Nanosheets for Cancer Theranostics

Stanene(Sn)-based materials have been extensively applied in industrial production and daily life,but their potential biomedical application remains largely unexplored,which is due to the absence of the appropriate and effective methods for fabricating Sn-based biomaterials.Herein,we explored a new approach combining cryogenic exfoliation and liquid-phase exfoliation to successfully manufacture two-dimensional(2D)Sn nanosheets(SnNSs).The obtained SnNSs exhibited a typical sheet-like structure with an average size of~100 nm and a thickness of~5.1 nm.After PEGylation,the resulting PEGylated SnNSs(SnNSs@PEG)exhibited good stability,superior biocompatibility,and excellent photothermal performance,which could serve as robust photothermal agents for multi-modal imaging(fluorescence/photoacoustic/photothermal imaging)-guided photothermal elimination of cancer.Furthermore,we also used first-principles density functional theory calculations to investigate the photothermal mechanism of SnNSs,revealing that the free electrons in upper and lower layers of SnNSs contribute to the conversion of the photo to thermal.This work not only introduces a new approach to fabricate 2D SnNSs but also establishes the SnNSs-based nanomedicines for photonic cancer theranostics.This new type of SnNSs with great potential in the field of nanomedicines may spur a wave of developing Sn-based biological materials to benefit biomedical applications.

Synthesis of lanthanum tris (mono-i-octyl phthalate) and its thermal stability for polyvinyl chloride

A novel type of thermal stabilizer-lanthanum tris (mono- i -octyl phthalate) (LTMP) was synthesized by double-decomposition reaction o f sodium mono- i -octyl phthalate with lanthanum chloride at 60 ℃. Sodium m ono- i -octyl phthalate was prepared by sodium hydrate and mono- i -octy l phthalate prepared by reaction of isooctyl alcohol and phthalic anhydride in th e presence of sulfuric acid catalyst at 110 ℃. The yield of lanthanum tris (mon o- i -octyl phthalate) is about 84.5%. Its thermal stabilities were measured by heat-ageing oven test when incorporated into PVC. The experimental results show that the heat stability time is about 40min at 190 ℃ when adding 3phr (pe r hundred resin) to PVC. The thermal stability of this product is better than th at of Ca-Zn complex and basic lead salt stabilizers, and equal to that of dibut yltin dilaurate.

Shedding light on the reversible deactivation of carbon-supported single-atom catalysts in hydrogenation reaction

Carbon-supported single-atom catalysts were found to suffer reversible deactivation in catalytic hydrogenation,but the mechanism is still unclear.Herein,nitro compounds hydrogenation catalyzed by N-doped carbon-supported Co single atom(Co1/NC)was taken as a model to uncover the mechanism of the reversible deactivation phenomenon.Co1/NC exhibited moderate adsorption towards the substrate molecules(i.e.,nitro compounds or related intermediates),which could be strengthened by the confinement effect from the porous structure.Consequently,substrate molecules tend to accumulate within the pore channel,especially micropores that host Co1,making it difficult for the reactants to access the active sites and finally leading to their deactivation.The situation could be even worse when the substrate molecules possess a large size.Nevertheless,the catalytic activity of Co1/NC could be restored via a simple thermal treatment,which could remove the adsorbates within the pore channel,hence releasing active sites that were originally inaccessible to reactants.

In-situ regeneration of Bi^(0) active site to renew surface activation for long-term stable and efficient CO_(2)-to-formate electrosynthesis

CO_(2)-to-formate electrosynthesis with high selectivity and stability has been a long-sought objective.Unfortunately,most catalysts undergo structural and valence state changes due to surface oxidation during operation or storage,resulting in decreased catalytic performance.Herein,we report a efficient and stable BiIn@Cu-foam electrode through the in-situ regeneration of Bi^(0) active sites to renew the surface activation.The electronic structure of Bi site can be regulated by introducing In,thereby enhancing the adsorption strength of*OCHO.The optimized electrode exhibits over 90%FE_(formate)at a wide potential window(-0.9–-2.2 V),and formation rate for 3.15 mM cm^(-1)h^(-1).Especially,the electrode can maintain the high performance at continuously electrolysis for more than 300 h,or for more than 50 cycles,even repeated operation and storage for more than 2 years.This work provides a promising candidate and new insight to construct industrially viable stable Bi-based catalyst for formate electrosynthesis.

Nanotandem-rocket releases messenger to disrupt metabolic communication for antitumor immunotherapy

Metabolic communication between intracellular metabolism and extracellular microenvironment is responsible for celluar metabolism balance and cell survival.Tumor cells adaptively regulate metabolic communication to promote hyperproliferation and immunosuppression.Herein,nanotandem-rockets(hyaluronic acid modified Mg_(5)(CO_(3))_(4)(OH)_(2)(H-MCH))are developed for stepwisely disrupting metabolic communication to activate antitumor immunity.Benefiting from the nanotandem-rocket structure,H-MCH nanoplates successively disrupt the extracellular metabolite transport and intracellular carbohydrate metabolism.Theoretical simulation together with metabolomic analysis discloses the underlying mechanism of H-MCH nanotandem-rockets.The extra-/intra-celluar interruption of metabolic communication provides H-MCH nanotandem-rockets with high efficiency in tumor eradication.Moreover,the interference of metabolic communication reverses immunosuppression to facilitate the intratumoral infiltration of immune cells.With H-MCH nanotandem-rockets as an in situ vaccine,systemic antitumor immunity and immune memory effect are fabricated to eliminate tumor metastasis and recurrence.Different from traditional metabolic poisons(e.g.,arsenic or cyanide),the structure of nanotandem-rockets endows chemical messengers with selective regulation to tumor metabolic communication,but with minimal influence to normal tissues.The nanotandem-rockets provide a powerful paltform to augment the regulating actitiy of chemical messengers in metabolic communication.We expect our discovery of disrupting tumor metabolic communication with chemical messengers will be a powerful strategy for tumor therapy with vast practical applications.