碱改性铜锰尖晶石室温催化氧化空气中甲醛

甲醛(FA)作为一种有致癌风险的有害污染物,在室内环境中普遍存在.为了高效去除甲醛,催化氧化技术成为了一种既经济又节能的选择,它不仅能降低材料成本(例如避免使用贵金属),也能在无光和室温的条件下进行.本文制备了一种成本效益高的碱改性锰酸铜尖晶石(CuMn^(2)O_(4))催化剂,并用于甲醛催化氧化反应中.实验结果表明,采用碱(1 mol L^(-1)氢氧化钾)改性的CuMn^(2)O_(4)(1-CuMn^(2)O_(4))作为催化剂,在室温条件下,当甲醛浓度为50 ppm,气体空速为4777 h^(-1)时,甲醛转化率(XFA)达到100%;此外,在甲醛转化率为10%时,其稳态反应速率达到了8.18×10^(-2) mmol g^(-1) h^(-1).原位漫反射红外傅立叶变换光谱结果表明,在催化剂的作用下,甲醛分子经过二氧亚甲基和甲酸酯中间体的转化,最终被氧化为水和二氧化碳.进一步结合密度泛函理论模拟发现,1-CuMn^(2)O_(4)具有较高的催化氧化甲醛性能,可归因于甲醛分子更牢固地吸附在1-CuMn^(2)O_(4)表面,甲醛吸附所需的能量较低,以及最终产物从催化剂表面脱附所需的能量也较低的综合效应.本研究为在无光和室温条件下,高效去除空气中甲醛提供了新型高效、成本效益高且无需贵金属的催化剂,从而为室内空气净化提供了新的科学见解.

In situ construction of protonated g-C3N4/Ti3C2 MXene Schottky heterojunctions for efficient photocatalytic hydrogen production

Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.

Accelerating photocatalytic hydrogen evolution and pollutant degradation by coupling organic co-catalysts with TiO_2

Accelerating the separation efficiency of photoexcited electron-hole pairs with the help of highly active co-catalysts has proven to be a promising approach for improving photocatalytic activity. Thus far, the most developed co-catalysts for semiconductor-based photocatalysis are inorganic materials;the employment of a specific organic molecule as a co-catalyst for photocatalytic hydrogen evolution and pollutant photodegradation is rare and still remains a challenging task. Herein, we report on the use of an organic molecule, oxamide (OA), as a novel co-catalyst to enhance electron- hole separation, photocatalytic H2 evolution, and dye degradation over TiO2 nanosheets. OA-modified TiO2 samples were prepared by a wet chemical route and demonstrated improved light absorption in the visible-light region and more efficient charge transport. The photocatalytic performance of H2 evolution from water splitting and rhodamine B (RhB) degradation for an optimal OA-modified TiO2 photocatalyst reached 2.37 mmol g^–1 h^–1 and 1.43 × 10^-2 min^-1, respectively, which were 2.4 and 3.8 times higher than those of pristine TiO2, respectively. A possible mechanism is proposed, in which the specific π-conjugated structure of OA is suggested to play a key role in the enhancement of the charge transfer and catalytic capability of TiO2. This work may provide advanced insight into the development of a variety of metal-free organic molecules as functional co-catalysts for improved solar-to-fuel conversion and environmental remediation.

Ultrahigh photocatalytic hydrogen evolution performance of coupled 1D CdS/1T-phase dominated 2D WS_(2) nanoheterojunctions

Solar-powered photocatalytic hydrogen production from water using semiconductors provides an eco-friendly and promising approach for converting solar energy into hydrogen fuel.Bulk semiconductors generally suffer from certain limitations,such as poor visible-light utilization,rapid recombination of charge carriers,and low catalytic capability.The key challenge is to develop visible-light-driven heterojunction photocatalysts that are stable and highly active during the water splitting process.Here,we demonstrate the integration of one-dimensional(1D)Cd S nanorods with two-dimensional(2D)1 T-phase dominated WS_(2) nanosheets for constructing mixed-dimensional heterojunctions for the photocatalytic hydrogen evolution reaction(HER).The resulting 1D CdS/2D WS_(2) nanoheterojunction exhibited an ultrahigh hydrogen-evolution activity of~70 mmol·g^(-1)·h^(-1) that was visible to the naked eye,as well as long-term stability under visible light illumination.The results reveal that the synergy of hybrid nanoarchitectures and intimate interfacial contact between the 1D Cd S nanorods and 1T-phase dominated 2D WS_(2) nanosheets facilitates charge carrier transport,which is beneficial for achieving superior hydrogen evolution.

Hierarchical AgAu alloy nanostructures for highly efficient electrocatalytic ethanol oxidation

The ethanol oxidation reaction is a significant anodic reaction for direct alcohol fuel cells.The most commonly used catalysts for this reaction are Pt‐based materials;however,Pt‐based electrocatalysts cause carbon monoxide poisoning with intermediates before the complete transformation of alcohol to CO_(2).Herein,we present hierarchical AgAu bimetallic nanoarchitectures for ethanol electrooxidation,which were fabricated via a partial galvanic reduction reaction between Ag and HAuCl_(4).The ethanol electrooxidation performance of the optimal AgAu nanohybrid was increased to 1834 mA mg^(‒1),which is almost 10 times higher than that of the pristine Au catalyst(190 mA mg^(‒1))in alkaline solutions.This was achieved by introducing Ag into the Au catalyst and controlling the time of the replacement reaction.The heterostructure also presents a higher current density than that of commercial Pt/C(1574 mA mg^(‒1)).Density functional theory calculations revealed that the enhanced activity and stability may stem from unavoidable defects on the surface of the integrated AgAu nanoarchitectures.Ethanol oxidation reactions over these defects are more energetically favorable,which facilitates the oxidative removal of carbonaceous poison and boosts the combination with radicals on adjacent Au active sites.

Co-delivery of paclitaxel and gemcitabine via folic acid-conjugated polymeric multi-drug nanoparticles (FA-PMDNPs) for the treatment of breast cancer

Multi-drug delivery focuses on different signaling pathways in cancer cells and has synergistic antiproliferative effects.In this manuscript,we developed folic acid(FA)-conjugated polymeric multi-drug nanoparticles(FA-PMDNPs)consisting of poly-L-lysine(PLL)and poly glutamic-conjugated PTX/GEM(PGA-PTX and PGA-GEM)for FA receptor-targeted synergistic breast cancer therapy.The carboxyl-rich structure of PGA provided plenty reaction sites and negative charge for drug loading.Transmission electron microscopy(TEM)results showed that FA-PMDNPs had uniform particle size and spherical morphology.The hemolysis study proved that FA-PMDNPs had good biocompatibility.In vitro cell viability and in vivo studies showed that FA-PMDNPs more effectively inhibited the proliferation of FA receptor(FR)-overexpressing breast cancer cells(4T1)than the pure drugs.Consequently,these results demonstrated that FA-PMDNPs could be effectively targeted at cancer cells compared with free drugs,indicating their strong potential as efficient multi-drug-carrying nano-platforms for cancer treatment.