不同盐沼湿地类型脱氮除磷效能及影响因素分析

采用沉水植物表面流湿地(沉水组)、挺水植物表面流湿地(挺水组)和浮床湿地(浮床组)3种盐沼湿地对长江口近岸低污染水体进行脱氮除磷效能的研究。结果表明,HRT为3 d时,水组、挺水组、浮床组对NO3^--N的去除率在高温时段分别为79.9%±13.2%、71.8%±15.2%、77.2%±13.2%,中温时段分别为39.4%±13.7%、31.5%±8.5%、18.4%±16.6%,低温时段分别为15.6%±14.6%、19.7%±8.6%、2.%5±8.6%。沉水组和挺水组对TP的去除率受温度影响较小,分别为66.4%±32.4%、55.5%±29.4%;而浮床组除磷效果受温度影响较大。当HRT缩短为1.5 d时,3组湿地系统在高温时段仍可达到相近的脱氮除磷效果,在中低温时段脱氮除磷效果都有不同程度的下降。     

Facile synthesis of black phosphorus directly grown on carbon paper as an efficient OER Electrocatalyst: Role of Interfacial charge transfer and induced local charge distribution

Black phosphorus (BP), as a new 2D material, is normally synthesized by a high-pressure and high-temperature (HPHT) method from white and red phosphorus, which severely hinders the further development of BP for any potential applications and leads to search for other potential applications of BP with big challenge. Herein, we develop a facile and efficient Thermal-Vaporization-Transformation (TVT) approach to prepare a highly active BP directly grown on carbon paper as the electrode for Oxygen evolution reaction (OER), showing a low onset potential of 1.45 V versus RHE. Simultaneously, the current density of BP-CP illustrates the excellent electro-catalysis stability only decreases by 3.4% after continuous operation for 10000 s. Meanwhile, the density functional theory (DFT) calculations further illustrates the P-doped carbon layer in the upper side of BP layer is actually responsible for its enhanced OER property, and the adjacent carbon atoms of the embedded P atoms are actually the active sites due to the induced local change distribution by intramolecular change transfer. Considering the facile, but efficient and scalable, TVT approach can directly synthesize BP-CP with excellent OER performance, which is promising for BP electrocatalysts used for OER in metal-air batteries, fuel cells, water-splitting devices, even other key renewable energy.     

Eco-friendly and degradable red phosphorus nanoparticles for rapid microbial sterilization under visible light

Pathogens pose a serious challenge to environmental sanitation and a threat to public health.The frequent use of chemicals for sterilization in recent years has not only caused secondary damage to the environment but also increased pathogen resistance to drugs,which further threatens public health.To address this issue,the use of non-chemical antibacterial means has become a new trend for environmental disinfection.In this study,we developed red phosphorus nanoparticles(RPNPs),a safe and degradable photosensitive material with good photocatalytic and photothermal properties.The red phosphorus nanoparticles were prepared using a template method and ultrasonication.Under the irradiation of simulated sunlight for 20 min,the RPNPs exhibited an efficiency of 99.98%in killing Staphylococcus aureus due to their excellent photocatalytic and photothermal abilities.Transmission electron microscopy and ultraviolet–visible spectroscopy revealed that the RPNPs exhibited degradability within eight weeks.Both the RPNPs and their degradation products were nontoxic to fibroblast cells.Therefore,such RPNPs are expected to be used as a new type of low-cost,efficient,degradable,biocompatible,and eco-friendly photosensitive material for environmental disinfection.     

Black phosphorous nanosheets–gold nanoparticles–cisplatin for photothermal/photodynamic treatment of oral squamous cell carcinoma

To improve five-year survival rate of oral squamous cell carcinoma (OSCC), the development of a novel composite material of black phosphorus nanosheets (BPNSs) and gold nanoparticles (AuNPs) for tumor treatment was carried out. The purpose of this study is to evaluate the cytostatic effects of BPNSs, AuNPs loaded with cisplatin (CDDP) on human tongue squamous cell carcinoma cells lines (SCC-9), and 7,12-dimethylbenz anthracene induced cheek squamous cell carcinoma was validated in golden hamsters animal models. The results showed that BPNSs could efficiently inhibit the metastasis and growth of OSCC compared with CDDP and AuNPs. And a combination composite of AuNPs–BPNSs loaded with CDDP could more effectively inhibit the metastasis and growth of OSCC, which might be due to the high drug-loading capacity, excellent photothermal properties and the combination of photodynamic and photothermal therapy of BPNSs and AuNPs, as well as the synergistic effects of AuNPs, BPNSs and CDDP.     

ZSM-5分子筛的P改性研究进展

P改性是调变ZSM-5分子筛催化性能的重要手段。ZSM-5分子筛的P改性方法主要由磷酸、磷酸盐水溶液及有机P化合物浸渍或通过气相沉积等方法进行。改性ZSM-5分子筛中,P与Al物种相互作用, P物种主要以四配位形式存在,调变分子筛的酸性,通过对表面的修饰阻止骨架Al的脱除,提高ZSM-5分子筛的水热稳定性。P改性后,HZSM-5分子筛的酸密度,尤其是表面强酸密度下降,降低正碳离子机理反应中的二次反应,减少氢转移及齐聚,促进轻烯烃的生成。P改性修饰HZSM-5分子筛的孔口,提高择形性能,部分进入体相的P减少裂化过程中ZSM-5交叉口处大分子正碳离子的形成,减少双分子裂化机理中间体的生成,提高轻烯烃选择性。P改性ZSM-5分子筛强酸密度降低,择形效应提高,焦炭生成得到抑制,催化剂寿命延长。     

钒渣钠化焙烧熟料浸出液除磷工艺研究

以钒渣钠化焙烧熟料浸出后得到的含钒溶液为原料，分析了二水硫酸钙在碱性条件下对含钒溶液中磷的去除机制，研究了二水硫酸钙用量、溶液pH、反应时间、反应温度等因素对磷去除率、钒损失率以及溶液中五氧化二钒与磷质量浓度比的影响。研究结果表明：在弱碱性条件下，二水硫酸钙可有效去除含钒溶液中的磷，磷去除率达到70%以上、钒损失率小于1%、五氧化二钒与磷质量浓度比大于2 300，满足后续沉钒的要求。确定的除磷工艺条件：二水硫酸钙与磷物质的量比为5.3，溶液pH为9.0，反应时间为30 min，反应温度为25 ℃。除磷后的含钒溶液经沉钒、洗涤、煅烧得到五氧化二钒产品，沉钒率大于99%，五氧化二钒产品质量满足YB/T 5304—2011《五氧化二钒》中99级的要求。     

线性富磷化阻燃剂在聚氨酯泡沫中的应用研究

通过界面聚合法合成了一种线性富磷化阻燃剂（LPRFR），将LPRFR与可膨胀石墨（EG）复配制备了阻燃聚氨酯泡沫（RPUF），使用红外光谱分析仪、核磁共振分析仪对阻燃剂LPRFR的化学结构进行了表征，并通过极限氧指数仪、锥形量热仪、扫描电子显微镜和红外光谱分析仪对RPUF的燃烧性能、微观形貌和化学结构进行了分析。结果表明，仅10 %（质量分数，下同）的LPRFR 与8 %EG复配后，RPUF的极限氧指数（LOI）便达到26.1 %；LPRFR和EG能大幅降低RPUF的热释放速率，并提高基体的成炭能力； LPRFR参与了燃烧过程中的成炭反应，形成了含P—O—C及P=O结构的高质量炭层，有效隔绝了氧气和热量；LPRFR是一种对于聚氨酯泡沫阻燃性能优异的新型阻燃剂。     

含磷模板和不同硅源对多级孔ZSM-5分子筛结构和催化性能的影响

通过采用不同比例的四丁基氢氧化磷（TBPOH）和四丙基氢氧化铵（TPAOH）混合作为模板剂合成多级孔ZSM-5分子筛，采用XRD，BET，SEM，TEM，NH3-TPD，MAS NMR等方法对分子筛进行物化表征，考察TPAOH和TBPOH的协同作用，期望得到较高结晶度的含P的多级孔ZSM-5。结果表明：以正硅酸乙酯（TEOS）为硅源，在TBPOH和TPAOH物质的量比为1∶1时，合成的多级孔ZSM-5形貌较为规整，由ZSM-5小晶粒堆积而成并呈现出丰富的介孔结构，具有较大的比表面积和孔体积，平均孔径分布于4～10 nm和50～70 nm。相比常规ZSM-5分子筛，合成的多级孔ZSM-5分子筛表现出更强的弱酸性和更多的总酸量。在1，3，5-三异丙苯的裂解反应中，相同转化率下，微孔ZSM-5分子筛表现出较好的苯和二异丙苯的选择性，而多级孔ZSM-5表现出更加优异的丙烯和异丙苯的选择性。     

前置除磷优化及对多级缺氧一好氧工艺的影响

为强化厌氧-多级缺氧-好氧(A-MAO)工艺,满足GB 3838-2002的地表IV水体要求,本研究对FeCl3、Fe2(SO4)3和聚合硫酸铁(PFS)3种铁盐前置化学除磷对TP、COD的去除效果和产泥量进行研究,并考察了前置化学除磷与A-MAO工艺耦合投加量。结果表明,FeCl3和Fe2(SO4)3对TP和SS去除可达到地表IV水体要求,并明显好于PFS;FeCl3对COD的去除和产泥量最多;与FeCl3相比,Fe2(SO4)3具有较好的COD保存能力,且产泥量少。AMAO工艺使用Fe2(SO4)3前置化学除磷,导致TN含量不达GB 18918-2002要求,优化的化学生物除磷耦合投加量为130 mg/L。