γ-Fe2O3抗As2O3中毒能力的分子模拟

采用密度泛函理论研究了γ-Fe₂O₃表面As₂O₃的吸附以及掺杂改性提高抗As₂O₃中毒性能的作用机理.计算了As₂O₃在完整以及O缺陷γ-Fe₂O₃（001）表面的吸附性能,包括吸附位点、吸附结构、吸附能、PDOS等.同时建立了Mo、Ti、Mg掺杂的γ-Fe₂O₃模型,探讨了助剂掺杂对抗砷中毒能力的作用机制,并考虑了掺杂量的影响.结果表明：As₂O₃倾向于以O端化学吸附在γ-Fe₂O₃（001）表面Fe_oct位,吸附过程发生强烈的相互作用和电荷转移.当表面存在O缺陷时,As₂O₃的吸附能得到提高.Mo、Ti、Mg倾向于掺杂在Fe_oct位,增强了对As₂O₃的吸附能力,并且增大Mo的掺杂量可以强化As₂O₃的吸附.As₂O₃倾向于与活性较强的Mo、Ti、Mg发生反应,从而保护活性Fe位不受砷中毒,Ti和Mg的掺杂还抑制了相邻Fe位对As₂O₃的吸附.Mo、Ti、Mg的掺杂还促进了催化剂表面对NH₃的吸附,增强了表面酸性强度,有利于SCR反应.Mo、Ti、Mg原子的掺杂有利于提高γ-Fe₂O₃催化剂的抗砷中毒性能.     

脯氨酸掺杂g-C3N4纳米片的制备及其对RhB的降解

通过简单的水热及煅烧方法制备了脯氨酸掺杂的g-C₃N₄纳米片,借助FTIR、XRD、SEM、BET、XPS、UV-vis DRS、PL、电化学工作站等手段对所制备的光催化剂进行结构、形貌、组成及光电性能表征分析.结果表明,脯氨酸的加入可以自主剥离前驱体,制成纳米片状的g-C₃N₄,增加催化剂的比表面积.此外脯氨酸的引入可以调节催化剂的能带结构,增加可见光吸收,提高光生载流子分离率.在模拟可见光照射下,考察其对罗丹明B (RhB)的光催化降解性能获得了最优掺杂条件.1%脯氨酸掺杂(PCN-1%)的催化剂经过60min可见光照射即可降解99%以上的污染物.降解速率得到显著提升,PCN-1%对RhB的降解速度(0.0271min^-1)达到传统体相氮化碳(BCN)降解速率(0.0027min^-1)的10.04倍,显著提高了g-C₃N₄的光催化能力.     

N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation

A series of nitrogen-doped CoAlO (N-CoAlO) were constructed by a hydrothermal route combined with a controllable NH₃ treatment strategy. The effects of NH₃ treatment on the physico-chemical properties and oxidation activities of N-CoAlO catalysts were investigated. In comparison to CoAlO, a smallest content decrease in surface Co³⁺ (serving as active sites) while a largest increased amount of surface Co²⁺ (contributing to oxygen species) are obtained over N-CoAlO/4h among the N-CoAlO catalysts. Meanwhile, a maximum N doping is found over N-CoAlO/4h. As a result, N-CoAlO/4h (under NH₃ treatment at 400°C for 4 hr) with rich oxygen vacancies shows optimal catalytic activity, with a T₉₀ (the temperature required to reach a 90% conversion of propane) at 266°C. The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co³⁺ for N-CoAlO/4h, leading to an enhanced oxygen mobility, which in turn promotes C₃H₈ total oxidation activity dominated by Langmuir-Hinshelwood mechanism. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis shows that N doping facilities the decomposition of intermediate species (propylene and formate) into CO₂ over the catalyst surface of N-CoAlO/4h more easily. Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH₃ treatment.     

Ni,Co掺杂对Mn-Ce/TiO_2催化剂脱硝活性的影响

以Ti O_2为载体,采用浸渍法制备Ni或Co掺杂的Mn-Ce/Ti O_2催化剂,用于烟气的选择性催化还原法低温脱硝。考察Ni或Co的掺加对Mn-Ce/Ti O_2催化剂活性的影响,并对各催化剂进行了BET,XRD,H_2-TPR,XPS表征。实验结果表明:在NO,NH_3,O_2的体积分数分别为6×10~(-4),6×10~(-4),6×10~(-2),空速为16 000 h~(-1)的条件下,Mn-Ce/Ti O_2、Mn-Ce-Ni_(0.4)/Ti O_2和Mn-Ce-Co_(0.2)/Ti O_2催化剂的NO去除率在120℃时分别为38%,68%,74%,在150℃时分别为64%,92%,近100%,这表明掺加Ni或Co后Mn-Ce/Ti O_2催化剂的脱硝活性明显提高;在进气中加入体积分数为1×10~(-4)的SO_2后,Mn-Ce/Ti O_2催化剂的NO去除率在300 min内从98.2%下降至57.2%,而Mn-CeCo_(0.2)/Ti O_2和Mn-Ce-Ni_(0.4)/Ti O_2催化剂的NO去除率分别为73.9%和69.8%,这表明Ni或Co的掺加有助于提高催化剂的抗硫性能。表征结果表明:Ni或Co的掺加基本不影响Mn和Ce在载体Ti O_2上的分散;Ce元素以Ce~(3+)和Ce~(4+)价态存在,且主要为Ce~(4+);催化剂的比表面积变化不大;Mn O_x与Ce O_x的结晶度降低,催化剂的氧化还原能力增强。     

以TiO2为载体的锰铈系低温SCR脱硝催化剂抗硫抗水性能研究进展

开发具有低温、高活性、高抗硫抗水性的NH₃-SCR脱硝催化剂成为目前广大学者的主要研究方向。锰铈催化剂因为其优异的低温活性而具有广阔的应用前景,但反应气氛中的SO₂和H₂O会使催化剂中毒。本文分析了以TiO₂为载体的锰铈基催化剂在低温氨选择性催化还原过程中SO₂和H₂O的中毒机理,重点从添加助剂和改变催化剂形貌两方面介绍了提高锰铈催化剂抗硫抗水性的研究进展。最后针对目前锰铈催化剂存在的问题对其研究方向进行了展望。     

CeO2 doping boosted low-temperature NH3-SCR activity of FeTiOx catalyst: A microstructure analysis and reaction mechanistic study

• CeO₂ doping significantly improved low-temperature NH₃-SCR activity on FeTiO_x. • The crystallinity of FeTiO_x was decreased dramatically after CeO₂ doping. • Unique Ce-O-Fe structure in FeCe_0.2TiO_x accounted for its superior redox property. • Facile activation of NH₃ to-NH₂ on FeCe_0.2TiO_x promoted the DeNO_x efficiency. FeTiO_x has been recognized as an environmental-friendly and cost-effective catalyst for selective catalytic reduction (SCR) of NO_x with NH₃. Aimed at further improving the low-temperature DeNO_x efficiency of FeTiO_x catalyst, a simple strategy of CeO₂ doping was proposed. The low-temperature (<250℃) NH₃-SCR activity of FeTiO_x catalyst could be dramatically enhanced by CeO₂ doping, and the optimal composition of the catalyst was confirmed as FeCe_0.2TiO_x, which performed a NO_x conversion of 90% at ca. 200℃. According to X-ray diffraction (XRD), Raman spectra and X-ray absorption fine structure spectroscopy (XAFS) analysis, FeCe_0.2TiO_x showed low crystallinity, with Fe and Ce species well mixed with each other. Based on the fitting results of extended X-ray absorption fine structure (EXAFS), a unique Ce-O-Fe structure was formed in FeCe_0.2TiO_x catalyst. The well improved specific surface area and the newly formed Ce-O-Fe structure dramatically contributed to the improvement of the redox property of FeCe_0.2TiO_x catalyst, which was well confirmed by H₂-temperature-programmed reduction (H₂-TPR) and in situ XAFS experiments. Such enhanced redox capability could benefit the activation of NO and NH₃ at low temperatures for NO_x removal. The detailed reaction mechanism study further suggested that the facile oxidative dehydrogenation of NH₃ to highly reactive-NH₂ played a key role in enhancing the low-temperature NH₃-SCR performance of FeCe_0.2TiO_x catalyst.     

Heterogeneous photocatalytic decomposition of benzene on lanthanum-doped TiO2 film at ambient temperature

Lanthanum-doped anatase TiO₂ thin films on glass prepared via a sol–gel process have been shown to have much higher photocatalytic activity for the degradation of gaseous benzene than pure anatase TiO₂ thin film. The photodecomposition of benzene on both types of TiO₂ films follows the first-order kinetics while the CO₂ and CO formation followed the zero-order kinetics. GC/MS identification of the intermediates produced during the photodegradation of benzene revealed that doping lanthanum into TiO₂ thin film favors a cleavage of benzene ring. An optimal lanthanum amount with respect to photocatalytic activity was about 2.5 wt% (La₂O₃/TiO₂).     

一步法制备磁性多孔碳及高效吸附卡马西平

为了资源化利用废弃农林生物质并有效去除水体中卡马西平(CBZ).受"发酵"策略的启发,以KHCO3为活化剂,FeCl3·6H2O为磁性前驱体,通过简便的一步法将杨木屑转化为具有发达孔结构的磁性多孔碳(MPC).通过调整原料配比得到了最佳产物MPC-2-0.3,其比表面积为1002.48m2/g,对50mg/L的CBZ吸...     

改性生物质材料对地表水中残余草甘膦异丙胺盐的吸附

有效处理农药残留引起的水环境污染问题是提升河湖水质的关键.采用浸渍法将Fe和Al双金属复合至花生壳粉末,成功制备改性生物质材料（Fe-Al-PS）,用于吸附水环境中残留的草甘膦异丙胺盐除草剂.Fe-Al-PS对10 mg·L^-1的草甘膦异丙胺盐在吸附剂用量和吸附时间分别为0.14 g和10 min时达到吸附平衡,去除率分别稳定在99.9 %和99.6 %.吸附过程遵循伪二级动力学和Freundlich吸附等温模型,属于多分子层化学吸附.Fe-Al-PS在较宽的pH（2~11）范围内对草甘膦异丙胺盐的去除率均大于95 %.热力学结果表明吸附是自发的放热过程.Fe-Al-PS材料易得、合成简便且能耗低,具有较高的抗干扰能力和可重复利用性,不仅可用于实际水体中草甘膦异丙胺盐除草剂的有效去除,还可用于无机磷的去除.     

球形压力容器中甲烷-氢气-空气爆炸过程数值模拟及实验研究

为研究受限空间内甲烷-氢气-空气混合气体爆炸特性参数分布规律,在20 L球形压力容器装置内开展甲烷-氢气-空气混合气体爆炸实验,探究掺氢比变化对当量比为1的甲烷-氢气-空气混合气体爆炸过程的影响;运用Fluent数值模拟软件,采用标准k-ε湍流模型,结合层流有限速率燃烧模型,探究混合气体爆炸过程中燃烧特性(爆炸温度、压力、密度等)与反应时间的变化规律。研究结果表明：爆炸过程中,添加一定氢气时爆炸压力峰值、爆炸压力上升速率峰值增大,而到达峰值时间缩短;反应初期,中心点火处密度下降,反应釜各处密度持续上升;距离点火点越远,密度变化越大,反应釜中压力分布基本相同。研究结果可为甲烷-氢气-空气混合燃料的安全使用提供相关参考。