Overestimate of remediation efficiency due to residual sodium persulfate in PAHs contaminated soil and a solution

Oxidation remediation is a commonly used technology for PAHs contaminated soil presently,but the overestimate of efficiency due to ongoing remediation by residual oxidants during extraction and testing has not been paid enough attention.In this study,persulfate was activated by Fe（Ⅱ） to inve stigate the effects of residual oxidants on PAHs removal during detection process and the elimination effects of adding Na₂ SO₃ and extending sampling time on residual oxidants.Results ...     

Measurement of tropospheric HO2 radical using fluorescence assay by gas expansion with low interferences

An instrument to detect atmospheric HO₂ radicals using fluorescence assay by gas expansion (FAGE) technique has been developed. HO₂ is measured by reaction with NO to form OH and subsequent detection of OH by laser-induced fluorescence at low pressure. The system performance has been improved by optimizing the expansion distance and pressure, the influence factors of HO₂ conversion efficiency are also studied. The interferences of RO₂ radicals were investigated by determining the conversion efficiency of RO₂ to OH during the measurement of HO₂. The dependence of the conversion of HO₂ on NO concentration was investigated, and low HO₂ conversion efficiency was selected to realize the ambient HO₂ measurement, where the conversion efficiency of RO₂ derived by propane, ethene, isoprene and methanol to OH has been reduced to less than 6% in the atmosphere. Furthermore, no significant interferences from PM_2.5 and NO were found in the ambient HO₂ measurement. The detection limits for HO₂ (S/N = 2) are estimated to 4.8 × 10⁵ cm^?3 and 1.1 × 10⁶ cm^?3 (${\rho }_{\mathrm{H}{\mathrm{O}}_2}$= 20%) under night and noon conditions, with 60 sec signal integration time. The instrument was successfully deployed during STORM-2018 field campaign at Shenzhen graduate school of Peking University. The concentration of atmospheric HOx radical and the good correlation of OH with j(O¹D) was obtained here. The diurnal variation of HOx concentration shows that the OH maximum concentration of those days is about 5.3 × 10⁶ cm^?3 appearing around 12:00, while the HO₂ maximum concentration is about 4.2 × 10⁸ cm^?3 appearing around 13:30.     

Ce-Mn/TiO2吸附剂的脱汞性能及抗SO2特性

采用浸渍法制备Mn/TiO₂（MT）、Ce/TiO₂（CT）和Ce-Mn/TiO₂（CMT）脱汞吸附剂,在固定床脱汞实验台上研究吸附剂的脱汞性能.结果表明,吸附温度为100~200℃时,3种吸附剂的脱汞性能均随温度的升高而增强;而在200~300℃范围内,脱汞效率均出现不同程度的降低.MT、CT及CMT吸附剂的脱汞效率在200℃时达到最高,分别为91%、58%和95%.MT和CT吸附剂的抗SO₂性能较弱,在N₂+6% O₂+1000×10^-6SO₂烟气条件下,30min内脱汞效率均下降到50%,而CMT吸附剂在2h内仍能保持80%以上的脱汞效率,表明在MT中掺杂Ce不仅可以提高吸附剂的脱汞性能,还可以增强抗SO₂性能.利用N₂吸附/脱附、X射线衍射（XRD）、H₂-程序升温还原（H₂-TPR）和X射线光电子能谱（XPS）等方法对吸附剂的物理化学性质进行表征,并对吸附产物进行热重分析（TG）和程序升温脱附实验（TPD）,阐明了CMT脱汞吸附剂的抗SO₂特性机理.Ce的掺杂,提高了活性组分在吸附剂表面的分散度及Mn⁴⁺的比例;相比于MnO₂,CeO₂可优先与SO₂反应,抑制了SO₂对Mn⁴⁺的毒害作用,从而提高了抗硫性能.     

Mn/TiO2和Mn-Ce/TiO2低温脱硝催化剂的抗硫性研究

在低温选择性催化还原(SCR)反应条件下考察了烟气残余SO2对Mn/TiO2和Mn-Ce/TiO2催化剂选择性催化还原活性的影响,同时对SO2的影响机理进行了探讨.结果发现,Mn/TiO2催化剂在SO2反应气氛中失活很快,硫铵盐的沉积和活性组分的硫酸化是催化剂失活的重要原因;Ce的加入可以有效地抑制催化剂活性组分的硫酸化,同时还能降低硫酸盐在催化剂表面的稳定性,从而可以提高催化剂的抗硫性.     

Recent advances in ionic liquids-based hybrid processes for CO2 capture and utilization

CO₂ capture and utilization (CCU) is an effective strategy to mitigate global warming. Absorption, adsorption and membranes are methods used for CO₂ separation and capture, and various catalytic pathways have also been developed for CO₂ utilization. Although widely researched and used in industry, these processes are energy-intensive and this challenge needs to be overcome. To realize further optimization, novel materials and processes are continuously being developed. New generation materials such as ionic liquids (ILs) have shown promising potential for cost-effective CO₂ capture and utilization. This study reviews the current status of ILs-based solvents, adsorbents, membranes, catalysts and their hybrid processes for CO₂ capture and utilization. The special properties of ILs are integrated into new materials through hybridization, which significantly improves the performance in the process of CCU.     

Enhanced photodegradation of phenolic compounds by adding TiO2 to soil in a rotary reactor

Photodegradation ofpentachlorophenol （PCP） and p-nitrophenol （PNP） in soil was carried out in a designed rotary reactor, which can provide the soil particles with continually uniform irradiation, and on a series of thin soil layers. TiO2, as a kind of environmental friendly photocatalyst, was introduced to the soil to enhance the processes. Compared with that on the soil layers, photodegradation of PCP at initial concentration of 60 mg/kg was improved dramatically in the rotary reactor no matter whether TiO2 was added, with an increase of 3.0 times in the apparent first-order rate constants. The addition of 1 wt% TiO2 furthered the improvement by 1.4 times. Without addition of TiO2, PNP （initial concentration of 60 mg/kg） photodegradation rate in the rotary reactor was similar to that on the soil layers. When 1 wt% additional TiO2 was added, PNP photodegradation was enhanced obviously, and the enhancement in the rotary reactor was 2 times of that on the soil layers, which may be attributed to the higher frequency of the contact between PNP on soil particles and the photocatalyst. The effect of soil pH and initial concentrations of the target compounds on the photodegradation in the rotary reactor was investigated. The order of the degradation rate at different soil pH was relative to the aggregation of soil particles during mixing in the rotary reactor. Photodegradation of PCP and PNP at different initial concentrations showed that addition of TiO2 to enhance the photodegradation was more suitable for contaminated soil with higher concentration of PCP, while was effective for contaminated soil at each PNP concentration tested in our study.     

溴代甲烷在SO42-/TiO2上的光催化降解

采用溶胶-凝胶法制备了SO₄^2-/TiO₂催化剂,运用XRD、BET比表面测定,FTIR等技术对催化剂进行了表征,并在微型常压连续反应装置上进行CH₃Br光催化反应性能考察.结果表明,SO₄^2-引入TiO₂体系使得催化剂的结构和光催化性能得到显著改善.SO₄^2-负载量为9%,烧结温度为450℃时,SO₄^2-/TiO₂催化剂的光催化活性最高;SO₄^2-/TiO₂催化剂对反应物料中的水汽有很好的耐受性;当反应温度低于85℃时,提高反应温度,有利于改善对CH₃Br的光催化反应活性,表观活化能约为19.6kJ·mol^-1,反应温度在85℃～105℃区间时,CH3Br的光催化降解表观活化能为0.     

V2O5/AC在含SO2气氛中对气态Hg0的吸附脱除研究

利用固定床反应器研究了模拟烟气(N_2、SO_2、O_2)气氛下,气态Hg~0在V_2O_5/AC催化剂上的吸附脱除行为.考察了V_2O_5担载量、SO_2浓度和吸附温度等对V_2O_5/AC吸附脱除Hg~0的影响,并对V_2O_5/AC上吸附汞的形态进行了XPS分析表征.研究发现,V_2O_5/AC对Hg~0的吸附能力远大于载体AC.汞的吸附量与V_2O_5/AC中V_2O_5的质量分数有关,随着V_2O_5质量分数从0.5%增加到1.0%,汞的吸附量从75.9 μg·g~(-1)增加到89.6 μg·g~(-1) (无氧) 和115.9 μg·g~(-1)增加到185.5 μg·g~(-1) (有氧),远高于相同吸附条件下的AC上的汞吸附量 (9.6 μg·g~(-1)和23.3 μg·g~(-1)).SO_2对Hg~0的吸附有促进作用,主要是由于SO_2和Hg~0在V_2O_5/AC上发生了化学反应.但是当SO_2体积分数从500×10~(-6)增加到2 000×10~(-6)时,V_2O_5/AC对汞的吸附量只增加了5%.不同温度下的实验结果表明,V_2O_5/AC催化剂在150℃左右的吸附脱除Hg~0的能力最高,汞的吸附量达到98.5 μg·g~(-1) (无氧) 和187.7 μg·g~(-1) (有氧).XPS 分析结果表明,在V_2O_5/AC催化剂表面有HgO和HgSO_4生成,证实了V_2O_5和SO_2的作用.     

Mo-Mn/TiO2催化剂的协同脱硝脱汞特性

采用浸渍法制备Mo-Mn/TiO₂催化剂,研究了反应温度、HCl和SO₂对其模拟烟气协同脱硝脱汞活性的影响.研究表明,过高的反应温度不利于汞的脱除过程,过低的温度则抑制脱硝反应的顺利进行,但在200℃时可兼具最优的脱硝和脱汞效率;HCl的加入促进汞的高效氧化,却明显降低催化剂对NO的转化;而烟气中SO₂的存在对催化剂的脱硝和脱汞过程均起到抑制作用.利用XRD、H₂-TPR和XPS等表征手段对硫中毒反应前后的催化剂进行了研究.结果表明,硫酸盐在催化剂表面的不断沉积和活性组分Mn⁴⁺及化学吸附氧O_α的消耗乃是致使催化剂失活的主要原因;另外,SO₂与NH₃和Hg⁰对催化剂表面活性位点的竞争吸附,也严重抑制催化剂的脱硝和脱汞反应.Mo-Mn/TiO₂的脱硝过程是通过Mn价态之间的相互转化来完成的,其中元素Mo和O₂是其转化得以实现的助剂;Mo-Mn/TiO₂对汞的脱除以催化氧化为主,金属氧化物中的晶格氧将Hg⁰转化为HgO而被脱除.     

高指数晶面TiO2对铬的吸附及光催化去除

由工业生产引起的铬污染是环境领域面临的一大挑战.二氧化钛(TiO_2)材料因其吸附催化的双重作用在铬的去除方面具有潜在应用前景.利用溶剂热法合成高指数晶面TiO_2{201},对其进行SEM、TEM、XRD及XPS表征,并用于Cr(Ⅲ/Ⅵ)的吸附及Cr(Ⅵ)的光催化还原,以达到从水体中去除铬的目的.所合成的TiO_2{201}为锐钛矿相,呈蒲公英状的层级结构. Langmuir吸附等温线结果表明,TiO_2{201}对Cr(Ⅲ)和Cr(Ⅵ)的最大吸附量分别为22. 7 mg·g-1和13. 2 mg·g-1,Freundlich模型拟合结果表明TiO_2{201}对Cr(Ⅲ)和Cr(Ⅵ)的吸附均易于进行,其1/n均小于0. 5.在紫外光照条件下,TiO_2{201}作为光催化剂可将毒性较强且吸附去除效果较差的Cr(Ⅵ)还原成Cr(Ⅲ),并以Cr(OH)3及Cr2O3的形式沉淀在TiO_2表面,XPS表征结果进一步证实了表面沉淀的存在.为探明TiO_2{201}光催化还原Cr(Ⅵ)的机制,分别研究光生空穴淬灭剂(EDTA-2Na)和光生电子淬灭剂(KBr O3)对Cr(Ⅵ)还原效率的影响,证明Cr(Ⅵ)的还原是由光生电子引起.     

二氧化钛对地下水中砷硅的吸附及再生回用

二氧化钛(TiO_2)材料作为性能优异的吸附材料被广泛应用于地下水砷(As)的去除中.结果表明,地下水中共存硅离子(Si)会占据TiO_2的吸附位点,从而影响As的吸附及TiO_2材料的再生回用.本文通过同步辐射扩展X射线吸收精细结构(EXAFS)研究了Si对As微观吸附机制的影响,表明Si的存在不会影响As在TiO_2上的吸附构型.衰减全反射傅里叶变换红外光谱(ATR-FTIR)原位研究表明Si在TiO_2表面形成Si单体、低聚体和多聚体,从而竞争As的吸附位点,同时增加TiO_2再生的难度.为了实现TiO_2材料的高效再生,本研究进一步考察了氟化钠(NaF)对TiO_2表面Si的脱附效果,发现NaF可以有效地洗脱Si,再生后的TiO_2吸附性能稳定.ATR-FTIR光谱原位分析发现,NaF的加入可有效脱附TiO_2表面的Si单体和多聚体.当利用NaF和Na OH共同洗脱TiO_2表面的As和Si时,3次循环中As的脱附率为86.8%~100.3%,Si的脱附率为67.9%~82.0%.本研究为地下水砷硅共吸附材料的再生提供了一种有效方法.     

H2O和SO2对Cr-Ce/TiO2催化氧化NO性能的影响

采用浸渍法在最佳制备条件下制备了新型Cr-Ce/TiO2催化剂,并对催化剂进行了BET和XRD表征.同时,考察了反应温度、H2O和SO2对该催化剂催化氧化NO性能的影响,并对中毒催化剂进行了FT-IR分析,讨论了中毒机理.结果表明,Cr-Ce/TiO2催化剂具有良好的NO氧化活性,在空速为10000h-1、O2体积分数8%(φ)、NO进口体积分数700×10-6条件下,反应温度250℃时NO转化率可达到59.7%,330℃时NO转化率可达到最大值80.7%.单独加入10%(φ)H2O或300×10-6(φ)SO2都可使催化剂活性降低,但在较高温度时影响较小.330℃下单独通入SO2和同时通入H2O与SO210h后,由于催化剂表面生成了少量硫酸盐和亚硫酸盐,活性下降并维持在62.4%左右,能够满足对NOx进行高效吸收的要求;停止通入H2O和SO2后,催化剂活性恢复到71.6%,加热处理后活性能进一步恢复到78.5%.该催化剂具有比文献中报道的其它NO氧化催化剂更强的抗H2O和SO2毒化能力.     

Pt-Cu/TiO2{001}纳米片用于CO2加氢制甲醇反应的研究

以高暴露{001}晶面的TiO₂纳米片为载体,利用共还原法负载0.5%的Pt和一定量的Cu得到Pt-Cu/TiO₂{001}催化剂,并在P=3.0 MPa,T=200~300℃,V（N₂）：V（H₂）：V（CO₂）=8：69：23,空速（WHSV）=3600 mL·g^-1·h^-1反应条件下评价了催化剂催化CO₂加氢制甲醇的反应性能.XRD、XPS、EPR和CO₂-TPD等的表征表明,与催化剂Cu/TiO₂相比,引入Pt后,催化剂由于金属Pt的电子促进作用使负载的金属与载体之间的相互作用更强,进而有利于稳定Cu颗粒尺寸且载体形成了更多缺陷（如氧空位、Ti³⁺）.因此,Pt-Cu/TiO₂{001}催化剂的金属与载体界面上的活性位点更多,从而表现出更好的CO₂活化能力和甲醇生成性能.     

Enhancement of solar-driven photocatalytic activity of oxygen vacancy-rich Bi/BiOBr/Sr2LaF7:Yb3+,Er3+ composites through synergetic strategy of upconversion function and plasmonic effect

For better use of solar energy,the development of efficient broadband photocatalyst has attracted extraordinary attention.In this study,a ternary composite consisting of Sr₂ LaF₇:Yb³⁺,Er³⁺ upconversion(UC) nanocrystals and Bi nanoparticles loaded BiOBr nanosheets with oxygen vacancies(OVs,SLFBB) was designed and synthesized by multistep solvent-thermal method.Mechanisms of in-situ formation of Bi nanoparticles and OVs in BiOBr/Sr₂ LaF_7<...     

Photocatalytic activity of TiO2 containing anatase nanoparticles and rutile nanoflower structure consisting of nanorods

A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.     

SCR气氛下Ce-W/TiO2催化剂的脱硝协同脱汞特性

在固定床反应器上研究了反应温度和烟气组分对Ce-W/TiO₂（物质的量比Ce：W=2：1）催化剂脱硝协同脱汞活性的影响.结果表明：反应温度对该催化剂的脱硝脱汞效率影响显著,在280~400℃温度区间,脱硝效率随温度升高而升高,而脱汞效率在温度为280℃与360℃的条件下较高,360℃时兼具最好的脱硝与脱汞效率.在SCR气氛中,HCl对Hg⁰的氧化脱除有极大的促进作用,低浓度的HCl也有利于脱硝效率的提高,但HCl浓度过高对NO的脱除有抑制作用;SO₂的存在对脱硝过程可起到促进作用,对Hg⁰的氧化有抑制作用.利用BET,XRD,SEM,TPD,XRF,NH3-TPD等分析手段对反应前后催化剂进行表征,结果表明：Ce-W/TiO₂无微孔结构,活性组分CeO₂和WO₃以高度分散的形式分布于载体表面.280℃条件下部分Hg以HgCl₂的形式吸附于反应后催化剂表面,随着反应温度的升高催化剂表面吸附态的汞急剧降低.SCR气氛中的HCl与SO₂会影响催化剂表面酸性,同时增加Cl和S元素含量,进而影响该催化剂的脱硝与脱汞效率.     

纳米二氧化钛胁迫对普生轮藻的毒性效应

纳米材料独特的理化性质使其得到了广泛的应用,但其可能带来的生物安全性问题也引起了广泛关注.实验研究了胁迫浓度梯度为0、0.01、0.10、1.0、10、100mg.L-1的纳米二氧化钛(nTiO2)悬浮液单一处理普生轮藻(CharavulgarisL.)的毒性效应,在胁迫24h、48h、72h、96h后分别测定其叶绿素a含量、脂质过氧化物丙二醛(MDA)含量、超氧化物歧化酶(SOD)活性和过氧化氢酶(CAT)活性.结果表明,随着胁迫浓度的增加和时间的延长,叶绿素a含量、SOD和CAT活性总体呈下降趋势,而MDA含量呈递增趋势,高浓度剂量组与对照组比较差异极显著,酶的活性降幅也较大,说明急性nTiO2暴露对普生轮藻具有毒性作用,且表现出剂量效应.     

VOx-MnOx/TiO2催化脱除氮氧化物与二英研究

二英会降低人类的免疫力,影响人体和神经发育;氮氧化物则会对人体的各项脏器和血液组织有严重危害,还会破坏臭氧层,加速酸雨的形成.商业钒钛催化剂既能脱除氮氧化物又能催化分解二英（邻二氯苯作为模拟物）,二英活性温度区为200~300℃,而脱硝活性温度为300~400℃.研究了VO_x/TiO₂、MnO_x/TiO₂以及VO_x-MnO_x/TiO₂等催化剂在200~300℃脱硝、脱除二英的情况.结果表明,在VO_x/TiO₂催化剂中掺入MnO_x促进脱硝活性温度区间由300~400℃往200~300℃偏移,当MnO_x和VO_x摩尔比为3：1时,催化剂在250℃脱硝和脱除二英的效果最好,催化NO和邻二氯苯效率分别为92.0%和89.0%.原位红外漫反射光谱研究表明,1V3M/T催化剂表面的脱硝反应在250℃遵循L-H机理,—NH₂、N_xH_yO_z、单齿亚硝酸盐和二齿硝酸盐是主要的反应中间体.     

负载量对氨水吸收CO2的影响规律及添加剂的作用研究

进行了氨法脱碳过程中吸收剂中CO2负载量对CO2脱除率影响的实验研究.结果发现,CO2脱除率随着负载量的增大而显著减小,高负载量(≥0.4)时,增加吸收液中总氨质量分数(吸收液中所有包含氨分子和铵离子的物质,并统一换算成NH3的质量分数)并不能有效地提高CO2的脱除率.同时,分别对有机和无机添加剂进行筛选,选取哌嗪(P...