Cu/Cr co-stabilization mechanisms in a simulated Al2O3-Fe2O3-Cr2O3-CuO waste system

• Cu and Cr can be mostly incorporated into CuFe_xAl_yCr_2−x−yO₄ with a spinel structure. • Spinel phase is the most crucial structure for Cu and Cr co-stabilization. • Compared to Al, Fe and Cr are easier to be incorporated into the spinel structure. • ‘Waste-to-resource’ by thermal process at attainable temperatures can be achieved. Chromium slag usually contains various heavy metals, making its safe treatment difficult. Glass-ceramic sintering has been applied to resolve this issue and emerged as an effective method for metal immobilization by incorporating heavy metals into stable crystal structures. Currently, there is limited knowledge about the reaction pathways adopted by multiple heavy metals and the co-stabilization functions of the crystal structure. To study the Cu/Cr co-stabilization mechanisms during thermal treatment, a simulated system was prepared using a mixture with a molar ratio of Al₂O₃:Fe₂O₃:Cr₂O₃:CuO= 1:1:1:3. The samples were sintered at temperatures 600–1300°C followed by intensive analysis of phase constitutions and microstructure development. A spinel phase (CuFe_xAl_yCr_2−x−yO₄) started to generate at 700°C and the incorporation of Cu/Cr into the spinel largely complete at 900°C, although the spinel peak intensity continued increasing slightly at temperatures above 900°C. Fe₂O₃/Cr₂O₃ was more easily incorporated into the spinel at lower temperatures, while more Al₂O₃ was gradually incorporated into the spinel at higher temperatures. Additionally, sintered sample microstructures became more condensed and smoother with increased sintering temperature. Cu / Cr leachability substantially decreased after Cu/Cr incorporation into the spinel phase at elevated temperatures. At 600°C, the leached ratios for Cu and Cr were 6.28% and 0.65%, respectively. When sintering temperature was increased to 1300°C, the leached ratios for all metal components in the system were below 0.2%. This study proposes a sustainable method for managing Cu/Cr co-exist slag at reasonable temperatures.     

SO2-4/TiO2对SO2-C7H16-TiO2复相光化学反应的影响

研究了TiO2与SO2,C7H16复相光化学反应的光催化活性.在SO2-C7H16-O2-TiO2光催化反应过程中,TiO2表面可形成SO2-4/TiO2结构,它的存在可提高庚烷的光催化氧化速率,利用IR和XPS研究了反应过程中TiO2表面形成的SO2-4/TiO2结构.     

KMnO4/H2SO4引发制备淀粉改性絮凝剂的研究

以高锰酸钾为引发剂,制备淀粉-丙烯酰胺接枝共聚物.研究酸浓度、引发剂浓度、单体浓度、温度和加料方式对接枝反应的影响.结果表明,少量KMnO4(0.45mmol·l-1)和H2SO4(0.8mmol·l-1)可有效引发淀粉-丙烯酰胺接枝共聚反应,接枝效率达到90%以上,分子量大大提高,对高岭土的絮凝效果较好.     

3D flower-like mesoporous Bi4O5I2/MoS2 Z-scheme heterojunction with optimized photothermal-photocatalytic performance

3D flower-like hierarchical mesoporous Bi₄O₅I₂/MoS₂ Z-scheme layered heterojunction photocatalyst was fabricated by oil bath and hydrothermal methods. The heterojunction with narrow band gap of ～1.95 eV extended the photoresponse to near-infrared region, which showed obvious photothermal effect due to the introduction of MoS₂ with broad spectrum response. MoS₂ nanosheets were anchored onto the surface of flower-like hierarchical m...     

Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst in the catalytic wet air oxidation (CWAO) of cationic red GTL under mild reaction conditions

Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. HO₂· and O₂·⁻ appeared as the main reactive species in the reaction. The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. Hydroperoxy radicals (HO₂·) and superoxide radicals (O₂⁻·) appeared as the main reactive species upon the CWAO of cationic red GTL.     

Self-assembly synthesis of phosphorus-doped tubular g-C3N4/Ti3C2 MXene Schottky junction for boosting photocatalytic hydrogen evolution

Establishing highly effective charge transfer channels in carbon nitride(g-C₃N₄) to enhance its photocatalytic activity is still a challenging issue. Herein, the delaminated 2D Ti₃C₂ MXene nanosheets were employed to decorate the P-doped tubular g-C₃N₄(PTCN)for engineering 1D/2D Schottky heterojunction(PTCN/TC) through electrostatic self-assembly. The optimized PTCN/TC exhibited the highest hydrogen evolution rate(565 μmol h^-...     

磷酸活化活性炭对Cu2+的吸附特征研究

寻求廉价而高效的吸附材料为目的,研究向日葵秸杆基活性炭对铜离子的吸附性能。以向日葵秸秆为原料,经H3PO4活化制备活性炭,通过静态实验研究了其对水溶液中Cu2+的吸附特性,考察了溶液pH值、吸附温度和离子强度对吸附的影响,探讨了吸附热力学、动力学和吸附机理。结果表明:溶液pH值为5～6时活性炭对Cu2+的去除效果最好;向50 mL 170 mg·L-1的溶液中加入0.5 g活性炭,温度为45℃、吸附时间为1 h时,对Cu2+的去除率可达98.3%;Langmuir方程能更好地描述Cu2+在活性炭上的等温吸附特征,静态吸附容量可达41.03 mg·g-1;吸附过程符合拟二级动力学过程,且为吸热的化学吸附过程,膜扩散为速率控制步骤,离子交换可能在吸附过程中起了重要作用。     

固定化微生物对养殖水体中NH4^＋—N和NO2^——N转化作用

采用聚乙烯醇（PVA）（ρ＝gL^-1)的方法对沼泽红假单胞菌、诺卡氏菌和假丝酵母3种菌株进行固定化,所得的凝胶颗粒机械强度好,经久耐用,运用这3种菌株的固定化细胞对养殖水体中NH4^ -N和NO2^-－N进行转化,其最适作用温度范围为25－30℃,最适pH范围分别为：6．5－8．5,7．0－7．5及5．5－7．0,且对水质初始氮浓度有很强的适应性,3菌株经固定化后,其对养殖水体中NH4^ -NT和NO2^-－N的转化效率明显优于其游离细胞,若将3菌株按2：1：2组合成复合菌株并固定化,其以养殖水体中的NH4^ -N和NO2^-－N论效果将更佳。     

Catalytic ozonation of organic compounds in water over the catalyst of RuO2/ZrO2-CeO2

This research investigates the performances of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment. The results show that RuO₂/ZrO₂-CeO₂ was active for the catalytic ozonation of oxalic acid and possessed higher stability than RuO₂/Al₂O₃ and Ru/AC. In the catalytic ozonation of dimethyl phthalate (DMP), RuO₂/ZrO₂-CeO₂ did not enhance the DMP degradation rate but significantly improved the total organic carbon (TOC) removal rate. The TOC removal in catalytic ozonation was 56% more than that in noncatalytic ozonation. However this does not mean the catalyst was very active because the contribution of catalysis to the overall TOC removal was only 30%. The adsorption of the intermediates on RuO₂/ZrO₂-CeO₂ played an important role on the overall TOC removal while the adsorption of DMP on it was negligible. This adsorption difference was due to their different ozonation rates. In the catalytic ozonation of disinfection byproduct precursors with RuO₂/ZrO₂-CeO₂, the reductions of the haloacetic acid and trihalomethane formation potentials (HAAFPs and THMFPs) for the natural water samples were 38%–57% and 50%–64%, respectively. The catalyst significantly promoted the reduction of HAAFPs but insignificantly improved the reduction of THMFPs as ozone reacts fast with the THMs precursors. These results illustrate the good promise of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment.     

六铝酸盐负载CuO催化还原NO性能

采用共沉淀法制备了LaAl12O19六铝酸盐载体,采用等体积浸渍法制备了不同负载量的CuO/LaAl12O19催化剂,并对其进行了XRD、H2-TPR和BET表征,考察了催化剂对CH4选择催化还原NO的性能.结果表明,CuO的负载并未改变六铝酸盐载体的结构,Cu在载体上以Cu2+的形式存在,活性组分CuO与载体LaAl12O19之间存在协同作用;CuO/LaAl12O19催化剂对CH4选择催化还原NO表现出良好活性,所制备的催化剂均能使NO的转化率达到99%;其中负载量为1.0 wt%的CuO/LaAl12O19催化剂的活性最好,完全反应温度T99%为560℃,且在80 h稳定性试验中表现出了良好的高温活性和热稳定性.     

Immobilization of Cu2+, Zn2+, Pb2+, and Cd2+ during geopolymerization

The present research explored the application of geopolymerization for the immobilization and solidification of heavy metal added into metakaolinte. The compressive strength of geopolymers was controlled by the dosage of heavy metal cations, and geopolymers have a toleration limit for heavy metals. The influence of alkaline activator dosage and type on the heavy metal ion immobilization efficiency of metakaolinte-based geopolymer was investigated. A geopolymer with the highest heavy metal immobilization efficiency was identified to occur at an intermediate Na₂SiO₃ dosage and the metal immobilization efficiency showed an orderly increase with the increasing Na⁺ dosage. Geopolymers with and without heavy metals were analyzed by the X-ray powder diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. No crystalline phase containing heavy metals was detected in geopolymers with heavy metal, suggesting that the crystalline phase containing heavy metals is not produced or most of the phases incorporating heavy metals are amorphous. FTIR spectroscopy showed that, with increasing heavy metal addition, an increase in NO3- peak intensity was observed, which was accompanied by a decrease in the CO32- peak.     

Heterostructuring noble-metal-free 1T' phase MoS2 with g-C3N4 hollow nanocages to improve the photocatalytic H2 evolution activity

In this work,we report the preparation of 1T’-MoS₂/g-C₃N₄ nanocage(NC) heterostructure by loading 2D semi-metal noble-metal-free 1T’-MoS₂ on the g-C₃N₄ nanocages(NCs).DFT calculation and experimental data have shown that the 1T’-MoS₂/g-C₃N₄ NC heterostructure has a stronger light absorption capacity and larger specific surface area than pure g-C₃N₄ NCs and g-C₃N     

Enhancing O2 electroreduction to H2O on Ag/MnO2-CHNTs by boosting a four-electron catalytic pathway

A fundamental question in the oxygen reduction reaction(ORR)is how to rationally control the electrocatalytic selectivity for opening a four-electron reaction pathway. However, it still lacks direct experimental evidence to understand the reaction mechanism. This work unravels that Ag nanoparticles and carbonizing halloysite nanotubes(CHNTs) can trigger the construction of oxygen defects in the MnO₂, which contribute to the generation of active sites. The Ag/MnO₂-CHNTs deli...     

Cu~(2+)、Zn~(2+)、Cd~(2+)、Cr~(6+)和Mn~(2+)对萼花臂尾轮虫联合急性毒性研究

为探究重金属复合污染对轮虫的毒性影响,以萼花臂尾轮虫为受试动物,选择Cu~(2+)、Zn~(2+)、Cd~(2+)、Cr6+和Mn~(2+)等5种重金属,采用水生毒理联合效应相加指数法开展了其24 h联合急性毒性作用的评价研究。结果显示,Cu~(2+)、Zn~(2+)、Cd~(2+)、Cr6+和Mn~(2+)等5种重金属对萼花臂尾轮虫24 h半数致死浓度分别为:0.00616 mg·L~(-1),12.62 mg·L-1,2.89 mg·L-1,17.29 mg·L-1和67.32 mg·L-1。联合急性毒性实验结果显示,等毒性配比的Cu~(2+)-Cr6+(0.00385-10.806 mg·L-1)和等浓度配比的Cu~(2+)-Zn~(2+)(0.0199-0.0199 mg·L-1)、Cu~(2+)-Cd~(2+)(0.0181-0.0181 mg·L-1)、Cu~(2+)-Cr6+(0.0118-0.0118 mg·L~(-1))、Zn~(2+)-Cd~(2+)(3.475-3.475 mg·L-1)二元联合测试液的作用结果显示为拮抗效应,其余二元联合测试液的作用结果则均显示是协同效应。等毒性配比的Cu~(2+)-Cr~(6+)-Mn~(2+)(0.00210-5.902-22.981 mg·L-1)和等浓度配比的Cu~(2+)-Cd~(2+)-Mn~(2+)(0.00727-0.00727-0.00727 mg·L-1)三元联合测试液的作用结果显示为拮抗效应,其余三元联合测试液的作用结果则均显示是协同效应。等浓度配比的Cu~(2+)-Zn~(2+)-Cd~(2+)-Cr6+(0.00907-0.00907-0.00907-0.00907 mg·L-1)、Cu~(2+)-Zn~(2+)-Cd~(2+)-Mn~(2+)(0.00898-0.00898-0.00898-0.00898 mg·L~(-1))、Cu~(2+)-Zn~(2+)-Cr6+-Mn~(2+)(0.00819-0.00819-0.00819-0.00819 mg·L~(-1))四元联合测试液的作用结果显示为拮抗效应,其余四元联合测试液的作用结果的则均显示是协同效应。Cu~(2+)-Zn~(2+)-Cd~(2+)-Cr~(6+)-Mn~(2+)等毒性(0.00074-1.520-0.348-2.082-8.107 mg·L~(-1))和等浓度(0.00582-0.00582-0.00582-0.00582-0.00582 mg·L-1)配比的五元联合测试液作用结果均显示是协同效应。     

ZnO-MgO/Al2O3吸附-臭氧催化氧化处理难降解有机废水

以活性氧化铝为载体,采用浸渍法制备催化剂,对甲基橙及草酸模拟废水进行处理.在中性条件下,臭氧催化氧化比单独臭氧氧化能提前30 min使得甲基橙溶液褪色,反应105 min时,臭氧催化氧化对TOC的去除率高达96.53%,比单独使用臭氧氧化对甲基橙TOC去除率提高了47.19%,在处理草酸废水时臭氧催化氧化对TOC去除率高达80.59%,比单独使用臭氧氧化对草酸TOC去除率提高了59.14%.在处理甲基橙及草酸的小试实验中催化剂对有机污染物的吸附作用起到了加快反应进行的作用.在对垃圾渗滤液超滤出水时,O₃与COD质量比为1:1时,臭氧催化氧化对COD去除率为49.09%,比单独使用臭氧氧化提高36.37%,臭氧催化氧化对TOC的去除率是单独使用臭氧氧化的2.54倍,在处理垃圾渗滤液纳滤浓水时,臭氧催化氧化对COD去除率高达88.72%,比单独使用臭氧氧化提高37.60%,并且臭氧催化氧化对TOC的去除率是单独臭氧氧化的1.6倍.臭氧催化氧化反应过程中产生的羟基自由基对有机物更快的反应速率.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

大气CO2、CH4、CO高精度观测混合标气配制方法

高精度、高准确度的大气CO2、CH4、CO浓度观测需使用以干洁大气为底气的标气.标气中水汽含量及CO2的δ13C对基于光学原理的观测系统有不可忽视的影响.本研究利用自组装的混合标气配制系统,以环境大气为底气,并通过添加高浓度气体或利用吸附剂吸附,调节目标物种浓度.CO2和CO吸附效率分别达99.7%和99.8%,标气水汽含量小于3.7×10-6(物质的量分数,下同),可配制不同浓度范围的CO2、CH4、CO混合标气.在青海瓦里关全球大气本底站配制环境大气浓度范围的标气,CO2、CH4、CO实际配制浓度同目标浓度的偏差小于10×10-6、30×10-9、30×10-9,CO2中δ13C同实际大气接近.本方法配制的标气已应用于我国本底站大气CO2、CH4、CO高精度观测,符合世界气象组织/全球大气观测(WMO/GAW)质量要求.     

Ce0.7Zr0.3O2纳米棒的制备及其对柴油车尾气碳颗粒的催化净化性能

本研究以硝酸铈、硝酸锆为原料使用溶剂热合成法,制备了CeO₂-ZrO₂纳米棒催化剂(Ce_0.7Zr_0.3O₂(NR)),并用于柴油车尾气碳颗粒催化净化.催化活性检测证实:Ce_0.7Zr_0.3O₂(NR)纳米棒催化剂可有效净化柴油车尾气碳烟颗粒.在Ce_0.7Zr_0.3O₂(NR)存在下,碳颗粒净化率为10%、50%和90%时,所需温度分别仅为375℃、414℃和455℃,比商用Ce_0.7Zr_0.3O₂和Ce0.3Zr0.7O2催化剂性能更优.采用氮吸附-脱附、X射线光电子能谱(XPS)、H2程序升温还原(H₂-TPR)、X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术对催化剂进行表征.XRD和Raman结果证实,Ce_0.7Zr_0.3O₂(NR)主要由立方相CeO₂构成,并掺杂了少量四方相氧化锆.SEM和TEM结果则显示,Ce_0.7Zr_0.3O₂(NR)催化剂颗粒明显由纳米棒堆积而成,特定的纳米形貌会影响其对碳颗粒的催化氧化活性.XPS结果证明Ce_0.7Zr_0.3O₂(NR)催化剂主要具有晶格氧、化学氧和表面吸附氧等氧物种;晶格氧是碳颗粒氧化的活性氧物种,其溢流到催化剂表面可与碳颗粒接触从而提高反应活性;化学氧和表面吸附氧均为表面氧物种,极易与表面固体碳颗粒直接接触,从而可在较低温度下促进碳颗粒的净化.H₂-TPR结果进一步证实了XPS结果,Ce_0.7Zr_0.3O₂(NR)催化剂的低温还原温度比商用Ce_0.7Zr_0.3O₂催化剂更低,且含有更多的易还原氧物种,这些低温易还原氧物种可以在较低温度下参与催化反应,促进柴油车尾气颗粒物的低温催化净化.     

Ultra-small UiO-66-NH2 nanoparticles immobilized on g-C3N4 nanosheets for enhanced catalytic activity

UiO-66-NH₂,an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It is very meaningful to produce UiO-66-NH₂ nanoparticles with ultrasmall size,but remains challenging.Herein,we synthesized UiO-66-NH₂ nanoparticles in size of 8-15 nm that are immobilized on g-C₃N₄ nanosheets.Compared with the UiO-66...     

Influence of arsanilic acid,Cu2+, PO43− and their interaction on anaerobic digestion of pig manure

The methanogenesis was severely inhibited with 0.46 mM ASA addition.PO₄³⁻ didn’t attenuate the methanogenesis inhibition in the existence of ASA.ASA was transformed to As(III), As(V), MMA and DMA in anaerobic digestion.Cu²⁺ mitigated the methanogenesis inhibition via impeding the degradation of ASA.Arsanilic acid (ASA), copper ion (Cu²⁺) and phosphate (PO₄³⁻) are widely used as feed additives for pigs. Most of these three supplemented feed additives were excreted in feces and urine. Anaerobic digestion is often used for the management of pig manure. However, the interaction of ASA with Cu²⁺ or PO₄³⁻ on anaerobic digestion is still not clear. In this study, the influence of ASA, Cu²⁺, PO₄³⁻ and their interaction on anaerobic digestion of pig manure and the possible mechanisms were investigated. The initial concentrations of ASA, Cu²⁺ and PO₄³⁻ were 0.46 mM, 2 mM and 2 mM in the anaerobic digester, respectively. The methanogenesis was severely inhibited in the assays with only ASA addition, only Cu²⁺ addition and ASA+ PO₄³⁻ addition with the inhibition index of 97.8%, 46.6% and 82.6%, respectively, but the methanogenesis inhibition in the assay with ASA+ Cu²⁺ addition was mitigated with the inhibition index of 39.4%. PO₄³⁻ had no obvious impacts on the degradation of ASA. However, Cu²⁺ addition inhibited the degradation of ASA, mitigating the methanogenesis inhibition. The existence of ASA would inhibit methanogenesis and generate more toxic inorganic arsenic compounds during anaerobic digestion, implying the limitation of anaerobic digestion for ASA- contaminated animal manure. However, the co-existence of ASA and Cu²⁺ could mitigate the inhibition. These results could provide useful information for the management of anaerobic digestion of pig manure containing ASA with Cu²⁺.