施用生物炭和秸秆还田对华北农田CO2、N2O排放的影响

以华北农田冬小麦-夏玉米轮作体系连续6a施用生物炭和秸秆还田的土壤为研究对象,于2013年10月—2014年9月,采用静态暗箱-气相色谱法,对CO_2、N_2O通量进行了整个轮作周期的连续观测,探究施用生物炭与秸秆还田对其排放通量的影响。试验共设4个处理:CK(对照)、C1(低量生物炭4.5 t hm~(-2)a~(-1))、C2(高量生物炭9.0 t hm~(-2)a~(-1))和SR(秸秆还田straw return)。结果表明:在整个轮作周期内,各处理CO_2、N_2O通量随时间的变化趋势基本一致。随着生物炭施用量的增加,CO_2排放通量分别增加了0.3%—90.3%(C1)、1.0%—334.2%(C2)和0.4%—156.3%(SR)。其中,C2处理对CO_2累积排放量影响最大,增幅为42.9%。对N_2O而言,C2处理显著降低了N_2O累积排放量,但增加了CO_2和N_2O排放的综合增温潜势,C1和SR处理对N_2O累积排放量及综合增温潜势均没有显著影响。相关分析表明,土壤温度和土壤含水量是影响CO_2通量最主要的因素,两者之间呈极显著的正相关关系;N_2O通量与土壤温度、土壤含水量、NO_3~--N和NH_4~+-N均表现出极显著的正相关关系,而与土壤p H值表现出极显著的负相关关系。由此可见,添加生物炭对于减少氮素的气体损失具有较大的潜力。     

新疆古尔班通古特沙漠土壤N_2O、CH_4和CO_2通量及其对氮沉降增加的响应

沙漠土壤在全球土壤主要温室气体通量中扮演着重要角色,但是在环境变化条件下的通量估算结果存在很大的不确定性。在新疆古尔班通古特沙漠设定N0、N0.5、N1、N3、N6和N24 6个样方,以0、0.5、1.0、3.0、6.0和24.0 g·m~(–2)·a~(–1) 6个不同模拟氮(N)沉降浓度进行N处理,两年后开始对施N样方进行为期两个生长季的N_2O、CH_4和CO_2通量测定。研究表明生长季对照样方(N0)的N_2O、CH_4和CO_2的平均通量分别为4.8μg·m~(–2)·h~(–1)、–30.5μg·m~(–2)·h~(–1)和46.7 mg·m~(–2)·h~(–1),季节变化显著影响3种气体的通量。N0、N0.5和N1在春季和夏季具有相似的N_2O排放速率,排放速率高于秋季,而N6和N24的N_2O排放主要受N输入时间影响;CH_4的吸收在春季和夏季相对较高,秋季较低;CO_2的排放量在第一年春季和夏季之间变化较小,但高于秋季排放量,第二年CO_2动态与N浓度相关。N增加通常能显著促进N_2O的排放,但受测定季节和年度的影响,且各处理的N_2O排放因子大小无明显规律;CH_4的吸收受N增加影响不显著;CO_2的排放在第一年不受N增加的影响,第二年高浓度N增加对春季和夏季CO_2排放具有限制作用,对秋季影响不显著。结构方程模型的研究表明,对N_2O、CH_4和CO_2的动态变化影响较大的因子分别是施N浓度、土壤温度或土壤含水量和植株密度。整个生长季由N带来的净通量和增温潜力非常小。     

不同氮肥对东北春玉米农田温室气体周年排放的影响

为探明不同氮肥条件下高纬度农田土壤的温室气体排放特性,采用静态箱-气相色谱法研究了常规施氮(CN)、施用缓释肥(SLN)、尿素添加硝化抑制剂和脲酶抑制剂(NIUI)、不施氮肥(NN)对东北春玉米农田土壤温室气体排放的影响.结果表明: CN、SLN和NIUI处理产量分别为9618、9376和9645 kg·hm^-2.与CN处理相比,SLN促进了玉米生长季土壤N₂O的排放,降低了非生长季土壤N₂O的排放;NIUI处理N₂O累积排放量比CN降低了39.0%;各处理土壤CO₂周年累积排放通量无显著差异;东北春玉米田是大气中CH₄的弱汇,NIUI处理较CN促进了玉米生长季土壤对CH₄的吸收.综上,尿素添加脲酶抑制剂和硝化抑制剂可以在实现玉米高产的同时有效减少土壤温室气体排放.     

生物炭施用3年后对稻麦轮作系统CH4和N2O综合温室效应的影响

本试验对比观测研究了在稻田土壤中经3年陈化后的生物炭(B_3)和新施入生物炭(B_0)对稻麦轮作系统CH_4和N_2O综合温室效应和温室气体强度的影响,旨在明确生物炭对土壤温室气体排放的长期效应.田间试验设置4个处理,分别为对照(CK)、施用氮肥不施用生物炭(N)、施用氮肥和新生物炭(NB_0)以及施用氮肥和陈化生物炭(NB_3)处理.结果表明:NB_0和NB_3处理均显著提高了稻田土壤pH值、有机碳和全氮含量,并且显著影响与温室气体排放相关的微生物潜在活性.与N处理相比,NB_3处理显著增加了作物产量,增幅14.1%,并且显著降低了CH_4和N_2O排放,降幅分别为9.0%和34.0%;而NB_0处理显著增加作物产量,增幅9.3%,显著降低N_2O排放,降幅38.6%,但增加了CH_4排放,增幅4.7%;同时NB_0和NB_3处理均能降低稻麦轮作系统的综合温室效应和温室气体强度,且NB_3处理能更有效地减少温室气体的排放并提高作物产量.在土壤中经3年陈化后的生物炭仍然具有固碳减排能力,因此,施用生物炭对稻麦轮作系统固碳减排和改善作物生产具有长期效应.     

博斯腾湖人工和天然芦苇湿地土壤CO2、CH4和N2O排放通量

为研究干旱区淡水湖泊人工、天然芦苇湿地土壤温室气体源汇强度及其影响因素,采用静态箱-气相色谱法,于2015年1月—12月对博斯腾湖人工和天然芦苇湿地土壤CO_2、CH_4和N_2O通量进行全年观测。结果表明,人工芦苇湿地土壤CO_2、CH_4和N_2O排放通量变化范围分别为:10.1—588.4mg m~(-2)h~(-1)、2.9—82.4μg m~(-2)h~(-1)和1.32—29.7μg m~(-2)h~(-1),天然芦苇湿地土壤CO_2、CH_4和N_2O排放通量变化范围分别为10.3—469.6mg m~(-2)h~(-1)、3.1—64.8μg m~(-2)h~(-1)和1.9—14.3μg m~(-2)h~(-1)。人工和天然芦苇湿地夏季土壤CO_2排放通量均明显高于其他季节,而土壤CH_4和N_2O排放通量较大值多集中在春末夏初。全年观测期间,人工芦苇湿地土壤CO_2、CH_4和N_2O排放通量高于天然芦苇湿地(P0.05);温度是影响人工、天然芦苇湿地土壤CO_2和N_2O排放通量的关键因素,近地面温度和5cm土壤温度与CO_2和N_2O排放通量呈现极显著的正相关关系(P0.01)。土壤CH_4排放通量是温度和水分二者共同影响的,由近地表温度、5cm土壤温度和土壤含水量共同拟合的方程可以分别解释人工、天然芦苇湿地土壤CH_4排放通量的71%、74.5%;土壤有机碳、pH、盐分、NH_4~+-N、NO_3~--N也是人工、天然芦苇湿地土壤CO_2、CH_4和N_2O排放通量的影响因素;人工和天然芦苇湿地土壤均是CO_2、CH_4和N_2O的"源"。基于100年尺度,由3种温室气体计算全球增温潜势得出,人工芦苇湿地全球增温潜势大于天然芦苇湿地(15150.18kg/hm~212484.21kg/hm~2)。     

中亚热带杉木人工林苔藓覆盖对土壤温室气体排放的影响

目前,国内尚无亚热带森林地区生物土壤结皮-土壤系统温室气体通量特征的研究,给区域尺度上温室气体通量的估算带来很大的不确定性。本研究选择中亚热带杉木人工林中地面广布的苔藓覆盖形成的结皮层及其下覆土壤为研究对象,采用对气体排放速率影响较小的等压取样法,探究去除苔藓土壤(BG)和苔藓覆盖土壤(BSCs)在光照和暗处理下其温室气体通量的变化特征,来模拟自然环境下白昼和黑夜时段苔藓覆盖的影响,同时采用随机森林模型来衡量光照与苔藓覆盖对温室气体通量的重要度。结果表明:苔藓覆盖、光照处理及其互作对CO_2通量有极显著的影响(P0.001),苔藓覆盖和光照处理对CH_4的吸收通量有极显著的影响(P0.001),光照及光照与苔藓覆盖交互作用对N_2O通量有极显著的影响(P0.001);暗处理下,与BG土壤相比,苔藓覆盖具有抑制土壤CO_2排放的趋势,苔藓覆盖略微增加N_2O的排放通量,但显著增加CH_4的吸收通量(P0.01);光照处理下BSCs的CO_2、CH_4和N_2O三种温室气体均出现负通量,苔藓覆盖显著降低CO_2、CH_4和N_2O的排放通量(P0.01),表明光照条件下苔藓-土壤系统是这三种温室气体重要的汇;由光照导致的BSCs的CO_2和N_2O的吸收通量显著高于BG土壤温室气体的吸收量(P0.01),但光照对CH_4吸收通量的影响无显著差异;随机森林分析表明,光照对于CO_2和N_2O通量的影响的重要性大于苔藓覆盖,而苔藓覆盖对CH_4通量的影响的重要性大于光照,表明CO_2和N_2O的通量与苔藓中的光能自养生物的代谢活性关联更大,CH_4通量与苔藓中的化能自养生物代谢活性有关联。     

华南地区尾巨桉和马占相思人工林地表温室气体通量

为探索华南地区尾巨桉人工林和马占相思人工林地表温室气体的季节排放规律、排放通量和主控因子,采用静态箱-气相色谱法,对两种林型地表3种温室气体(CO_2、CH_4、N_2O)通量进行为期1年的逐月测定。结果表明:(1)尾巨桉人工林和马占相思人工林均为CO_2和N_2O的排放源,CH_4的吸收汇。马占相思林地表N_2O通量显著(P0.01)高于尾巨桉林,CO_2通量和CH_4通量无明显差异。(2)两种林型3种温室气体通量有着相似季节变化规律,地表CO_2通量均呈现雨季高旱季低的单峰规律;地表CH_4吸收通量表现为旱季高雨季低的单峰趋势;地表N_2O通量呈现雨季高旱季低且雨季内有两个峰值的排放规律。(3)地表CO_2、N_2O通量和土壤5 cm温度呈极显著(P0.01)正相关,3种温室气体地表通量同土壤含水量呈极显著(P0.01)或显著相关(P0.05)。(4)尾巨桉林和马占相思林温室气体年温室气体排放总量为31.014 t/hm~2和28.782 t/hm~2,均以CO_2排放占绝对优势(98.46%—99.15%),CH_4和N_2O处于次要地位。     

模拟水位变化对杭州湾芦苇湿地夏季温室气体日通量的影响

水位是影响湿地温室气体排放的重要因子。采用静态箱-气相色谱法研究了模拟条件下不同水位(0、5、10 cm和20 cm)对芦苇湿地温室气体(CO_2、CH_4、N_2O)夏季昼夜通量变化的影响。结果表明,1)4种不同水位CO_2通量日变化均表现为昼低夜高,且白天为汇,夜间为源,整体均表现为CO_2的汇;不同水位CH_4通量日变化则均表现为昼高夜低,且整体上均表现为CH_4的源;N_2O通量总体上水淹后均表现为昼高夜低而0cm水位表现为昼低夜高;2)随着水位的增加CH_4和CO_2平均通量呈现先增加后降低的趋势,且10cm水位下CH_4和CO_2平均通量最高,N_2O通量则在5cm水位最高;3)通过相关性和主成分分析表明,气温、水温是土壤CH_4、N_2O通量日变化的主导因子,而土壤温度是CO_2日变化通量的主导因子,同时,土壤p H、Eh及水体p H、Eh是CO_2通量日变化的重要因子之一。     

大兴安岭永久冻土区7种沼泽类型土壤温室气体排放特征

气候变暖及永久冻土退化将会增加冻土湿地的温室气体排放,但关于大兴安岭永久冻土区沼泽湿地温室气体通量及主控因子尚不明确。采用静态箱-气相色谱法,同步原位观测大兴安岭永久冻土区7种天然沼泽类型(草丛沼泽-C、灌丛沼泽-G、毛赤杨沼泽-M、白桦沼泽-B、落叶松苔草沼泽-LT、落叶松藓类沼泽-LX、落叶松泥炭藓沼泽-LN)土壤CO_2、CH_4和N_2O通量及土壤温度、水位、化冻深度及土壤碳氮含量、碳氮比、pH值及含水量,揭示永久冻土区沼泽土壤温室气体通量及其主控因子。结果表明:1) 7种沼泽类型土壤CO_2年均通量(125.12—163.33 mg m~(-2) h~(-1))相近;2) CH_4年均通量(-0.007—0.400 mg m~(-2) h~(-1))呈草丛显著高于其他沼泽5.6—65.7倍(P0.01);3) N_2O年均通量(1.52—37.90μg m~(-2) h~(-1))呈阔叶林沼泽显著高于其他类型2.0—23.9倍,针叶林沼泽显著高于草丛、灌丛沼泽2.9—6.2倍(P0.05);4) CO_2主控因子为土壤温度和水位;CH_4主控因子为土壤温度和化冻深度;N_2O受到多种环境因子综合调控,共同可以解释N_2O变化的26%—99%;5)土壤增温潜势(11.05—15.37 t CO_2 hm~(-2) a~(-1))相近,且均以CO_2占绝对优势地位,但草丛以CH_4占次要地位,森林沼泽则以N_2O占次要地位。综合对比国内外现有研究结果发现目前大兴安岭永久冻土区沼泽土壤仍处于CO_2、CH_4和N_2O低排放阶段。     

神农架主要森林土壤CH4、CO2和N2O排放对降水减少的响应

研究降水格局改变后森林土壤温室气体排放格局,可为森林温室气体排放清单制定提供科学依据。以神农架典型森林类型常绿落叶阔叶混交林和2种人工林马尾松和杉木林为研究对象,研究了降水格局改变后,其土壤CH_4吸收、CO_2和N_2O的排放格局和可能机制。结果表明:常绿落叶阔叶混交林吸收CH_4通量为(-36.79±13.99)μg Cm~(-2)h~(-1),显著大于马尾松和杉木两种人工林的CH_4吸收通量,其吸收通量分别为(-14.10±3.38)μg Cm~(-2)h~(-1)和(-7.75±2.80)μg Cm~(-2)h~(-1)。马尾松和杉木两种人工林CO_2排放通量分别为(107.03±12.11)μg Cm~(-2)h~(-1)和(80.82±10.29)μg Cm~(-2)h~(-1),显著大于常绿落叶阔叶混交林(71.27±10.59)μg Cm~(-2)h~(-1)。常绿落叶阔叶混交林N_2O排放通量为(8.88±6.75)μg Nm~(-2)h~(-1),显著大于杉木人工林(5.93±2.79)μg Nm~(-2)h~(-1)和马尾松人工林(1.64±1.02)μg Nm~(-2)h~(-1)。分析3种森林土壤CH_4吸收量与其环境因子之间的关系发现,常绿落叶阔叶混交林的CH_4吸收通量与其土壤温度呈现显著的指数负相关关系(P0.01)。常绿落叶阔叶混交林、马尾松林和杉木林的土壤CO_2排放通量与其空气温度和土壤温度之间均呈现显著的指数正相关关系(P0.01)。常绿落叶阔叶混交林和马尾松林土壤N_2O排放通量与空气温度之间均呈现显著的指数正相关关系(P0.01),而马尾松林与土壤温度之间呈显著正相关(P0.05),与土壤湿度之间均无显著相关。降水减半后,减少降水对常绿落叶阔叶混交林和马尾松林土壤CH_4吸收通量均具有明显的促进作用,但对杉木林土壤CH_4吸收量具有抑制作用,对常绿落叶阔叶混交林和杉木林土壤CO_2平均排放通量均具有明显的促进作用,而对马尾松林土壤CO_2平均排放通量明显抑制作用,对常绿落叶阔叶混交林、马尾松和杉木林土壤N_2O排放量具有明显的抑制作用。     

Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2

Adding one equivalent of H₂O₂ to compounds of stoichiometry MoCl₂(O)₂(OPR₃)₂, OPR₃ = OPMePh₂ or OPPh₃, leads to the formation of oxo-peroxo compounds MoCl₂(O)(O₂)(OPR₃)₂. The compound MoCl₂(O)(O₂)(OPMePh₂)₂ crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl₂(O)(O₂)(OPPh₃)₂, was not isolated in pure form, co-crystallized with MoCl₂(O)₂(OPPh₃)₂ in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on ¹⁸O isotopic studies and involves exchange between the alcohol and metal bonded O atoms.     

Solution-mediated syntheses and characterizations of two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3]

Two new zincophosphites [C₆H₁₄N₂]_0.5[Zn(H₂PO₃)₂] 1 and [C₄H₁₂N₂]_0.5[(CH₃)₂NH₂][Zn₂(HPO₃)₃] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO₄ and HPO₂(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO₄ and HPO₃ units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.     

Synthesis, structure and properties of TTF-carboxylate bridged paddlewheel dirhodium complexes, Rh2(BuCO2)3(TTFCO2) and Rh2(BuCO2)2(TTFCO2)2

Reaction of tetrathiafulvalene carboxylic acid (TTFCO₂H) with paddlewheel dirhodium complex Rh₂(Bu^tCO₂)₄ yielded TTFCO₂-bridged complexes Rh₂(Bu^tCO₂)₃(TTFCO₂) (1) and cis- and trans-Rh₂(Bu^tCO₂)₂(TTFCO₂)₂ (cis- and trans-2). Their triethylamine adducts [1(NEt₃)₂] and cis-[2(NEt₃)₂] were purified and isolated with chromatographic separation, and characterized with single crystal X-ray analysis. Trans-[2(NEt₃)₂] is not completely separated from a mixture of cis- and trans-[2(NEt₃)₂], but its single crystals were obtained from a solution of the mixture. A three-step quasi-reversible oxidation process was observed for 1 in MeCN. The first two steps correspond to the oxidation of the TTFCO₂ moiety and the last one is the oxidation of the Rh₂ core. The oxidation of cis-2 is observed as a two-step process with very similar E_1/2 values to those of the first two processes for 1. Both 1⁺ and cis-2²⁺ in MeCN at room temperature show isotropic ESR spectra with a g value of 2.008 and a_H = 0.135 mT for two equivalent H atoms and a_H = 0.068 mT for one H atom. The redox and ESR data of cis-2 suggest that the intramolecular interaction between the TTF moieties is very small.     

Syntheses and characterization of the W(II) and W(III) N2 complexes, [WCl2(PMe3)3]2N2 and [WCl3(PMe3)2]2N2

Refluxing WCl₄(PMe₃)₃ under a nitrogen atmosphere in the presence of two equivalents of sodium amalgam leads to a reduction to the W(II) complex [cis,mer-WCl₂(PMe₃)₃]₂N₂ (1), which can be converted to [mer,trans-WCl₃(PMe₃)₂]₂N₂ (2) via appropriate oxidation/chlorination. Structural data have been obtained for both complexes, and demonstrate significantly increased steric crowding in 1 due to PMe₃/PMe₃ interactions. The N-N bond distances in the two compounds are similar, at 1.279(4) and 1.243(18) Å, respectively.     

New preparations and molecular structures of cis-MCl2(Ph2PCH2PPh2)2, M = Ru,Os and trans-RuCl2(Ph2PCH2PPh2)2

The title compounds were made by reacting bis(diphenylphosphino)methane (dppm) with reduced solutions of OsCl₆^4? and Ru₂OCl₁₀^4?. The crystal and molecular structures of these compounds have been determined form three-dimensional X-ray study. The cis-isomers crystallize with one CHCl₃ per molecule of the complex. All three compounds crystallize in the monoclinic space group P2₁/n with unit cell dimensions as follows: Cis-OsCl₂(dppm)₂·CHCl₃: a = 13.415(4) Å, b = 22.859(4) Å, c = 16.693(3) Å, β = 105.77(3)°, V = 4926(3) ų, Z = 4. cis-RuCl₂(dppm)₂·CHCl₃: a = 13.442(3) Å, b = 22.833(7) Å, c = 16.750(4) Å, β = 105.53(2)°, V = 4953(3) ų, Z = 4. trans-RuCl₂(dppm)₂: a = 11.368(7) Å, b = 10.656(6) Å, c = 18.832(12) Å; β = 103.90(6)°, V = 2213(7) ų; Z = 2. The structures were refined to R = 0.044 (R_w = 0.055) for cis-OsCl₂(dppm)₂·CHCl₃; R = 0.065 (R_w = 0.079) for cis-RuCl₂(dppm)₂·CHCl₃ and R = 0.028 (R_w = 0.038) for trans-RuCl₂(dppm)₂. The complexes are six coordinate with stable four-membered chelate rings. The PMP angle in the chelate rings is ca. 71° in each case.     

Comparative study of three magnetic nano-particles (FeSO4, FeSO4/SiO2, FeSO4/SiO2/TiO2) in plasmid DNA extraction

Recent updates on Magnetic Nano-Particles (MNPs) based separation of nucleic acids have received more attention due to their easy manipulation, simplicity, ease of automation and cost-effectiveness. It has been indicated that DNA molecules absorb on solid surfaces via hydrogen-bonding, and hydrophobic and electrostatic interactions. These properties highly depend on the surface condition of the solid support. Therefore, surface modification of MNPs may enhance their functionality and specification. In the present study, we functionalized Fe₃O₄ nano-particle surface utilizing SiO₂ and TiO₂ layer as Fe₃O₄/SiO₂ and Fe₃O₄/SiO₂/TiO₂ and then compare their functionality in the adsorption of plasmid DNA molecules with the naked Fe₃O₄ nano-particles. The result obtained showed that the purity and amount of DNA extracted by Fe₃O₄ coated by SiO₂ or SiO₂/TiO₂ were higher than the naked Fe₃O₄ nano-particles. Furthermore, we obtained pH 8 and 1.5 M NaCl as an optimal condition for desorption of DNA from MNPs. The result further showed that, 0.2 mg nano-particle and 10 min at 55 °C are the optimal conditions for DNA desorption from nano-particles. In conclusion, we recommended Fe₃O₄/SiO₂/TiO₂ as a new MNP for separation of DNA molecules from biological sources.     

Hydrothermal synthesis and structure of an open framework Co0.7Zn1.3(PO4)2(NH3-CH2CH2NH3) and Co6.2(OH)4(PO4)4Zn1.80, a new adamite type phase

The hydrothermal reaction of cobalt(II)oxalate di-hydrate, zinc oxide, and triethyl-orthophosphate, using 1,2-diaminoethane as structure directing template in water, produced two major crystal phases in almost equal amount: the purple crystals of [NH₃-CH₂CH₂NH₃][Co_0.7Zn_1.3(PO₄)₂] (1) and the red burgundy crystals of Co_6.2(OH)₄(PO₄)₄Zn_1.80 (2), a new adamite type phase. The structure of [NH₃-CH₂CH₂NH₃] [Co_0.7Zn_1.3(PO₄)₂] (1) exhibits a 3D open framework built from PO₄ and (Co/Zn)O₄ tetrahedra, and (Co/Zn)O₅ trigonal bipyramids, forming two major channels, an 8-membered ring channel and a 16-membered ring channel, that host the ethanediammonium ions. The Co_6.2(OH)₄(PO₄)₄Zn_1.80 (2) is isomorphous with adamite-type M₂(OH)XO₄ structure, with a condensed vertex and edge sharing network of (Co/Zn)O₅, and distorted CoO₆, and PO₄ subunits. The cobalt preference for higher coordination numbers is displayed in this structure, where the octahedral sites are wholly occupied by cobalt. Thermal analysis confirmed that these compounds display high thermal stability.     

Photophysical properties of Eu(SiW11O39)2 and Eu(BW11O39)2

The photophysical properties (absorption, emission, and excitation spectra; luminescence quantum yields; luminescence decay lifetimes ) of K₁₃[Eu(SiW₁₁O₃₉)₂] and K₁₅[Eu(BW₁₁O₃₉)₂] in aqueous solution and in the solid state are reported. Both complexes exhibit broad and very intense O → W charge transfer bands in the U.V. region and weak and narrow f → f Eu₃₊ bands in the visible. At 77 K the luminescence emission of both complexes, which consists of ⁵D_O → ⁷F_J bands split by the local crystal field, can be pumped very efficiently via both the O → W CT and the f → f Eu³⁺ levels, whereas at 298 K only pumping via the f → f Eu³⁺ is efficient. The values of the luminescence decay lifetimes in H₂O and D₂O solution are quite similar, showing that no water molecule is coordinated to the central Eu₃₊ ion. The high resolution emission spectra are discussed in an attempt to define the coordination symmetry of Eu₃₊.     

Rb2[B12(OH)12]·2H2O and Rb2[B12(OH)12]·2H2O2: Hydrate and perhydrolate of rubidium dodecahydroxo-closo-dodecaborate

The orthorhombically crystallizing salts Rb₂[B₁₂(OH)₁₂]·2H₂O (a = 1576.81(9), b = 813.08(5), c = 1245.32(7) pm) and Rb₂[B₁₂(OH)₁₂]·2H₂O₂ (a = 1616.54(9), b = 814.29(5), c = 1260.12(7) pm) could be prepared from Rb₂[B₁₂H₁₂] and hydrogen peroxide. Both crystal structures were determined by X-ray single crystal diffraction and refined in the space group Cmce. They are not isostructural to the other compounds containing icosahedral dodecahydroxo-closo-dodecaborate dianions [B₁₂(OH)₁₂]²⁻ and potassium, rubidium or cesium cations already known to literature, but both title compounds crystallize quasi-isotypically exhibiting Rb⁺ cations in 10-fold oxygen coordination. The hydrogen peroxide adduct (Rb₂[B₁₂(OH)₁₂]·2H₂O₂) is explosive on shock and heat, while the hydrate (Rb₂[B₁₂(OH)₁₂]·2H₂O) is not.