钚 | 7440-07-5

• 物质功能分类: 无机化工 - 单质
• 分子结构分类: 无机化合物 - 均相金属化合物 - 均相锕系化合物
• 中文名称: 钚
• 英文名称: plutonium
• CAS: 7440-07-5
• 化学式: Pu
• 分子量: 244.064
• InChiKey: OYEHPCDNVJXUIW-UHFFFAOYSA-N

物化性质

• 熔点：
  640 ±2°
• 沸点：
  3228°C (estimate)
• 密度：
  d21 19.86; d190 17.70; d235 17.14; d320 15.92; d405 16.00; d490 16.51
• 颜色/状态：
  Silver, white metal, monoclinic /Plutonium metal/
• 溶解度：
  Soluble in hydrochloric acid; insol in nitric acid and concentrated hydrogen sulfide /Plutonium metal/
• 汽化热：
  345.2 kJ/mol at 298 deg K (range 1200-1790 deg K) /Plutonium metal/
• 表面张力：
  437-475 dyne/cu m (liquid)
• 稳定性/保质期：
  银白色金属，具有强放射性，有6种变体。熔点为639.5℃，沸点约为3235℃，其6种变体的密度分别为19.84克/立方厘米、17.70克/立方厘米、17.14克/立方厘米、15.92克/立方厘米、16.00克/立方厘米和16.51克/立方厘米。它的化学性质非常活泼，加热时能迅速被空气中的氧气氧化，并能直接与卤素化合，溶于盐酸而不溶于硝酸和浓硫酸。自然界中钚仅以微量存在于含铀矿物中。

计算性质

• 辛醇/水分配系数(LogP)：
  0.0
• 重原子数：
  1
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

钚-238可以通过摄入或吸入影响人体。当吸入时，钚-239倾向于在肺部积聚，尽管它也分布到肝脏和骨骼。摄入的钚可以在肝脏和骨骼中找到。钚的新陈代谢主要是由水解反应和与蛋白质和非蛋白质配体形成复合物，如白蛋白、球蛋白、铁蛋白、柠檬酸盐和乳酸盐。钚通过粪便和尿液排出。

Plutonium-238 can affect the body following ingestion or inhalation. When inhaled, Pu-239 tends to accumulate in the lungs, though it also distributes to the liver and skeleton. Ingested plutonium is found in the liver and bone. Plutonium metabolism consists primarily of hydrolytic reactions and formation of complexes with protein and nonprotein ligands, such as albumin, globulins, ferritin, citrate, and lactate. Plutonium is excreted in feces and urine. (L1841)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

钚发射的阿尔法辐射不能穿透皮肤，但当钚被吸入或摄入时，它可以照射到内部器官。尤其是骨骼，它很可能会被骨表面吸收，以及肝脏，钚在那里聚集并浓缩。钚产生的电离辐射会导致细胞损伤，包括DNA断裂、准确或不准确的修复、凋亡、基因突变、染色体改变和遗传不稳定。这导致正常细胞和组织的稳态丧失，并发展成恶性肿瘤。不直接损伤DNA的电离辐射可以产生反应性氧中间体，这些中间体直接影响细胞周期调节中重要的酶p53的稳定性，并通过对DNA中单个碱基的氧化损伤和DNA复制过程中的错配产生点突变。(L1837, L1841)

The alpha radiation plutonium emits does not penetrate the skin but can irradiate internal organs when plutonium is inhaled or ingested. Particularly at risk are the skeleton, where it is likely to be absorbed by the bone surface, and the liver, where it collects and becomes concentrated. The ionizing radiation produced by plutonium causes cellular damage that includes DNA breakage, accurate or inaccurate repair, apoptosis, gene mutations, chromosomal change, and genetic instability. This leads to loss of normal cell and tissue homeostasis, and development of malignancy. Ionizing radiation that does not directly damage DNA can produce reactive oxygen intermediates that directly affect the stability of p53, an important enzyme in cell-cycle regulation, and produce oxidative damage to individual bases in DNA and point mutations by mispairing during DNA replication. (L1837, L1841)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

有充分证据表明，人类吸入钚-239气溶胶会导致肺癌、肝癌和骨肉瘤。暴露于钚-239也意味着暴露于钚-240和其他同位素。/钚-239/

There is sufficient evidence in humans that inhalation of plutonium-239 aerosols causes lung cancer, liver cancer and bone sarcoma. Exposure to plutonium-239 also entails exposure to plutonium-240 and other isotopes. /Plutonium-239/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

混合α粒子发射体（镭-224、镭-226、钍-227、钍-228、钍-230、钍-232、镎-237、钚-238、钚-239（与钚-240一起）、镅-241、锔-244、锎-249和锎-252）在实验动物中具有致癌性的证据是充分的。/混合α粒子发射体/

There is sufficient evidence in experimental animals for the carcinogenicity of mixed alpha-particle emitters (radium-224, radium-226, thorium-227, thorium-228, thorium-230, thorium-232, neptunium-237, plutonium-238, plutonium-239 (together with plutonium-240), americium-241, curium-244, californium-249 and californium-252). /Mixed-alpha particle emitters/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

钚-239（239-Pu）对人类具有致癌性（第1组）。在做此总体评估时，工作组注意到人类接触239-Pu可能也包括接触240-Pu。

Plutonium-239 (239-Pu) is carcinogenic to humans (Group 1). In making this overall evaluation, the Working Group noted that human exposure to 239-Pu may also include exposure to 240-Pu.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

国际癌症研究机构致癌物：钚

IARC Carcinogenic Agent:Plutonium

来源:International Agency for Research on Cancer (IARC)

吸收、分配和排泄

吸入：通过对人类尸检材料中由于核武器大气测试产生的钚-239进行测量，结果显示相对较高比例的钚-239被保留在肺部组织和气管支气管淋巴结中，这与钚-239的低溶解性一致。/钚-239/

Inhalation: Measurements in human autopsy material of plutonium-239 resulting from the atmospheric testing of nuclear weapons show that a relatively high proportion of plutonium-239 is retained in lung tissue and tracheobronchial lymph nodes, consistent with low solubility. /Plutonium-239/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

吸入：据报道，大鼠和狗吸入钚硝酸盐以及大鼠和狒狒吸入钚三丁基磷酸盐具有中等溶解度。钚的氧化物是研究得最彻底的锕系气溶胶。通常，可以从呼吸道吸收到血液的两个阶段加以区分。一小部分，通常小于1%，在大约一天内被吸收，其余部分以数年为半衰期被清除。溶解度被发现高度依赖于气溶胶的形成方式。/钚硝酸盐和钚三丁基磷酸盐/

Inhalation: Intermediate solubility has been reported for plutonium nitrate inhaled by rats and dogs and plutonium tributyl-phosphate inhaled by rats and baboons. The oxides of plutonium are the most thoroughly studied of the actinide aerosols. Generally, two phases of absorption from the respiratory tract to blood can be distinguished. A small fraction, typically less than 1%, is absorbed within about one day, and the remainder is cleared with half-times of the order of years. The solubility has been shown to be highly dependent on how the aerosol is formed. /Plutonium nitrate and plutonium tributyl-phosphate/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

吞咽：新生仓鼠和豚鼠对钚的吸收在出生后的第一天最大，吸收值约为0.02-0.03，在哺乳期间逐渐降低，到断奶时（大约21到22天）达到成年值。/钚，NOS/

Ingestion: The absorption of plutonium in newborn hamsters and guinea-pigs has been shown to be greatest on the first day of life, with values of about 0.02-0.03, and to decrease progressively during the period of suckling to reach adult values by about the time of weaning at 21 to 22 days. /Plutonium, NOS/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

摄入：动物摄入硝酸、氯化物或碳酸氢盐形式给予的钚后，其分数吸收值在1X10-5到1X10-4的范围内。禁食已被证明可以增加一个数量级的吸收率。……通常情况下，摄入的质量和价态对吸收的影响很小；然而，当摄入大量五价钚时，吸收率可能会增加一个数量级，正如在狒狒中所示。以有机配合物形式或掺入食物中给予动物的钚的分数吸收通常大于无机形式的吸收率。/钚盐/

Ingestion: The fractional absorption values after uptake of plutonium administered to animals as the nitrate, chloride or bicarbonate are in the range of 1X10-5 to 1X10-4. Fasting has been shown to increase absorption by up to an order of magnitude. ... In general, the ingested mass and valence appear to have little effect on absorption; however, when large masses of pentavalent plutonium are ingested, absorption may be increased by an order of magnitude, as demonstrated ... in baboons. The fractional absorption of plutonium administered to animals as organic complexes or incorporated into food is generally greater than that of inorganic forms. /Plutonium salts/

来源:Hazardous Substances Data Bank (HSDB)

制备方法与用途

简介

钚（英语：Plutonium），原子序数为94，元素符号是Pu，是一种具有放射性的超铀元素。其半衰期约为24.5万年。钚属于锕系金属，外表呈银白色，接触空气后容易锈蚀、氧化，在表面生成无光泽的二氧化钚。

钚共有六种同位素和四种氧化态，并且容易与碳、卤素、氮、硅发生化学反应。当钚暴露在潮湿空气中时会生成氧化物和氢化物，其体积最大可膨胀70%；而屑状的钚还可能自燃。因此，钚是一种放射性毒物，在骨髓中富集，操作或处理钚元素具有一定的危险性。

理化性质

钚的化学性质非常活泼，即使在潮湿空气中甚至干燥的氩气中也会迅速氧化，产生氧化物和氢化物。粉末状态下的钚、其氢化物以及三氧化二钚都容易自燃，因此通常只能保存在干燥的氮气或氩气气氛中。

反应信息

• 作为反应物：
  描述：

  钚 在 ammonia 作用下， 以 aq. HNO₃ 为溶剂， 生成 plutonium(IV) hydroxide
  参考文献：
  名称：

  Disproportionation of Pu(V) in aqueous HCOOH solutions

  摘要：

  The behavior of Pu(VI), Pu(V), and Pu(IV) in the HCOOH-H2O system was studied by spectrophotometry. The Pu(VI) absorption spectrum in solutions containing less than 1 mM HClO4 changes on adding HCOOH to a concentration of 0.53 M. Along with a decrease in the intensity of the absorption maximum at 830.6 nm, corresponding to an f-f transition in the PuO22+ aqua ion, a new band arises with the maximum shifted to 834.5 nm. These transformations are due to formation of a Pu(VI) formate complex (1 : 1). The Pu(IV) absorption spectra in HCOOH solutions vary insignificantly in going from 3.0 to 9.0 M HCOOH and are similar to the spectrum of Pu(IV) in a 0.88 M HCOOH + 0.41 M NaHCOO + 0.88 M NaClO4 solution, which indicates that the composition of the Pu(IV) formate complexes is constant. Pu(V) is unstable in HCOOH solutions and disproportionates to form Pu(VI) and Pu(IV). The reaction rate is approximately proportional to [Pu(V)](2) and grows with an increase in [HCOOH]. The reaction products affect the reaction rate: Pu(IV) accelerates the process, and Pu(VI) decelerates the consumption of Pu(V) by binding Pu(V) in a cation-cation complex. The disproportionation occurs via formation of a Pu(V)-Pu(V) cation-cation complex whose thermal excitation yields an activated complex with its subsequent decomposition to Pu(VI) and Pu(IV).

  DOI：

  10.1134/s106636221001008x
• 作为产物：
  描述：

  plutonium(III) chloride 在 calcium 作用下， 以 neat (no solvent) 为溶剂， 生成 钚
  参考文献：
  名称：

  anonymous, 1960, vol. 3, p. 48 - 48

  摘要：

  DOI：
• 作为试剂：
  描述：

  americium(IV) oxide 、 vanadia 在 镎 、 钚 作用下， 生成 americium vanadate
  参考文献：
  名称：

  两种钒酸镅 AmVO3 和 AmVO4 的合成、表征和稳定性

  摘要：

  为了寻找用于太空应用的放射性同位素源的具有高功率密度的化学稳定的镅化合物，通过固相反应制备了AmVO 3和 AmVO 4 。我们在这里展示了它们在室温下的晶体结构，通过粉末 X 射线衍射结合 Rietveld 精修来解析。研究了它们的热稳定性和自辐射稳定性。镅的氧化态由 Am M 5确认边缘高分辨率X射线吸收近边缘结构（HR-XANES）技术。人们研究这种陶瓷作为放射性同位素热电发电机等太空应用的潜在电源，并且它们必须承受包括真空、高温或低温以及内部辐射在内的极端条件。因此，相对于其他具有高镅含量的化合物，测试并讨论了它们在惰性和氧化气氛中自辐照和热处理下的稳定性。

  DOI：

  10.1021/acs.inorgchem.3c00251

文献信息

• Synthesis and Coordination Chemistry of Phosphine Oxide Decorated Dibenzofuran Platforms
  作者：Daniel Rosario-Amorin、Eileen N. Duesler、Robert T. Paine、Benjamin P. Hay、Lætitia H. Delmau、Sean D. Reilly、Andrew J. Gaunt、Brian L. Scott

  DOI：10.1021/ic300301d

  日期：2012.6.18

  A four-step synthesis for 4,6-bis(diphenylphosphinoylmethyl)dibenzofuran (4) from dibenzofuran and a two-step synthesis for 4,6-bis(diphenylphosphinoyl)dibenzofuran (5) are reported along with coordination chemistry of 4 with In(III), La(III), Pr(III), Nd(III), Er(III), and Pu(IV) and of 5 with Er(III). Crystal structure determinations for the ligands, 4·CH3OH and 5, the 1:1 complexes [In(4)(NO3)3]

  报道了由二苯并呋喃四步合成4,6-双（二苯基膦酰基甲基）二苯并呋喃（4）和两步合成4,6-双（二苯基膦酰基）二苯并呋喃（5）以及4与In（）的配位化学。III），La（III），Pr（III），Nd（III），Er（III）和Pu（IV），以及5个带有Er（III）的化合物。配体4 ·CH 3 OH和5、1：1配合物[In（4）（NO 3）3 ]，[Pr（4）（NO 3）3（CH 3 CN）]·0.5的晶体结构测定CH 3 CN，[Er（4）（NO 3）3（CH 3 CN）]·CH 3 CN，[Pu（4）Cl 4 ]·THF和2：1络合物[Nd（4）2（NO 3）2 ] 2（NO 3）描述了2 ·（H 2 O）·4（CH 3 OH）。在这些络合物中，配体4通过两个氧化膦O原子以双齿POP'O'模式配位。二苯并呋喃环的O原子指向中心金属阳离子，但在每种情况下，都比金属高4Å。在5和5之间形成
• Electronic absorption spectra of gaseous PuCl3, PuBr3 and PuCl4
  作者：D.M. Gruen、C.W. DeKock

  DOI：10.1016/0022-1902(67)80182-9

  日期：1967.10

  The electronic absorption spectra of gaseous PuCl3, PuBr3 and PuCl4 have been measured in the range 4000–30,000 cm−1 at temperatures of ∼1000°. Intraconfigurational 5fn → 5fn transitions and interconfigurational 5fn → 5fn−16d transitions have been identified. The thermodynamics of the reaction: PuCl3(l) + 12Cl3 ⇌ PuCl4(g) has been studied spectroscopically. The molar free energy change of this reaction

  气态PuCl 3，PuBr 3和PuCl 4的电子吸收光谱在〜1000 °C的温度范围为4000–30,000 cm -1处测量。已经确定了构内的5 f n →5 f n过渡和构图的5 f n →5 f n -1 6 d过渡。反应的热力学：PuCl3（l）+ 12Cl3 = PuCl4（g）已进行了光谱学研究。该反应的摩尔自由能变化由等式ΔF = 23,000-14·1 T（cal）表示。
• Lattice constants and melting points of actinide-group IVA-VIA compounds with NaCl-type structures
  作者：O.L. Kruger、J.B. Moser

  DOI：10.1016/0022-3697(67)90257-0

  日期：1967.11

  Abstract Compounds of the actinides and group V and VI nonmetals were prepared by reaction of high-purity metals with gases and arc-fusion of the elements. Lattice constants and melting points of the compounds are reported. These properties were correlated with the electronic configuration of the actinides and the position of the nonmetal component in the period table.

  摘要 通过高纯金属与气体反应和元素电弧聚变制备了锕系元素与V、VI族非金属的化合物。报告了化合物的晶格常数和熔点。这些特性与锕系元素的电子构型和非金属成分在周期表中的位置相关。
• Complexation and redox chemistry of neptunium, plutonium and americium with a hydroxylaminato ligand
  作者：Jing Su、Thibault Cheisson、Alex McSkimming、Conrad A. P. Goodwin、Ida M. DiMucci、Thomas Albrecht-Schönzart、Brian L. Scott、Enrique R. Batista、Andrew J. Gaunt、Stosh A. Kozimor、Ping Yang、Eric J. Schelter

  DOI：10.1039/d1sc03905a

  日期：——

  monitoring and remediation efforts. Here, we report syntheses and characterization of Np(IV), Pu(IV) and Am(III) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(tBuNO)py]−(interchangeable hereafter with [(tBuNO)py]−), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(tBuNO)py]4 (An = Pu, 1; Np, 2) have been synthesized, characterized

  人们对可以稳定氧化态的锕系元素离子的配体非常感兴趣，这些配体可用于化学区分 5f 和 4f 元素。应用范围从开发用于核工业加工的大规模锕系元素分离策略到进行支持环境监测和修复工作的分析研究。这里，我们报告合成和Np个表征（IV），普（IV）和AM（III）配合物的N-叔丁基- ñ - （吡啶-2-基）hydroxylaminato，[2-（吨BUNO）吡啶] -（以后可与 [( t BuNO)py互换] -)，一种先前被发现赋予+4氧化态铈显着稳定性的配体。An[( t BuNO)py] 4 (An = Pu, 1 ; Np, 2 ) 已合成，通过 X 射线衍射、X 射线吸收、1 H NMR 和 UV-vis-NIR 光谱以及循环伏安法表征，以及计算建模和分析。在Pu的情况下，在与[( t BuNO)py] -配体络合后观察到Pu( III )氧化成Pu( IV ) 。Pu复合物1和Np复合物2也直接从Pu(
• Synthesis and extraction studies with a rationally designed diamide ligand selective to actinide(<scp>iv</scp>) pertinent to the plutonium uranium redox extraction process
  作者：Shikha Sharma、Surajit Panja、Arunasis Bhattacharyya、Prem S. Dhami、Preetam M. Gandhi、Sunil K. Ghosh

  DOI：10.1039/c6dt00748a

  日期：——

  extraction of Pu(IV) and Np(IV) over other actinide species, viz., U(VI), Np(V), Am(III), lanthanides and fission products contained in a nuclear waste from the PUREX process. DFT calculations predicted the charge density on each of the coordinating ‘O’ atoms of OTDA supporting its high Pu(IV) selectivity over other ions studied and also provided the energy optimized structure of OTDA and its Pu(IV) complex

  合理设计了一类新的构象受限的氧桥联三环二甲酰胺（OTDA）配体，用于选择性萃取与P铀氧化还原萃取（PUREX）过程有关的四价act系元素。合成了两个设计的二酰胺配体，并从HNO 3培养基中提取了Pu（IV）。通过研究饲料HNO 3，NaNO 3和OTDA浓度等各种参数，研究了提取机理。发现提取物的性质为[Pu（NO 3）4（OTDA）]。OTDA配体之一经过精心测试，显示出对Pu（IV）和Np（IV）超过PUREX工艺核废料中所含的其他act系元素，即U（VI），Np（V），Am（III），镧系元素和裂变产物。DFT计算预测了OTDA的每个配位'O'原子的电荷密度，支持了其对其他研究离子的高Pu（IV）选择性，还提供了OTDA及其Pu（IV）配合物的能量优化结构。