CN101082546A - Compounds used for element forming volatile matter - Google Patents
Compounds used for element forming volatile matter Download PDFInfo
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- CN101082546A CN101082546A CNA2007100577786A CN200710057778A CN101082546A CN 101082546 A CN101082546 A CN 101082546A CN A2007100577786 A CNA2007100577786 A CN A2007100577786A CN 200710057778 A CN200710057778 A CN 200710057778A CN 101082546 A CN101082546 A CN 101082546A
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Abstract
The invention relates to the compound used in element formation the volatile matter and this compound molecule composition is HnBmMp and H represents hydrogen n is not less than six and not greater than thirty and B represents boron m is not less than 2 and not greater than 20 and M presents lithium, natrium, kalium, ammonium, chorine, bromine, iodine or organic molecule or organic ion p is not less than 0 and not greater than 3. Adopt one kind or multiple kinds mixture of the compound liquor to react with the water liquor with the measuring element is no only make the arsenic, antimony, bismuth, germanium, tin, lead, selenium, tellurium, hydrargyrum which can easy to form the hydride in tradition formed the volatile matter also makes the other multiple tens elements (gold, silver, colalt, palladium, manganese, calcium and so on) formed the hydride. The compound can apply in the atomic spectrum analysis of the sample inlet so it can enhance the sensitivity of analysis detection and reduces the detection limit also can used in chemistry vapour deposition and the production of inorganic metallic-membrane plating gassy precursor.
Description
Technical Field
The invention belongs to the technical field of instrument analysis, and relates to a compound for preparing a gaseous precursor for element chemical vapor deposition and inorganic coating. And compounds that convert elements that form less volatile under normal conditions into volatiles.
Background
In 1969, Holak combines the classical arsine generation reaction with atomic spectroscopy, and establishes a hydride generation-atomic spectroscopy analysis combined technology. The method is that under certain reaction conditions, certain elements can generate nascent hydrogen as a reducing agent or perform chemical reaction, analytical elements in a sample solution are reduced into volatile covalent hydrides, and the volatile covalent hydrides are introduced into an atomic spectrum analysis system by means of carrier gas flow for quantitative determination. The flow injection-electrochemical hydride generation technology is reported for the first time in 1990, such As Huang Ben Li, and the like, elements generated by the electrochemical hydride are expanded to As, Sb, Se and the like, and the generation efficiency is greatly improved; and because the interference of the electrochemical generation method is greatly reduced by adopting the flow injection technology, the electrochemical hydride generation method gradually draws attention and is widely applied in recent years. At present, most hydride generation sample injection systems used in atomic spectrometers use sodium (potassium) borohydride as a hydride generation reduction reagent, and after elements in a sample solution are reduced to gaseous hydrides by hydrogen in the sodium (potassium) borohydride, the elements are measured in the atomic spectrometers. Compared with the conventional pneumatic atomization sampling in atomic spectrum, the hydride sampling efficiency has higher sampling efficiency (the conventional pneumatic atomization sampling is only 3-5%, the determination sensitivity is lower, and the hydride sampling efficiency is close to 100%), so the hydride sampling efficiency has the characteristics of higher sensitivity and lower detection limit in determination. It has been used that hydrides of sodium (potassium) borohydride and nine elements (arsenic, antimony, bismuth, germanium, tin, lead, selenium, tellurium, mercury) which are traditionally easy to form hydrides are formed and measured by an atomic spectrometer.
In recent years, with the continuous and intensive research of science and technology personnel, some workers engaged in analysis have successively found that other elements can also be subjected to hydrogenation reaction with sodium (potassium) borohydride, and have published a plurality of research papers. For example, Guowei et al 1995 discovered that zinc and cadmium in an acidic aqueous solution at room temperature can be reduced to volatile hydrides by a sodium borohydride solution, and the measurement of the content of zinc and cadmium in the actual sample was performed on atomic fluorescence using the hydrogenation occurring sample entering the system. Aderval.s Luna and p.pohl reported in the following 2000 and 2001, respectively, that some elements such as gold, silver, copper, manganese, titanium, etc. can also react with sodium (potassium) borohydride to form hydrides at normal temperature. However, the method reported in the above document has disadvantages of low hydride formation efficiency and serious residue phenomenon, and thus the practical use of the method is hindered.
For another example, Xu chuan Duan et al, JAAS 2002, reported a monitoring method in which gold, silver, cobalt, nickel, manganese, zinc, cadmium, copper, and other elements are reduced online using sodium borohydride as volatiles, but the experimental result is very unstable and difficult to reproduce despite the relatively high efficiency of formation.
The inventor also filed in 2003 for a patent entitled: the invention patent of atomic spectrometer sample entry method, publication number CN1527044A, reports the use of modified polymeric borohydrides as the element volatile forming agents, but the patent does not indicate the specific molecular formula and preparation method of the used agents, and does not have sufficiently specific theoretical expressions, making it difficult for the same professional to repeat the experiment.
Disclosure of Invention
The object of the present invention is to overcome the drawbacks and disadvantages of the prior art and to provide a compound for elemental volatile formation.
It is a further object of the invention to provide the use of the compounds for the preparation of volatile compounds from elements which are difficult to hydrogenate.
Another object of the invention is to use the compound as a hydrogen-containing reducing agent for hydride injection in atomic spectroscopy.
It is yet another object of the invention to disclose the preparation of the compounds as precursors for elemental chemical vapor deposition.
It is a further object of the invention to disclose the preparation of the compounds as gaseous precursors for inorganic coatings.
The inventor of the present invention surprisingly found in experiments that the high borane or high borohydride compound formed by chemical reaction using sodium (potassium) borohydride or diborane or high borane as raw material can not only make arsenic, antimony, bismuth, germanium, tin, lead, selenium, tellurium and mercury form hydride, but also make elements other than these elements: such as gold, silver, cobalt, nickel, manganese, zinc, cadmium, copper, platinum, ruthenium, palladium, iridium, scandium, titanium, vanadium, zirconium, iron, chromium, rhodium, calcium, etc., form hydrides with high generation efficiency, and the present invention has been completed based on this.
The technical scheme of the invention is as follows:
a compound for elemental volatile formation having the structure of formula I:
MpHnBm
I
wherein, the H represents element hydrogen 6 and n are respectively more than or equal to 30;
b represents an element boron 2 and m are not less than 20;
m represents elements of lithium, sodium, potassium, ammonium, chlorine, bromine, iodine, carbon or organic molecules or organic ions;
0≤p≤3。
the compound is borohydride salt or compound containing reduced hydrogen formed by chemical reaction of sodium borohydride, potassium borohydride, lithium borohydride or ammonium borohydride.
Preferred compounds of the invention are the higher boranes or compounds derived from higher boranes.
Another preferred compound of the invention is a reduced hydrogen-containing borohydride salt or compound formed by reacting diborane with other chemical species.
The compound of the invention is characterized in that when m is 2 and n is 6, p is more than 1. When p is 0, m is greater than or equal to 6, and n is greater than or equal to 6.
Further compounds according to the invention are the following:
1. the molecular formula is BmHnBoranes (m.gtoreq.6), e.g. B6H10，B8H12，B10H14、B4H10，B5H11，B6H12，B8H14And so on.
2. Ionic formula is BnHn+3 -Boron hydrogen salts, e.g. NaB5H8、KB10H13、B10H13MgX (X: halogen), B5H8X (X: halogen), NaB11H14、B2H5Cl, and the like.
4. Ionic formula is BnHn+ 5Such as B2H7 -，B3H8 -，B5H10 -And a borohydride salt of lithium, sodium, potassium, ammonium, chlorine, bromine, iodine, carbon, e.g. KB3H8、LiB3H8And so on.
5 ion formula is BnHn+4 2-Boron hydrogen salts, e.g. Na2B2H6、Na2B10H14And so on.
6. Ionic as BnHn2-Borohydride salt of (n-6-12): such as B10H10 2-B11H11 2-B12H12 2-B7H7 2-B8H8 2-B9H9 2-And borohydrides of lithium, sodium, potassium, ammonium, chlorine, bromine, iodine, organic ions, e.g. Na2B11H11、Na2B12H12、(CH)3NH(B12H12) And so on.
7. Molecular formula or ionic formula is respectively BnC2Hn+2(n＝3-10)、BnC2Hn+3 -(n-3-10) and BnCHn+1 -Carborane of (n-4-11);
the preferred mixture of the present invention is KB3H8Undecaborane monosodium salt and dodecaborane disodium salt, wherein the weight part ratio of undecaborane monosodium salt to dodecaborane disodium salt is KB3H8The mixture has obvious enhancementeffect on element forming volatile matters, namely, undecaborane monosodium salt and dodecaborane disodium salt, namely, 1: 1.
Another preferred mixture of the invention is KB3H8、Na2B12H12And Na2B11H11The mixture of (A) and (B) in parts by weight3H8∶Na2B12H12∶Na2B11H11The ratio is 1: 1.
The preparation method of the compound for forming volatile matters by elements comprises the step of reacting a solution of one or a mixture of a plurality of compounds with an acidic aqueous solution containing trace elements to be detected by adopting a conventional preparation method to enable the acidic aqueous solution containing the elements to form the volatile matters.
The invention further provides for the use of the compounds for the preparation of volatile compounds from elements which are difficult to hydrogenate.
The application of the volatile substance forming compound is that one or a mixture solution in the compound is prepared into 1.0-2.0% aqueous solution, the solution is continuously mixed on line by a peristaltic pump, then sample solution containing elements of gold, silver, copper, platinum, ruthenium, palladium and iridium is uniformly mixed and separated in a gas-liquid separator, generated volatile substance gas hydride is sent to an inductively coupled plasma emission spectrum by carrier gas for detection, and the detected element sensitivity is 50-100 times of that of the compound not containing the mixture under the same condition.
The method is suitable for reaction detection of hydride formation in the range of acidity of 0.05M to 5M, wherein the content of elements to be detected in the solution is below 500 mu g/ml.
In order to more clearly illustrate the compounds of the invention used for the element forming the volatile, the invention is described in detail below.
It is known that boron hydrides not only have the simplest molecules such as sodium (potassium) borohydride and diborane, but also have higher boranes and higher borohydrides with relatively large molecular weights. The preparation of high-element borane and high-element borohydride is carried out by sodium (potassium) borohydride or diborane through reaction. The following is a typical preparative equation (pertaining to conventional preparative methods).
6B2H6+2R3N→2(R3NH+)(B12H12)2-+11H2
B10H14+NaOH→NaB10H13+H2O
B10H14+NaBH4→NaB11H14+2H2
B2H6+NaBH4→NaB3H8+H2
B2H6+2Na→Na2B2H6
B2H6+HCl→B2H5Cl+H2
The molecular composition M according to the claims of the present inventionpHnBmIs the general formula for the reaction product above. When the reaction product is a homoborane, p is 0 and the molecular composition as claimed in the claims becomes HnBnSuch as B10H14Etc.; when the product is a higher borohydride salt or compound, p>0, e.g. KB3H8、Na2B12H12、LiB3H8、NaB11H14、(R3NH+)、(B12H12)2-NaB10H13，Na2B2H6Or B2H5Cl, and the like.
Compared with the prior art, the compound used for element forming volatile matter has the following remarkable positive effects:
the component to be detected is separated from the reaction liquid in a gas form through chemical reaction (hydride generation), so that the interference of the reaction liquid is reduced, the component to be detected is enriched, and the sample introduction efficiency is greatly improved. The reaction between the solution of one or several compounds and the water solution containing elements to be tested can form volatile matter from As, Sb, Bi, Ge, Sn, Pb, Se, Te and Hg, which are easy to form hydride, or form hydride from other dozens of elements (Au, Ag, Co, Pd, Mn, Ca, etc.). Particularly, after the compound is mixed to prepare a solution, the hydrogenation yield of gold, silver, cobalt, palladium, manganese,calcium, nickel, copper, manganese, iron and the like which are difficult to hydrogenate is obviously improved, the sensitivity of analysis and determination in atomic spectrum analysis is increased, and the detection limit is reduced. Meanwhile, the residual effect is eliminated, and the accuracy of sample analysis is improved. The practical results prove that when one or a mixture of several prepared by the invention is used for measuring the content of the element to be measured, the measured element sensitivity is 80-160 times that of the element without the compound under the same condition.
Detailed Description
To more fully explain the practice of the invention, the following examples of preparative embodiments of the compounds of the invention are provided for specific applications of the elements to form hydrides. These examples are merely illustrative and do not limit the scope of the invention.
Example one
According to a common synthesis method, after sodium borohydride is synthesized into dodecaborane disodium salt, the product dodecaborane disodium salt is prepared into 1.2% aqueous solution, then the solution and sample solution (the element content is 100ppb, the nitric acid acidity is 0.6M) containing elements of gold, silver, copper, platinum, ruthenium, palladium and iridium are continuously mixed on line by a peristaltic pump, the mixed solution is separated in a gas-liquid separator, the generated volatile gas hydride is conveyed to an inductively coupled plasma emission spectrum by carrier gas for detection, and the detected element sensitivity is 80-90 times that of the dodecaborane disodium salt solution under the same condition.
Example two
According to a common synthesis method, after sodium borohydride is used for synthesizing undecaborane monosodium salt, the product is prepared into 1.2% aqueous solution, then a peristaltic pump is used for continuously mixing the solution and sample solution (the element content is 100ppb, the nitric acid acidity is 0.2M) containing elements of cobalt, nickel, manganese, vanadium, yttrium, zirconium and scandium in an online manner, the mixed solution is separated in a gas-liquid separator, the generated volatile gas hydride is conveyed to an inductively coupled plasma emission spectrum by carrier gas for detection, and the detected element sensitivity is 150 times of 100 times of that when the solution does not contain undecaborane monosodium salt under the same condition.
EXAMPLE III
KB Synthesis according to the usual Synthesis method3H8(potassium octa-trihydroborate), preparing the product into a 1.2% aqueous solution, then continuously mixing the solution with a sample solution (the element content is 100ppb and the nitric acid acidity is 0.2M) containing elements of cobalt, nickel, manganese, vanadium, yttrium, zirconium and scandium on line by using a peristaltic pump, separating the mixed solution in a gas-liquid separator, sending the generated volatile gas hydride into an inductively coupled plasma emission spectrum by using a carrier gas for detection, wherein the detected element sensitivity is that the solution does not contain KB under the same condition3H8(potassium octaboronate) is 100 times and 120 times.
Example four
Will KB3H8Mixing (potassium octaborohydride), undecaborane monosodium salt and dodecaborane disodium salt according to the proportion of 1: 1, preparing the product into 1.2% aqueous solution, then continuously mixing the solution and sample solution (the element content is 100ppb and the nitricacid acidity is 0.2M) containing cobalt, nickel, manganese, vanadium, yttrium, zirconium and scandium on line by using a peristaltic pump, separating the mixed solution in a gas-liquid separator, conveying the generated volatile gas hydride into an inductively coupled plasma emission spectrum by using carrier gas for detection, and detecting the detected element sensitivity, wherein the solution does not contain the mixture (KB) under the same condition3H8(potassium octaboronate), undecaborane monosodium salt and dodecaborane disodium salt are mixed according to the proportion of 1: 1) by 160 times.
EXAMPLE five
Will KB3H8∶Na2B12H12∶Na2B11H11l are mixed according to the proportion of 1: 1, the product is prepared into 1.2 percent aqueous solution, then the solution and sample solution containing elements of cobalt, nickel, manganese, vanadium, yttrium, zirconium and scandium (the element content is 100ppb, the nitric acid acidity is 0.2M) are continuously mixed on line by a peristaltic pump, the mixed solution is separated in a gas-liquid separator, and the generated volatile gas hydride is sent to an electric generator by carrier gasThe sensitivity of the element is measured in the inductively coupled plasma emission spectrum under the same condition that the solution does not contain the mixture (KB)3H8∶Na2B12H12∶B2H5Cl mixed at a ratio of 1: 0.5) 120 times.
It will be apparent to those skilled in the art that various changes and modifications can be made in the above embodiments without departing from the scope and spirit of the invention, and it is intended that all simple changes, equivalents and modifications made to the above embodiments in accordance with the technical spirit of theinvention shall fall within the scope of the invention. And the invention is not limited to the embodiments of the examples given in the description.
Claims (9)
1. A compound for elemental volatile formation having the structure of formula I:
MpHnBm
I
wherein, the H represents element hydrogen 6 and n are respectively more than or equal to 30;
b represents an element boron 2 and m are not less than 20;
m represents lithium, sodium, potassium, ammonium, chlorine, bromine, iodine, carbon or an organic molecule or has
Organic ions; p is more than or equal to 0 and less than or equal to 3.
2. A compound according to claim 1, wherein the compound is a higher borane or a compound derived from a higher borane.
3. The compound of claim 1 wherein the compound is diborane formed by reaction with other chemical species to form a reduced hydrogen containing borohydride salt or compound.
4. The compound of claim 1, wherein said compound is a reduced hydrogen-containing borohydride salt or compound formed by a chemical reaction of sodium borohydride, potassium borohydride, lithium borohydride, or ammonium borohydride.
5. A compound according to claim 1, wherein when m is 2 and n is 6, then p>1.
6. A compound according to claim 1, wherein when p is 0, then m.gtoreq.6,
n≥6。
7. use of a compound according to any one of claims 1 to 6 as a hydrogen-containing reducing agent for hydride injection in atomic spectroscopic analysis.
8. Preparation of a compound according to any one of claims 1 to 6 as an elemental chemical vapour deposition precursor.
9. The preparation of a compound according to any one of claims 1 to 6 as a gaseous precursor for inorganic coatings.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105241867A (en) * | 2014-07-07 | 2016-01-13 | 苏州电器科学研究院股份有限公司 | Detection method of content of ruthenium element in electronic materials |
| CN106226252A (en) * | 2016-07-15 | 2016-12-14 | 天津师范大学 | The forming method of a kind of element evaporation thing and device |
| CN107525776A (en) * | 2016-07-15 | 2017-12-29 | 天津师范大学 | A kind of method and apparatus of atom spectrometer sample feeding |
| CN108414504A (en) * | 2018-03-16 | 2018-08-17 | 清远先导材料有限公司 | A method of measuring the reagent and a kind of special Gas content of measurement of special Gas content |
-
2007
- 2007-06-29 CN CNA2007100577786A patent/CN101082546A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105241867A (en) * | 2014-07-07 | 2016-01-13 | 苏州电器科学研究院股份有限公司 | Detection method of content of ruthenium element in electronic materials |
| CN106226252A (en) * | 2016-07-15 | 2016-12-14 | 天津师范大学 | The forming method of a kind of element evaporation thing and device |
| CN107525776A (en) * | 2016-07-15 | 2017-12-29 | 天津师范大学 | A kind of method and apparatus of atom spectrometer sample feeding |
| CN107525776B (en) * | 2016-07-15 | 2020-01-31 | 天津师范大学 | Sample feeding method and device for atomic spectrometers |
| CN108414504A (en) * | 2018-03-16 | 2018-08-17 | 清远先导材料有限公司 | A method of measuring the reagent and a kind of special Gas content of measurement of special Gas content |
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