CN103115951B - Tellurium-gold composite material as well as preparation and application thereof - Google Patents
Tellurium-gold composite material as well as preparation and application thereof Download PDFInfo
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- CN103115951B CN103115951B CN201310044241.1A CN201310044241A CN103115951B CN 103115951 B CN103115951 B CN 103115951B CN 201310044241 A CN201310044241 A CN 201310044241A CN 103115951 B CN103115951 B CN 103115951B
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Abstract
The invention discloses a tellurium-gold composite material as well as a preparation method thereof and an application to preparing an arsenic ion electrochemical detection electrode. The tellurium-gold composite material is prepared by the following steps of: dissolving an organic tellurium source into an organic solvent; adding absolute ethyl alcohol a under the effect of a reducing agent; closing and reacting for 3-5 hours under the condition of 120-150 DEG C in a stainless steel high-pressure kettle with a polytetrafluoroethylene liner to obtain a tellurium dendritic crystal; mixing the tellurium dendritic crystal with ethylene glycol and a gold-containing precursor; shaking under a closed condition of 60 DEG C to react; tracking and monitoring until ultraviolet absorption peaks of gold ions in reaction liquid disappear; after completely reacting, centrifuging and separating the reaction liquid; and taking sediment b and drying to obtain the tellurium-gold composite material. The anti-interference capability of the tellurium-gold composite material disclosed by the invention is strong; a pre-treatment method of the arsenic ion electrochemical detection electrode is simple and an electrochemical polarization process under a high electric potential is avoided; and the pre-treatment method can be realized by simple immersion and the sensitivity of sensing detection is improved.
Description
(1) technical field
The present invention relates to nano material preparation and Electrochemical Detection field, be specifically related to tellurium metal/composite material and preparation and application and the tellurium metal/composite material modified electrode electrochemical method for detection of trace trivalent inorganic arsenic.
(2) background technology
Water pollution is one of major issue threatening human health and social development, heavy metal pollution is a main aspect in water pollution, heavy metal mainly refers to the significant mercury of bio-toxicity, cadmium, plumbous, chromium and heavy metal arsenic, heavy metal in environment can pass through food chain enrichment in vivo, multiple systems to body cause damage, the compound of arsenic all has severe toxicity, trivalent arsenic compound is stronger than other arsenic compound toxicity, as intake exceeds standard, will be the liver of human body, kidney, lung, accumulate at the positions such as spleen, enzyme system in cell is combined, the biological agent of enzyme is suppressed to lose activity, thereby cause poisoning, in addition arsenic also has carcinogenesis.Therefore set up highly sensitive, the inorganic trivalent arsenic ion measurement of trace method accurately, significant to safeguarding the aspect such as Environmental security and human health.National Specification Arsenic in Drinking Water concentrations must not be greater than 0.01mg/L (GB5479-2006), specify according to the national drinking water standard method of inspection-metal index (GB/T5750.6-2006), arsenic detects and adopts By Hg-afs, although atomic fluorescence method method is sensitive and accurate, but complex operation, time are longer, need expensive checkout equipment, and in order to ensure the accuracy of working curve, need suitable concentration range to guarantee that arsenic content can be proportional with its fluorescence intensity.By contrast, electrochemical assay is both economical and convenient, therefore prepares the good sensitive material for detection of arsenic just very valuable.As the arsenious electrochemical method of a kind of detection being widely used, in mensuration process, mainly there is two problems, the poor sensitivity of measurement result and the copper ion serious interference to measurement result in stripping voltammetry.Nano material has the design features such as extra small structural unit, higher specific surface area, and reducing of material yardstick, has not only increased specific surface area, and the more important thing is has increased surperficial energy, thereby has improved the utilization factor in material activity site.Therefore make sensing electrode and can improve the detection performance of electrode by nano material, and the regulation and control of the affine character of the selectivity of nano composite material self and Preconcentration can strengthen the selectivity of sensing electrode, reduce the interference of other metallic ion.The present invention utilizes the tellurium metal/composite material modified glassy carbon electrode of preparation to make that sensing electrode can detect arsenic ion and selectivity is good.
(3) summary of the invention
The present invention seeks to detect for existing electrochemical techniques the problem of the narrow and poor anti jamming capability of arsenious method poor sensitivity, the range of linearity, and the tellurium gold nano compound substance modified electrode providing is for detection of the electrochemical method of trace trivalent inorganic arsenic; The present invention is by taking organic tellurium source and weak reductant as raw material, prepare tellurium dendrite template, and add containing golden presoma and prepare the golden dendrite micro Nano material with hybrid structure with this template, be i.e. the arsenious sensing electrode of described detection tellurium gold composite nano materials used.
The technical solution used in the present invention is:
The invention provides a kind of tellurium metal/composite material, described tellurium metal/composite material is prepared as follows: (1) tellurium dendrite: organic tellurium source is dissolved in organic solvent, under the effect of reductive agent, add absolute ethyl alcohol a, in the stainless steel autoclave of inner liner polytetrafluoroethylene, confined reaction 3 ~ 5h under 120 ~ 150 DEG C of conditions, after reaction finishes, reactant liquor is naturally cooled to room temperature (25 DEG C), get still bottom product centrifuging (preferably 8000rpm, 5min), get precipitation a and use successively pure water, after absolute ethyl alcohol b washing, at 50 DEG C, be dried 5 hours again, obtain tellurium dendrite, described organic tellurium source is the mixing of one or more arbitrary proportions in sodium tellurite, biphenyl two telluriums, tellurium diethyl dithiocarbamate, bromination benzyl dibutyl tellurid, p-anisyl tellurium oxide, described reductive agent is the one in dithio-salicylic acid, sodium citrate or glucose, described organic solvent is the mixing of one or both arbitrary proportions in chloroform, absolute ethyl alcohol, ethylene glycol or isopropyl alcohol, the volumetric usage of described organic solvent is counted 38.5 ~ 82.5ml/mmol with the amount of substance of tellurium in organic tellurium source, and the volumetric usage of described absolute ethyl alcohol a is counted 60 ~ 80ml/mmol with the amount of substance of tellurium in organic tellurium source, in described organic tellurium source, tellurium amount of substance is 1:2 ~ 5 with the ratio of reductive agent amount of substance, (2) tellurium metal/composite material: the tellurium dendrite that step (1) is obtained mixes with ethylene glycol with containing golden precursor, vibration under 60 DEG C of air-proof conditions (preferably 260rpm) reaction, tracking and monitoring is until the ultraviolet absorption peak of gold ion disappearance in reactant liquor (is got the micro-upper strata stillness of night with surveying its ultraviolet-visible absorption spectroscopy after deionized water dilution in course of reaction, there is no golden absorption peak at 200 ~ 400nm place, golden presoma reacts completely, if there is golden absorption peak, continue reaction, until there is no golden absorption peak at 200 ~ 400nm place), react completely, by reactant liquor centrifuging (preferably 8000rpm, 5min), get precipitation b dry (preferably 70 DEG C of vacuum drying 2h), obtain tellurium metal/composite material, described is the one in gold chloride, potassium chloroaurate, chlorauride or citric acid gold potassium containing golden presoma.
Further, in step (2), be preferably the one in gold chloride or gold potassium chloride containing golden presoma.
Further, in step (2), add with the form of 4 ~ 12mmol/L aqueous solution of chloraurate containing gold chloride in golden precursor.
Further, the consumption of tellurium dendrite is in metallic tellurium amount of substance the amount of substance of tellurium in the original organic tellurium source adding (in) in step (2), contain the consumption of golden precursor to contain gold ion amount of substance in golden precursor, described tellurium is 1:0.15 ~ 0.4 with the ratio of gold ion amount of substance.
Further, in step (2) volumetric usage of ethylene glycol in metallic tellurium amount of substance in the tellurium dendrite amount of substance of tellurium in the original organic tellurium source adding (taking) as 133 ~ 400ml/mmol.
Further, the described reaction of step (2) is oscillating reactions 3 ~ 5h under 60 DEG C of air-proof conditions.
The present invention also provides a kind of described tellurium metal/composite material in the application of preparing in arsenic ion electrochemical detection electrode.
Further, described tellurium metal/composite material is preparing being applied as in arsenic ion electrochemical detection electrode: 1) by glass-carbon electrode aluminum oxide suspension, at chamois leather, (chamois leather is the good material that polishing electrode is used, this material is just by electrode mirror polish, also can adopt other materials well known in the art by electrode mirror polish) upper sanding and polishing becomes minute surface, then supersound washing 1 ~ 3min in acetone, absolute ethyl alcohol and pure water successively, by pure water rinsing, in 0.5mol/L aqueous sulfuric acid, soak 10 minutes again, obtain pretreated glass-carbon electrode; Described glass-carbon electrode diameter is 2 ~ 5mm; 2) described tellurium metal/composite material is dispersed in the ethanolic solution of perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer (nafion), ultrasonic dispersion 10 ~ 20min, the mixed solution that acquisition mixes, mixed solution is dripped on pretreated glass-carbon electrode, 60 DEG C of standing and drying, obtain arsenic ion electrochemical detection electrode (being the glass-carbon electrode that tellurium metal/composite material is modified); The volumetric usage of the ethanolic solution of described perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer (nafion) is counted 2 ~ 5ml/mg with tellurium metal/composite material quality, and in the ethanolic solution of described perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer (nafion), teflon and absolute ethyl alcohol volume ratio are 1:10 ~ 40.Described perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer is the DES1020CS type nafion ethanolic solution that Du Pont produces, and concentration is 10%(w/w).
Arsenic ion electrochemical detection electrode electrochemical response method of testing of the present invention is: taking arsenic ion electrochemical detection electrode (being the glass-carbon electrode that tellurium metal/composite material is modified) as working electrode, taking silver-silver chloride as contrast electrode, platinum is to electrode, in the common electrochemical investigating pond that inserts the hydrochloride solution that contains arsenic, each electrode is connected on electrochemical workstation by corresponding relation, and described electrochemical workstation is by computer control.First use constant voltage technology, be set to-0.3V of voltage ~-0.5V, set of time is 100 ~ 120 seconds, preenrichment arsenic ion be reduced to arsenic simple substance with this understanding, then adopts square wave Stripping Voltammetry technology for detection arsenic ion, and condition is: sweep limit is-0.5V ~ 0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 2 seconds.There is oxidation reaction in the glass-carbon electrode surface of in scanning process, the arsenic of enrichment being modified at tellurium metal/composite material, detects its electrochemical response by computer program.The arsenic linear detection range of arsenic ion electrochemical detection electrode of the present invention is concentration 0.1 ~ 10 μ g/L, and detection sensitivity is 6.35 μ A/ (μ g/L).
The method of testing of anti-other metals of arsenic ion electrochemical detection electrode of the present invention is: in hydrochloric acid substrate solution, add other heavy metallic salt ion (being the metallic ion beyond arsenic ion), then according to arsenic ion electrochemical response method of testing is carried out.After each concentration detects, not containing in the hydrochloric acid solution of any salt ion, select time current technique on computers, current potential is set to 0.4V, 60 seconds time, the arsenic on end of run rear electrode surface can be completely oxidized to trivalent arsenic desorption, after desorption, tellurium metal/composite material modified electrode is taken out from electrolytic cell, clean rear stand-by by pure water rinsing; Be specially: if also contain other heavy metal ion in hydrochloric acid solution, cadmium, lead, chromium, nickel, iron, cobalt, mercury, zinc, manganese, calcium, their concentration is all that 5 ~ 50 μ g/L(preferred concentrations are 20 μ g/L), the glass-carbon electrode of modifying taking tellurium metal/composite material is as working electrode, silver-silver chloride is contrast electrode, platinum is to electrode, in the common electrochemical investigating pond that inserts the hydrochloride solution that contains variable concentrations arsenic, each electrode is connected on electrochemical workstation by corresponding relation, and described electrochemical workstation is by computer control.First use constant voltage technology, be set to-0.3V of voltage ~-0.5V, set of time is 100 seconds to 120 seconds, preenrichment trivalent arsenic be reduced to arsenic simple substance with this understanding, then adopts square wave Stripping Voltammetry technology, and parameter setting is that sweep limit is-0.5V ~ 0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 10 seconds.There is oxidation reaction in the glass-carbon electrode surface of in scanning process, the arsenic of enrichment being modified at tellurium metal/composite material, detects its electrochemical response by computer program.Then the electrode of tellurium metal/composite material being modified is not containing in the hydrochloric acid solution of any salt ion, select time current technique, current potential is set to 0.4V, 60 seconds time, the remaining arsenic in end of run rear electrode surface can be completely oxidized to trivalent arsenic desorption, after desorption, tellurium metal/composite material modified electrode is taken out from electrolytic cell, clean by pure water rinsing, electrode is reusable.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
(1) to prepare the preprocess method of arsenic ion electrochemical detection electrode simple in the present invention, avoided the activation polarization process under noble potential, just can realize, and improved the sensitivity of this sensing detection by simple immersion.
(2) tellurium metal/composite material antijamming capability of the present invention is strong, experiment shows: in the hydrochloric acid buffer solution of 1.0M, the glass-carbon electrode that utilizes tellurium metal/composite material to modify, can effectively separate with the oxidizing potential of metallic copper, and reduce the ability of copper ion in electrode surface enrichment, get rid of the interference of copper ion in water.
(3) detection time of the arsenic ion electrochemical detection electrode that prepared by tellurium metal/composite material of the present invention is short, adopt constant potential enrichment 100s, the range of linearity can reach 0.1 ~ 10 μ g/L, detects lower limit far below drinking water standard, can be accurately for the arsenious detection of actual sample.
(4) the arsenic ion electrochemical detection electrode that prepared by tellurium metal/composite material of the present invention can be used for arsenious detection in actual sample, stability and the selectivity ratios of electrode are higher, electrode, in the solution that contains a large amount of other metallic ions, still can be used for trivalent arsenic and detects.
(4) brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the tellurium dendrite prepared of embodiment 1: (a) for amplifying the scanning electron microscope diagram of 6000 times, (b) for amplifying the scanning electron microscope diagram of 12000 times, (c) be the transmission electron microscope picture of second branch tip portion, (d) be the high-resolution-ration transmission electric-lens figure of second branch tip portion, (e) being the transmission electron microscope picture of trunk tip portion, is (f) the high-resolution-ration transmission electric-lens figure of trunk tip portion.
Fig. 2 is the Electronic Speculum figure of the tellurium gold dendrite prepared of embodiment 1: (a) amplify the scanning electron microscope diagram of 6000 times; (b) amplify the scanning electron microscope diagram of 12000 times; (c) transmission electron microscope (HADDF) figure is joined in the details in a play not acted out on stage, but told through dialogues of high angle annular; (d) x-Ray Energy Spectrum Analysis figure; (e) transmission electron microscope picture; (f) be the high-resolution-ration transmission electric-lens figure in region shown in circle in (e).
Fig. 3 is the square wave Stripping Voltammetry curve of the arsenic ion electrochemical detection electrode prepared of embodiment 3 in the arsenious hydrochloric acid solution of variable concentrations.
Fig. 4 is arsenic ion electrochemical detection electrode prepared by embodiment 3 carry out electrochemical response test in variable concentrations arsenic solution time, the linear relationship chart of trivalent arsenic concentration and oxidation peak current.
Fig. 5 is the relation curve of the linear detection range of the arsenic ion electrochemical detection electrode prepared of embodiment 4.
Fig. 6 is arsenic ion electrochemical detection electrode prepared by embodiment 4 carry out electrochemical response test in variable concentrations arsenic solution time, the linear relationship chart of arsenic concentration and oxidation peak current.
Fig. 7 is the square wave Stripping Voltammetry curve map in the hydrochloric acid solution that coexists at copper ion and the trivalent arsenic of variable concentrations of arsenic ion electrochemical detection electrode prepared by embodiment 4.
Fig. 8 is the column diagram of the oxidation current of the arsenic ion electrochemical detection electrode prepared of embodiment 6 to different toxic metals ions, and wherein arsenious concentration is 1 μ g/L, and other ion concentration is all 10 μ g/L.
Fig. 9 is the cylindricality enlarged drawing of the metallic ion of other except arsenic ion in Fig. 8.
Figure 10 is the selectivity that the arsenic ion electrochemical detection electrode prepared of embodiment 4 detects arsenic.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer is the DES1020CS type nafion ethanolic solution that Du Pont produces, and concentration is 10%(w/w).
Embodiment 1
Tellurium three lopwood crystalline substances synthetic: in the stainless steel autoclave of the inner liner polytetrafluoroethylene of 50mL volume, get 0.15g(tellurium 0.208mmol) tellurium diethyl dithiocarbamate (TDEC) is dissolved in 10mL CHCl
3in, then adding successively 0.20g(0.65mmol) absolute ethyl alcohol of dithio-salicylic acid (DTBA) and 15mL is to 50% of volume, autoclave is sealed in the baking oven that is placed on 130 DEG C, react after 5 hours, reactant liquor naturally cools to room temperature (25 DEG C), get reactor bottom product centrifuging (8000rpm, 5min), obtain black product (precipitation), use successively pure water, absolute ethanol washing 3 times, centrifuging (8000rpm after washing, 5min) get precipitation and in 50 DEG C of vacuum drying chambers, be dried 4 hours again, obtain tellurium dendrite 23.6mg, productive rate is 89.6%.Tellurium dendrite scanning electron microscope (SEM) photograph see in Fig. 1 (a) and (b) shown in, from scheming, single tellurium dendrite is to be made up of three trunks and second branch, second branch is positioned on each trunk and Parallel Symmetric distributes, between three trunks, be 120 degree symmetrical, trunk length is 25～35 μ m, the length of branch approximately 1～5 μ m, and second branch length is successively decreased along the opposite direction of trunk point of crossing.In Fig. 1 (c) and (d) be transmission electron microscope picture and the high-resolution electron microscope figure of the tip portion of second branch, in figure, lattice fringe is high-visible, and its spacing is 0.385nm, consistent with (100) interplanar distance of six side's telluriums.Show that its second branch is along being parallel to the growth of (100) crystal face.Meanwhile, in Fig. 1 (e) and (f) be transmission electron microscope picture and the high-resolution electron microscope figure of the tip portion of trunk, its spacing of lattice is also 0.385nm, consistent with (100) interplanar distance of six side's telluriums.Show that its trunk is also along being parallel to the growth of (100) crystal face.
Tellurium metal/composite material (AuTe) three lopwood crystalline substances, be arsenic ion Electrochemical Detection sensor sensing material) synthetic: in the test tube of 30mL volume, the tellurium dendrite that adds successively the ethylene glycol of 20mL and the above-mentioned steps of 0.15mmol (1) to obtain, stir 10min at room temperature (25 DEG C) lower magnetic force, then adding 4mL concentration is the HAuCl of 10mM
4aqueous solution (gold content is 0.04mmol), test tube sealing is placed on in the oscillator of 60 DEG C, vibrate (hunting speed is 260rpm) at 3 o'clock, in course of reaction, get the micro-upper strata stillness of night with surveying its ultraviolet-visible absorption spectroscopy after deionized water dilution, there is no golden absorption peak at 200 ~ 400nm place, invisible spectro product is carried out to centrifuging (8000rpm, 5min), get precipitation and use successively pure water, absolute ethanol washing, centrifuging (8000rpm after washing, 5min) get and be deposited in dry 2h in 60 DEG C of vacuum drying chambers, obtain described arsenic ion Electrochemical Detection sensor sensing material (AuTe tri-lopwood crystalline substances) 29.3mg, through ICP-MS(agilent 7500, Agilent company) determine that afterwards the massfraction of gold in golden dendrite is that 28.4%(is with respect to AuTe dendrite), productive rate is 94.6%.AuTe tri-lopwood crystal structures are analyzed: from Fig. 2 (a) and (b) known, the AuTe hybrid structure of generation does not destroy the structure of original tellurium template, just in tellurium template, has been coated the film that one deck is made up of golden nanometer particle.In Fig. 2, (c) is HAADF picture, confirmed too this clad structure of AuTe.In Fig. 2, (d) is the EDS figure of this structure, can find out clearly that this clad structure is made up of Te and Au from figure.In Fig. 2 (e) and (f) be respectively its transmission electron microscope photo and corresponding high-resolution transmission photo.The Au particle that high-resolution photo demonstrates nano particle clearly covers the top layer that is embedded in Te, the wherein spacing of lattice clear-cut texture of gold grain, and spacing 0.208nm, consistent with (200) interplanar distance of gold.Synthesizing map 2 is known, the perfect formation of AuTe clad structure taking hierarchy tellurium material as template, and surface is overmolding to layer structure by Au nano particle.And do not destroy original structure in experiment.
Embodiment 2
The preparation of arsenic ion Electrochemical Detection sensor sensing material
(1) Te dendrite is synthetic: in the stainless steel autoclave of the inner liner polytetrafluoroethylene of 50mL volume, get 0.13mmol biphenyl two telluriums and be dissolved in 16.5mL CHCl
3in, then add successively the absolute ethyl alcohol of 0.65mmol dithio-salicylic acid (DTBA) and 16mL to 65% of volume, autoclave is sealed in the baking oven that is placed on 120 DEG C, react after 3 hours, reactant liquor naturally cools to room temperature (25 DEG C), get reactor bottom product centrifuging (8000rpm, 5min), obtain black product (precipitation), use successively pure water, absolute ethanol washing 3 times, centrifuging (8000rpm after washing, 5min), get precipitation and in 50 DEG C of vacuum drying chambers, be dried 4 hours again, obtain tellurium dendrite 30.2mg, productive rate is 91.6%.Three structural integrities of tellurium dendrite, the average-size of trunk is 30 microns, and the Size Distribution of branch is inhomogeneous, and average-size is 5 microns.
(2) tellurium metal/composite material, be the synthetic of arsenic ion Electrochemical Detection sensor sensing material (AuTe dendrite): in the test tube of 30mL volume, the tellurium dendrite that adds successively the ethylene glycol of 20mL and the step of 0.05mmol (1) to prepare, stir 5min at room temperature (25 DEG C) lower magnetic force, then add the potassium chloroaurate of 0.04mmol, test tube sealing is placed on in the oscillator of 60 DEG C, vibrate 3 hours (hunting speed is 260rpm), in course of reaction, get the micro-upper strata stillness of night with surveying its ultraviolet-visible absorption spectroscopy after deionized water dilution, there is no golden absorption peak at 200 ~ 400nm place, invisible spectro product is carried out to centrifuging (8000rpm, 5min), get precipitation and use successively pure water, absolute ethanol washing, centrifugal (8000rpm after washing, 5min), get and be deposited in dry 2h in 70 DEG C of vacuum drying chambers, obtain described arsenic ion Electrochemical Detection sensor sensing material (AuTe dendrite) 28.3mg, after high efficiency transmission electronic microscope photos, the lattice of the tellurium metal/composite material of preparing with embodiment 1 is identical, through ICP-MS(agilent 7500, Agilent company) determine that afterwards the massfraction of gold in tellurium metal/composite material is 28.9%, calculating productive rate is 96.4%.Confirm through Electronic Speculum picture, three structures of tellurium do not have destroyed, and tellurium metal/composite material structure is still preserved three complete structures, crystal structure high-sequential.
Embodiment 3
The preparation of the working electrode of arsenic ion Electrochemical Detection sensor
(1) glass-carbon electrode of diameter 2mm is become to minute surface with aluminum oxide suspension sanding and polishing on chamois leather of particle diameter 1.0 μ m and 0.3 μ m respectively, 40KHz supersound washing 1 ~ 3min in acetone, absolute ethyl alcohol and pure water successively, electrode surface is clean by pure water rinsing, in 0.5M aqueous sulfuric acid, soak 10 minutes, obtain pretreated glass-carbon electrode.
(2) powder of getting the arsenic ion Electrochemical Detection sensor sensing material of 1mg embodiment 1 is distributed in 2mL nafion ethanolic solution (volume ratio of nafion and absolute ethyl alcohol is 1:20), at the ultrasonic dispersion of 40KHz 30min, obtain the mixed solution mixing.Mixed solution is dripped to respectively on the pretreated glass-carbon electrode of step (1), 40 DEG C of standing and drying, can obtain arsenic ion electrochemical detection electrode.
(3) electrochemical response test: test platform is CHI660C electrochemical workstation (Shanghai Chen Hua instrument company), adopt traditional three-electrode system, the arsenic ion electrochemical detection electrode of preparing taking above-mentioned steps (2) is as working electrode, be respectively electrode and contrast electrode with platinum filament and saturated silver-silver chloride electrode, taking 1mol/L hydrochloric acid solution as substrate electrolytic solution, the final concentration of arsenic ion is 0.1 μ g/L successively, 0.5 μ g/L, 0.9 μ g/L, 1.3 μ g/L, 1.7 μ g/L, 2.1 μ g/L, 2.5 μ g/L, 2.9 μ g/L, 3.3 μ g/L, 3.7 μ g/L, 4.1 μ g/L, 4.5 μ g/L, 5.0 μ g/L, adopt constant voltage technology, be set to-0.3V of voltage, set of time is 100 seconds, preenrichment trivalent arsenic be reduced to arsenic simple substance with this understanding, then adopt square wave Stripping Voltammetry technology, parameter setting is that sweep limit is-0.5V ~ 0.5V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 2 seconds.In scanning process, the arsenic simple substance that is enriched in arsenic ion electrochemical detection electrode surface is oxidized, by oxidation peak current and its electrochemical response of potentiometric detection.
The results are shown in Figure 3 and Fig. 4, Fig. 4 is the linear relationship of arsenic concentration and oxidation peak current.From Fig. 3 and Fig. 4, the oxidation peak current potential of arsenic is 0.07V, oxidation peak current is along with arsenic concentration increases and becomes large, detection sensitivity is 6.39 μ A/ (μ g/L), detecting lower limit is 0.05 μ g/L, be significantly less than state-set standard (GB5479-2006), can be for arsenious detection in actual sample.
Embodiment 4
The preparation of arsenic ion Electrochemical Detection sensor electrode
(1) glass-carbon electrode of diameter 5mm is become to minute surface with aluminum oxide suspension sanding and polishing on chamois leather of particle diameter 1.0 μ m and 0.3 μ m respectively, 40KHz supersound washing 1 ~ 3min in acetone, absolute ethyl alcohol and pure water successively, electrode surface is clean by pure water rinsing, in 0.5M aqueous sulfuric acid, soak 10 minutes, obtain pretreated glass-carbon electrode.
(2) powder of getting arsenic ion Electrochemical Detection sensor sensing material prepared by 1mg embodiment 2 is distributed in 3 parts of 2mL nafion ethanolic solutions (volume ratio of nafion and absolute ethyl alcohol is 1:20), the ultrasonic dispersion of 40KHz 30min, obtains respectively the mixed solution mixing.Mixed solution is dripped to respectively on the pretreated glass-carbon electrode of step (1), 40 DEG C of standing and drying, obtain respectively arsenic ion electrochemical detection electrode, numbering is electrode 1#, electrode 2# and electrode 3#.
(3) electrochemical response test: test platform is CHI660C electrochemical workstation (Shanghai Chen Hua instrument company), adopt traditional three-electrode system, prepare arsenic ion electrochemical detection electrode 1# as working electrode taking above-mentioned steps (2), be respectively electrode and contrast electrode with platinum filament and saturated silver-silver chloride electrode, taking 1mol/L hydrochloric acid solution as substrate electrolytic solution, the final concentration of arsenic ion is 1.5 μ g/L successively, 3.0 μ g/L, 4.0 μ g/L, 6.0 μ g/L, 7.5 μ g/L, 9.0 μ g/L, 10.5 μ g/L, adopt constant voltage technology, be set to-0.3V of voltage, set of time is 100 seconds, preenrichment trivalent arsenic be reduced to arsenic simple substance with this understanding, then adopt square wave Stripping Voltammetry technology, parameter setting is that sweep limit is-0.5V ~ 0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 2 seconds.In scanning process, the arsenic simple substance that is enriched in arsenic ion electrochemical detection electrode surface is oxidized, by oxidation peak current and its electrochemical response of potentiometric detection.
The results are shown in Figure 5 and Fig. 6, Fig. 6 is the linear relationship chart of arsenic concentration and oxidation peak current.From Fig. 5 and Fig. 6, arsenic ion electrochemical detection electrode is to the non-constant width of the sensing range of arsenic, in the scope of 0.1 ~ 10.5 μ g/L, there is good linear relationship, corresponding working curve equation is Y (μ A)=6.59+6.36X (μ g/L), basic identical with the sensitivity in embodiment 3, illustrate that arsenic ion electrochemical detection electrode has good reappearance and stability.The existing good detection lower limit of arsenic ion electrochemical detection electrode, also has the wider range of linearity, applicable to the relatively large water quality detection of concentration change.
Embodiment 5
The anti-copper ion jamming performance test of arsenic ion electrochemical detection electrode Electrochemical Detection arsenic
(1) get the 2# arsenic ion electrochemical detection electrode of making in embodiment 4 in CHI660C electrochemical workstation (Shanghai Chen Hua instrument company), adopt traditional three-electrode system, be respectively electrode and contrast electrode with platinum filament and saturated silver-silver chloride electrode, taking 1mol/L hydrochloric acid solution as substrate electrolytic solution, add arsenic ion and copper ion simultaneously, the final concentration of arsenic ion is 0.6 μ g/L successively, 1.0 μ g/L, 1.6 μ g/L, 2.0 μ g/L, 2.4 μ g/L, 3.2 μ g/L, the final concentration of corresponding copper ion is 30 μ g/L successively, 50 μ g/L, 80 μ g/L, 100 μ g/L, 120 μ g/L, 160 μ g/L, adopt constant voltage technology, be set to-0.3V of voltage, set of time is 100 seconds, preenrichment trivalent arsenic be reduced to arsenic simple substance with this understanding, then adopt square wave Stripping Voltammetry technology, parameter setting is that sweep limit is-0.5V ~ 0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 2 seconds.In scanning process, the arsenic simple substance that is enriched in arsenic ion electrochemical detection electrode surface is oxidized, by oxidation peak current and its electrochemical response of potentiometric detection.After each concentration detects, not containing in the hydrochloric acid solution of any salt ion, select time current technique on computers, current potential is set to 0.4V, 60 seconds time, the arsenic on end of run rear electrode surface can be completely oxidized to trivalent arsenic desorption, after desorption, arsenic ion electrochemical detection electrode is taken out from electrolytic cell, clean rear stand-by by pure water rinsing.
The results are shown in Figure 7, the oxidation peak current potential of copper is 0.16V, and the oxidation peak current potential of arsenic is 0.06V, and two oxidation peak only have fraction overlapping, still can accurately judge differentiation.The linear equation that separately obtains arsenic concentration and oxidation peak current according to the Fitting Calculation is Y (μ A)=5.28+5.16X (μ g/L), while comparing independent detection, sensitivity declines 18.8%, and the concentration of copper ion and peak current linear equation are Y (μ A)=7.64+0.05X (μ g/L), sensitivity is 1% of arsenic detection, therefore, the electrode (being arsenic ion electrochemical detection electrode) that utilizes tellurium metal/composite material to modify, 103 times of copper to the detection sensitivity of arsenic, the spike potential of oxidation peak differs 100mv, these character can be used for getting rid of the impact that copper ion common in actual water sample detects arsenic, therefore electrode pair copper ion has good antijamming capability.
Embodiment 6
The impact test of other common metallic ion on arsenic ion electrochemical detection electrode Electrochemical Detection arsenic
(1) diameter 2mm glass-carbon electrode is become to minute surface with aluminum oxide suspension sanding and polishing on chamois leather of particle diameter 1.0 μ m and 0.3 μ m respectively, 40HKz supersound washing 1 ~ 3min in acetone, absolute ethyl alcohol and pure water successively, electrode surface is clean by pure water rinsing, in 0.5M aqueous sulfuric acid, soak 10 minutes, obtain pretreated glass-carbon electrode.
(2) powder of getting arsenic ion Electrochemical Detection sensor sensing material prepared by 1mg embodiment 1 is distributed in the ethanolic solution (volume ratio of nafion and absolute ethyl alcohol is 1:20) of 10 parts of 2mL nafion, the ultrasonic dispersion of 40HKz 30min, obtains respectively the mixed solution mixing.Mixed solution is dripped on the pretreated glass-carbon electrode of step (1), 40 DEG C of standing and drying, obtain arsenic ion electrochemical detection electrode, totally 10 electrodes, number by numerical order.
Test platform is CHI660C electrochemical workstation (Shanghai Chen Hua instrument company), adopt traditional three-electrode system, prepare arsenic ion electrochemical detection electrode as working electrode taking above-mentioned steps (2), be respectively electrode and contrast electrode with platinum filament and saturated silver-silver chloride electrode, taking 1mol/L hydrochloric acid solution as substrate electrolytic solution, add respectively other ionizable metal salt, they are respectively cadmiums, plumbous, chromium, nickel, iron, cobalt, mercury, zinc, manganese, calcium, their final concentration is all 10 μ g/L, 10 parts of electrodes that previous step is made are tested respectively these the 10 kinds solution containing different metal salt ion.Enrichment adopts constant voltage technology, be set to-0.3V of voltage, set of time is 100 seconds, salt ion in preenrichment solution be reduced to simple substance with this understanding, then adopts square wave Stripping Voltammetry technology, and parameter setting is that sweep limit is-0.5V ~ 0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 2 seconds.In scanning process, by being enriched in the metal simple-substance oxidation on arsenic ion electrochemical detection electrode surface, detect its electrochemical response by oxidation current.
The results are shown in Figure 8 and Fig. 9 shown in, due to the high selectivity of arsenic ion electrochemical detection electrode to arsenic, the oxidation peak that do not have in the time detecting of other 10 kinds of ionizable metal salts occurs, only that oxidation current becomes greatly, when not adding the substrate solution of slaine, there is milder bulge in the shape of scanning curve.Get the place of two curve electric current difference maximums as oxidation current, Fig. 8 and Fig. 9 can find out that in the concentration of other ion be 10 μ g/L, and arsenic concentration is 1 μ g/L, the oxidation current of arsenic is the more than 100 times of other ion, therefore electrode has the selectivity of height, is mainly because tellurium gold composite nanostructure is larger and select suitable deposition voltage than other ion to arsenious affinity.
Embodiment 7
The selectivity test of tellurium metal/composite material modified electrode (being arsenic ion electrochemical detection electrode)
(1) get the 3# arsenic ion electrochemical detection electrode of making in embodiment 4 in CHI660C electrochemical workstation (Shanghai Chen Hua instrument company), adopt traditional three-electrode system, be respectively electrode and contrast electrode with platinum filament and saturated silver-silver chloride electrode, contain with (being to contain so many metals in a electrolytic solution) copper that final concentration is all 40 μ g/L, cadmium, plumbous, chromium, nickel, iron, cobalt, mercury, zinc, manganese, the 1mol/L hydrochloric acid solution of calcium is electrolytic solution, add respectively the arsenic of variable concentrations, the final concentration of arsenic is 0 successively, 1.2 μ g/L, 1.6 μ g/L, 2.0 μ g/L, 2.4 μ g/L, 2.8 μ g/L, 3.2 μ g/L, adopt constant voltage technology, be set to-0.3V of voltage, set of time is 100 seconds, preenrichment trivalent arsenic be reduced to arsenic simple substance with this understanding, then adopt square wave Stripping Voltammetry technology, parameter setting is that sweep limit is-0.5V ~ 0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose 2 seconds.In scanning process, the arsenic simple substance that is enriched in arsenic ion electrochemical detection electrode surface is oxidized, by oxidation peak current and its electrochemical response of potentiometric detection.After each concentration detects, not containing in the hydrochloric acid solution of any salt ion, select time current technique on computers, current potential is set to 0.4V, 60 seconds time, the arsenic on end of run rear electrode surface can be completely oxidized to trivalent arsenic desorption, after desorption, tellurium gold modified electrode is taken out from electrolytic cell, clean rear stand-by by pure water rinsing.
The results are shown in Figure 10, is the oxidation peak of copper at 0.15V place, because the concentration of copper ion is changeless, so its peak current and spike potential do not change substantially.In arsenic detects, the interference of copper is the most serious, and this electrode can be distinguished the oxidation peak of arsenic and copper really, in the same manner as in Example 5, the anti-copper ion interference performance of this electrode is very strong, and other ion occurs without any oxidation peak at scanning curve, and therefore this electrode can be used for the arsenic detection of actual water sample.The oxidation peak current potential of arsenic is 0.02V, differ 120mv with copper oxidation peak current potential, Y (μ A)=5.28+5.23X (μ g/L) by the linear fit equation that calculates arsenic concentration and oxidation peak current, the sensitivity of remolding sensitivity embodiment 5 has increased 1.34%, and therefore anti-interference the and stability of electrode is good.
Claims (8)
1. a tellurium metal/composite material, it is characterized in that described tellurium metal/composite material prepared as follows: (1) tellurium dendrite: organic tellurium source is dissolved in organic solvent, under the effect of reductive agent, add absolute ethyl alcohol a, in the stainless steel autoclave of inner liner polytetrafluoroethylene, confined reaction 3～5h under 120～150 DEG C of conditions, after reaction finishes, reactant liquor is naturally cooled to room temperature, get the centrifuging of still bottom product, get precipitation a successively with after pure water, absolute ethyl alcohol b washing, then be dried 5 hours at 50 DEG C, obtain tellurium dendrite; Described organic tellurium source is the one in biphenyl two telluriums, tellurium diethyl dithiocarbamate; Described reductive agent is dithio-salicylic acid; Described organic solvent is the mixing of one or both arbitrary proportions in chloroform, absolute ethyl alcohol, ethylene glycol or isopropyl alcohol; The volumetric usage of described organic solvent is counted 38.5～82.5ml/mmol with the amount of substance of tellurium in organic tellurium source, and the volumetric usage of described absolute ethyl alcohol a is counted 60～80ml/mmol with the amount of substance of tellurium in organic tellurium source; In described organic tellurium source, tellurium amount of substance is 1:2～5 with the ratio of reductive agent amount of substance; (2) tellurium metal/composite material: the tellurium dendrite that step (1) is obtained mixes with ethylene glycol with containing golden precursor, oscillating reactions 3-5h under 60 DEG C of air-proof conditions, tracking and monitoring is until the ultraviolet absorption peak of gold ion disappearance in reactant liquor, react completely, by reactant liquor centrifuging, get precipitation b dry, obtain tellurium metal/composite material; Described is the one in gold chloride, potassium chloroaurate, chlorauride or citric acid gold potassium containing golden presoma.
2. tellurium metal/composite material as claimed in claim 1, is characterized in that in step (2) being the one in gold chloride or gold potassium chloride containing golden presoma.
3. tellurium metal/composite material as claimed in claim 1, is characterized in that adding with the form of 4～12mmol/L aqueous solution of chloraurate containing gold chloride in golden precursor in step (2).
4. tellurium metal/composite material as claimed in claim 1, it is characterized in that the consumption of tellurium dendrite in step (2) is in metallic tellurium amount of substance, contain the consumption of golden precursor to contain gold ion amount of substance in golden precursor, described tellurium is 1:0.15～0.4 with the ratio of gold ion amount of substance.
5. tellurium metal/composite material as claimed in claim 1, is characterized in that the volumetric usage of ethylene glycol in step (2) is counted 133～400ml/mmol with metallic tellurium amount of substance in tellurium dendrite.
Described in a claim 1 tellurium metal/composite material in the application of preparing in arsenic ion electrochemical detection electrode.
As claimed in claim 6 tellurium metal/composite material in the application of preparing in arsenic ion electrochemical detection electrode, described in it is characterized in that, be applied as: 1) glass-carbon electrode aluminum oxide suspension sanding and polishing on chamois leather is become to minute surface, then supersound washing 1～3min in acetone, absolute ethyl alcohol and pure water successively, by pure water rinsing, in 0.5mol/L aqueous sulfuric acid, soak 10 minutes again, obtain pretreated glass-carbon electrode; Described glass-carbon electrode diameter is 2～5mm; 2) described tellurium metal/composite material is dispersed in the ethanolic solution of perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer, ultrasonic dispersion 10～20min, the mixed solution that acquisition mixes, mixed solution is dripped on pretreated glass-carbon electrode, 60 DEG C of standing and drying, obtain arsenic ion electrochemical detection electrode; The volumetric usage of the ethanolic solution of described perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer is counted 2～5ml/mg with tellurium metal/composite material quality, and in the ethanolic solution of described perfluorinated sulfonic acid-polytetrafluoroethyl-ne alkene copolymer, teflon and absolute ethyl alcohol volume ratio are 1:10～40.
Described in a claim 7 tellurium metal/composite material in the application of preparing in arsenic ion electrochemical detection electrode, the method that it is characterized in that described arsenic ion electrochemical detection electrode detection arsenic ion is: taking arsenic ion electrochemical detection electrode as working electrode, taking silver-silver chloride as contrast electrode, taking platinum as to electrode, taking the hydrochloride solution of arsenic as electrolytic solution, at voltage-0.3V～-0.5V, under 100～120 seconds time condition, carry out preenrichment reaction, then at scanning voltage-0.5V～0.3V, 4 millivolts of current potential increments, 20 millivolts of amplitudes, 40 hertz of frequencies, time of repose adopts square wave stripping voltammetry to detect arsenic ion for 2 seconds under condition.
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