CN108682868A - A kind of preparation method and application of carbon nanotube loaded transition metal oxide material - Google Patents
A kind of preparation method and application of carbon nanotube loaded transition metal oxide material Download PDFInfo
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- CN108682868A CN108682868A CN201810233327.1A CN201810233327A CN108682868A CN 108682868 A CN108682868 A CN 108682868A CN 201810233327 A CN201810233327 A CN 201810233327A CN 108682868 A CN108682868 A CN 108682868A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
Abstract
A kind of preparation method and application of carbon nanotube loaded transition metal oxide material.First CNTs annealing process is handled, then dissolving, ultrasound, suction filtration film forming, cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, manganese chloride, ammonium fluoride, urea, cetyl trimethylammonium bromide are dissolved in 80ml deionized waters again, wherein cabaltous nitrate hexahydrate 1.74g, Nickelous nitrate hexahydrate 0.436g, the molar ratio of cabaltous nitrate hexahydrate and manganese chloride between 0.05 0.4, cabaltous nitrate hexahydrate, ammonium fluoride, urea and cetyl trimethylammonium bromide molar ratio be 6:9:20:4.The solution of formation and carbon nanotube are transferred to reaction kettle, carbon nanotube loaded transition metal oxide material is prepared under hydro-thermal method.Preparation process of the present invention is simply at low cost, and material structure uniformity is good, large specific surface area, excellent electrochemical performance, overcomes the shortcomings that noble metal catalyst is of high cost, preparation process is complicated and industrialization difficult to realize.
Description
Technical field
The present invention relates to a kind of preparation method and applications of carbon nanotube loaded transition metal oxide material, and in particular to
Material chemistry technical field.Oxygen reduction catalyst for making metal-air battery.
Background technology
It is well known that energy crisis caused by fossil fuel exhaustive exploitation, resource exhaustion, and using these fuel to ring
Border pollute and health caused by endanger, be the Tough questions that today's society faces, thus caused by high power and
The renewable green energy resource of high-energy density and the demand of energy storage device constantly increase, and have quickly pushed electrochemical energy storage device
Development.In recent years, metal-air battery due to operational risk it is small, discharge is low, and transport capacity is strong, and energy density is high, light-weight,
The feature of environmental protection is good and is concerned.They are just showing unprecedented huge glamour in the modern life.
Zinc-air battery（ZAB）Be it is a kind of it is novel have efficiently and the fuel cell of clean energy resource, ZAB is with higher
Theoretical energy density（〜2500Wh·kg-1）, the advantages of about six times of lithium ion, ZAB includes stable discharge voltage, peace
Complete and environmental-friendly, good shelf-life and at low cost.In addition, ZAB has high volume energy density.It is large-scale and high-power
ZAB is being developed for portable and electrical source of power, such as bicycle, automobile and bus.And zinc is a kind of fabulous sun
Pole material has unique attribute, including low equilibrium potential, electrochemical reversibility, the stability in aqueous electrolyte, high ratio
It energy, high volume energy density, low cost, hypotoxicity and is easily handled.However, air cathode oxygen reduction reaction（ORR）Power
It learns Retarder theory and has become the most important factor for hindering ZAB development, and 10 times slower than the oxygen evolution reaction rate of anode of cathode ORR
Left and right, this makes ORR become the key factor of limitation battery overall performance.Therefore, new and effective, inexpensive ORR elctro-catalysts
Development have become accelerate ZAB practical applications key.
So far, it is known that platinum（Pt）Sill is the best elctro-catalyst of ORR.Kim et al. passes through chemical method（Kim.
KW, Kim. SM, Choi. S, Kim. J, Lee. IS, Electroless Pt deposition on Mn3O4
nanoparticles via the galvanic replacement process: electrocatalytic
nanocomposite with enhanced performance for oxygen reduction reaction[J]. Acs
Nano. 2012,6(6):5122-5129.）In Mn3O4Pt is deposited on nano particle, realizes the purpose of enhancing oxygen reduction reaction.It is logical
It crosses electrochemical displacement process and Mn is steadily fixed on evenly dispersed state by highdensity ultra-fine Pt is nanocrystalline3O4Nanometer
The rate of proton exchange membrane, obtained Pt/Mn are improved in oxygen reduction reaction in grain surface3O4Nanocomposite is shown
Go out high electro-chemical activity and stability, chemical property, due to the presence of Pt, makes close to even more than business Pt/C
Obtain the high expensive of material.
Jin et al. uses two one-step hydrothermals（Jin. GH, et al, Co3O4 nanoparticles-modified
alpha-MnO2 nanorods supported on reduced graphene oxide as cathode catalyst
for oxygen reduction reaction in alkaline media [J]. Nanosale.2016, 11(11):
1650126.）It has been synthesized under alkaline condition with Co3O4-MnO2/ RGO（RGO：Redox graphene）It is as main component
Co3O4Nano-particle modified α-MnO2（α phase manganese dioxide）Nanometer rods, as the ORR catalyst of high activity, but the height of RGO
The precision manufactureing of cost and low yield and RGO seriously hinder large-scale production and the practical application of its catalysis material.Therefore,
There is an urgent need to develop low cost, method simple for process and expansible produces the efficient ORR catalyst for practical application.
Invention content
The invention discloses a kind of preparation method and application of carbon nanotube loaded transition metal oxide material, transition gold
The combination for belonging to oxide and CNTs makes electrocatalysis characteristic be greatly improved；Material obtained has high intensity, high tenacity, knot
The advantages that brilliant degree is high, pattern is uniform and large specific surface area.Preparation process of the present invention is simple, it is at low cost, reproducible, to environment without
Harm, and can realize industrialization, effectively overcome existing preparation method complex process, the shortcomings of cost is higher.
The technical scheme is that be achieved：
A kind of preparation method of carbon nanotube loaded transition metal oxide material, first, by carbon nanotube（CNTs）Lehr attendant
Skill processing, then, dissolving, is filtered into carbon film ultrasound；Again by cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, manganese chloride, ammonium fluoride,
Urea, cetyl trimethylammonium bromide are dissolved in 80ml deionized waters, and the homogeneous solution of formation and carbon film are transferred to reaction
In kettle, under hydro-thermal method, carbon nanotube loaded transition metal oxide material is prepared, specific preparation method is as follows：
1）CNTs is made annealing treatment, then, dissolving, is filtered into carbon film ultrasound；
2）Cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, ammonium fluoride, urea are dissolved in deionized water, formed under magnetic stirring
Pink solution；
3）Manganese chloride is added in above-mentioned pink solution, continuing magnetic force stirring；
4）Cetyl trimethylammonium bromide is added to step 3）In prepared solution, magnetic agitation to solution becomes pink colour
Liquid；
5）By step 1）Gained carbon film and step 4）Gained pink colour liquid, which is transferred in reaction kettle, carries out hydrothermal synthesis reaction, reaction
Kettle temperature degree is between 120 DEG C -180 DEG C, and the reaction time is between 3-14h；
6）By step 5）Products obtained therefrom takes out from reaction kettle, is washed with deionized after naturally cooling to room temperature, obtains carbon film
The grayish purple solid of upper load；
7）By step 6）The grayish purple solid of gained is placed in drying in vacuum drying chamber, and vacuum drying chamber temperature is 60 DEG C, dry
12 hours time；Then it is made annealing treatment, 300 DEG C -400 DEG C of annealing temperature, is made annealing treatment 2 hours, 3 DEG C of heating rate/
Min obtains carbon nanotube loaded transition metal oxide material.
Step 1）500 DEG C, time 30min, 3 DEG C/min of heating rate of the annealing temperature of CNTs, carbon nanotube ultrasonic power
225W, ultrasonic time 30min.
Various added materials：Cabaltous nitrate hexahydrate 1.74g, Nickelous nitrate hexahydrate 0.436g, cabaltous nitrate hexahydrate and chlorination
The molar ratio of manganese between 0.05-0.4, cabaltous nitrate hexahydrate, ammonium fluoride, urea and cetyl trimethylammonium bromide mole
Than being 6:9:20:4, deionized water 80ml, carbon nanotube 6mg.
Carbon nanotube loaded transition metal oxide material prepared by the present invention is used for the hydrogen reduction of zinc-air battery cathode
Catalyst.
The advantage of the invention is that：
（1）Using hydro-thermal method technique, transition metal oxide and CNTs are combined, material obtained have high intensity, high tenacity,
Not only crystallinity is high, pattern is uniform and large specific surface area so that electrocatalysis characteristic is greatly improved.
（2）Preparation process of the present invention is simple, of low cost, reproducible, non-hazardous to environment, and can realize industrialization,
It is slow effectively to overcome prior art cathode ORR oxygen evolution reaction rates, complex process, the shortcomings of cost is higher.
Description of the drawings
Fig. 1：（a）The SEM of the CNTs carrying transition metal oxide materials for the Mn element dopings that embodiment 1 is prepared；
（b）The SEM for the CNTs carrying transition metal oxide materials without Mn element dopings that comparative example is prepared schemes；
Fig. 2：The XRD spectrum for the CNTs carrying transition metal oxide materials that embodiment 1 and comparative example are prepared；
Fig. 3：（a）、（b）The ratio for the CNTs carrying transition metal oxide materials that respectively embodiment 1 and comparative example are prepared
Surface area and graph of pore diameter distribution；
The XPS of the CNTs carrying transition metal oxide materials for the Mn element dopings that Fig. 4 embodiments 1 are prepared（X-ray photoelectricity
Sub- energy spectrum analysis）Collection of illustrative plates；
The hydrogen reduction test analysis for the CNTs carrying transition metal oxide materials that Fig. 5 embodiments 1 and comparative example are prepared；
The sample hydrogen reduction test of different cobalt manganese molar ratios prepared by Fig. 6 embodiments 2.
Specific implementation mode
It in order to better understand the present invention, below will the present invention will be described in detail by specific embodiment.
【Comparative example】
The preparation process of CNTs carrying transition metal oxide materials without Mn element dopings is as follows：
（1）CNTs is made annealing treatment, 500 DEG C, time 30min, 3 DEG C/min of heating rate of the annealing temperature of carbon nanotube,
Then, dissolving, ultrasound, suction filtration film forming, carbon nanotube ultrasonic power 225W, ultrasonic time 30min（Purpose：CNTs is evenly dispersed
In the solution）, filter the round carbon film that carbon film is cut into a diameter of 12mm, weight about 1.2 ± 0.05mg.
（2）1.74g cabaltous nitrate hexahydrates, 0.436g Nickelous nitrate hexahydrates, 0.37g ammonium fluorides, 1.2g urea are dissolved in
In 80ml deionized waters, pink solution is formed under magnetic stirring；
（3）1.422g cetyl trimethylammonium bromides are added to step 2）In prepared pink solution, magnetic agitation
Become pink colour liquid to solution；
（4）By step 1）Gained carbon nanotube and step 3）Gained liquid, which is transferred in reaction kettle, carries out hydrothermal synthesis reaction,
At 160 DEG C, 12 hours are kept the temperature, then cooled to room temperature.
（5）By step 4）Products obtained therefrom takes out from reaction kettle, is washed with deionized and dries（60 DEG C of vacuum drying 12
Hour）, obtain the grayish purple solid loaded in carbon nanotube
（6）By step 5）Obtained solid carries out annealing 2 hours at 350 DEG C, and 3 DEG C/min of heating rate obtains black
CNTs carrying transition metal oxide materials, as a contrast.
【Embodiment 1】
The preparation process of CNTs carrying transition metal oxide materials containing Mn element dopings is as follows：
（1）CNTs is made annealing treatment, 500 DEG C, time 30min, 3 DEG C/min of heating rate of the annealing temperature of carbon nanotube,
Then, dissolving, ultrasound, suction filtration film forming, carbon nanotube ultrasonic power 225W, ultrasonic time 30min（Purpose：CNTs is evenly dispersed
In the solution）, filter the round carbon film that carbon film is cut into a diameter of 12mm, weight about 1.2 ± 0.05mg.
（2）1.74g cabaltous nitrate hexahydrates, 0.436g Nickelous nitrate hexahydrates, 0.37g ammonium fluorides, 1.2g urea are dissolved in
In 80ml deionized waters, pink solution is formed under magnetic stirring；
（3）By 0.151g manganese chlorides（The molar ratio of cabaltous nitrate hexahydrate and manganese chloride is 1 at this time：0.2）Step 2 is added）In, magnetic
Power stirring makes it fully dissolve, and solution colour becomes dark pink.
（4）1.422g cetyl trimethylammonium bromides are added to step 3）In prepared dark pink solution, magnetic
Power, which is stirred to solution, becomes pink colour liquid；
（5）By step 1）Gained carbon film and step 4）Gained liquid, which is transferred in reaction kettle, carries out hydrothermal synthesis reaction, at 160 DEG C
Under, 12 hours are kept the temperature, then cooled to room temperature.
（6）By step 5）Products obtained therefrom takes out from reaction kettle, is washed with deionized and dries（60 DEG C of vacuum drying 12
Hour）, obtain the puce solid loaded in carbon nanotube
（7）By step 6）Obtained solid carries out annealing 2 hours at 350 DEG C, and 3 DEG C/min of heating rate obtains black
CNTs loads the transition metal oxide material containing additive Mn.
【Embodiment 2】
The preparation process of CNTs carrying transition metal oxide materials containing different proportion Mn element dopings is as follows：
（1）CNTs is made annealing treatment, 500 DEG C, time 30min, 3 DEG C/min of heating rate of the annealing temperature of carbon nanotube,
Then, dissolving, ultrasound, suction filtration film forming, carbon nanotube ultrasonic power 225W, ultrasonic time 30min（Purpose：CNTs is evenly dispersed
In the solution）, filter the round carbon film that carbon film is cut into a diameter of 12mm, weight about 1.2 ± 0.05mg.
（2）1.74g cabaltous nitrate hexahydrates, 0.436g Nickelous nitrate hexahydrates, 0.37g ammonium fluorides, 1.2g urea are dissolved in
In 80ml deionized waters, pink solution is formed under magnetic stirring.
（3）By manganese chloride（The molar ratio of cabaltous nitrate hexahydrate and manganese chloride is respectively at this time：1：0.5、1：0.1、1：0.4）
Step 2 is added）In, magnetic agitation makes it fully dissolve, and solution colour becomes dark pink.
（4）1.422g cetyl trimethylammonium bromides are added to step 3）In prepared pink solution, magnetic force
Stirring to solution becomes pink colour liquid.
（5）By step 1）Gained carbon film and step 4）Gained liquid, which is transferred in reaction kettle, carries out hydrothermal synthesis reaction,
At 160 DEG C, 12 hours are kept the temperature, then cooled to room temperature.
（6）By step 5）Products obtained therefrom takes out from reaction kettle, is washed with deionized and dries（60 DEG C of vacuum drying 12
Hour）, obtain the puce solid loaded in carbon nanotube
（7）By step 6）Obtained solid carries out annealing 2 hours at 350 DEG C, and 3 DEG C/min of heating rate obtains black
CNTs loads the transition metal oxide material of different proportion additive Mn.
The pattern for the CNTs carrying transition metal oxides that the embodiment of the present invention 1 and comparative example are prepared is respectively such as Fig. 1
（a）With（b）It is shown, Fig. 1（a）It is middle to there is linear and spherical two kinds of structures, and favorable dispersibility, the average diameter of linear structure are
The average diameter of 150nm, chondritic are 1.69 μm, which is conducive to the same O of air cathode2Come into full contact with and promote electronics,
The transmission of ion improves electrocatalysis characteristic；Fig. 1（b）In predominantly bowknot shape nanometer linear structure, nanometer linear structure
Average diameter is 230nm.The X-ray diffractogram of embodiment 1 and comparative example is as shown in Fig. 2, what it can be seen from the figure that CNTs was loaded
Transition metal oxide belongs to spinel structure, and in the peaks XRD of embodiment 1 and comparative example the peak without NiO, but the peaks XRD and mark
Quasi- PDF#74-2120-Co3O4~ 0.1 ° of offset, this is that the addition of Ni elements makes XRD shift, the peaks XRD in embodiment 1
Corresponding PDF#74-2120-Co3O4And PDF#71-0635-Mn2O3, a little change occurs for the structure of crystal after Mn elements are added,
The result peak value display of XRD tests deviates to the left.Fig. 3（a）、(b）Respectively illustrate the specific surface integral of embodiment 1 and comparative example
It Wei not 92.24 and 64.47 m2 g-1, the raising of specific surface area can promote catalyst with the contact of oxygen, improve chemical property.
The results are shown in Figure 4 for the XPS analysis for the CNTs carrying transition metal oxides that embodiment 1 is prepared, and shows it includes Co,
Five kinds of elements of Ni, Mn, O and C.It is hydrogen reduction below（ORR）The test of performance, Fig. 5 are embodiment 1, Pt/C and comparative example
The rotating speed of ORR performance tests, disk electrode is 1600rpm, and sweep speed is 10mV s-1, load 0.33mg cm-2, wherein
（a）The limiting current density of middle embodiment 1（5.98mA cm-2 ）>Comparative example (4.42 mA cm-2), and close to the ORR of Pt/C
Performance（6.05mA cm-2）, figure（b）The ORR performance tests for being embodiment 1 under different rotating speeds, illustration are lower to be calculated by K-L
Electron transfer number of the gained in different voltages（~4.0）.Fig. 6 is the ORR performance tests of different cobalt manganese ratio samples in embodiment 2,
Disk electrode rotating speed 1600rpm, sweep speed are 10mV s-1, load 0.33mg cm-2, wherein Co/Mn (1:0.1)(5.76
mA cm-2)> Co/Mn(1:0.4) (5.63 mA cm-2)> Co/Mn(1:0.05) (5.25 mA cm-2), show material
The doping ratio of ORR performances and Mn have prodigious relationship.To sum up, ORR of the ORR performances of embodiment 1 compared with comparative example and embodiment 2
Performance is high, and ORR performances are substantially equal to the performance of the ORR of Pt/C, so CNTs loads mole prepared by the embodiment of the present invention 1
Than for Co/Mn (1:0.2) catalyst of transition metal oxide has prodigious researching value and market application potential.
Claims (5)
1. a kind of preparation method of carbon nanotube loaded transition metal oxide material, it is characterised in that：CNTs is annealed first
Process, then dissolving, ultrasound, filter film forming, then by cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, manganese chloride, ammonium fluoride,
Urea, cetyl trimethylammonium bromide are dissolved in 80ml deionized waters, and the homogeneous solution of formation and carbon film are transferred to reaction
In kettle, under hydro-thermal method, carbon nanotube loaded transition metal oxide material is prepared, specific preparation method is as follows：
1）CNTs is made annealing treatment, then carbon film is cut into a diameter of 12mm, weight by dissolving, ultrasound, suction filtration at carbon film
The round carbon nanotube of 1.2 ± 0.05mg；
2）Cabaltous nitrate hexahydrate, Nickelous nitrate hexahydrate, ammonium fluoride, urea are dissolved in deionized water, formed under magnetic stirring
Pink solution；
3）Manganese chloride is added to step 2）In the solution of preparation, continuing magnetic force stirring；
4）Cetyl trimethylammonium bromide is added to step 3）In prepared pink solution, magnetic agitation to solution becomes
For pink colour liquid；
5）The cabaltous nitrate hexahydrate 1.74g of the addition, Nickelous nitrate hexahydrate 0.436g, cabaltous nitrate hexahydrate and manganese chloride rub
Your ratio between 0.05-0.4, cabaltous nitrate hexahydrate, ammonium fluoride, urea and cetyl trimethylammonium bromide molar ratio be 6:
9:20:4, deionized water 80ml, carbon nanotube 6mg；
6）By step 1）Gained carbon nanotube and step 4）It is anti-that the pink colour liquid of gained is transferred to progress hydrothermal synthesis in reaction kettle
It answers；
7）By step 6）Products obtained therefrom takes out from reaction kettle, is washed with deionized after naturally cooling to room temperature, obtains carbon film
The grayish purple solid of upper load；
8）By step 7）Obtained solid is placed in drying in vacuum drying chamber, is then made annealing treatment, is obtained carbon nanotube loaded
The nano wire of transition metal oxide and the composite construction of nanosphere, size uniformity, stable appearance and controllability are strong.
2. a kind of preparation method of carbon nanotube loaded transition metal oxide material according to claim 1, feature
It is：Step 1）500 DEG C, time 30min, 3 DEG C/min of heating rate of the annealing temperature of CNTs, carbon nanotube ultrasonic power
225W, ultrasonic time 30min.
3. a kind of preparation method of carbon nanotube loaded transition metal oxide material according to claim 1, feature
It is：Step 6）Described in temperature of reaction kettle range between 120-180 DEG C, the reaction time be 3-14 hours, hydro-thermal is anti-
Temperature is answered to influence the structure of product and chemical property.
4. a kind of preparation method of carbon nanotube loaded transition metal oxide material according to claim 1, feature
It is, step 8）Described in vacuum drying chamber temperature be 60 DEG C, drying time 12-15 hour；The annealing temperature 300-
It 400 DEG C, makes annealing treatment 2 hours, 3 DEG C/min of heating rate.
5. a kind of application of carbon nanotube loaded transition metal oxide material according to claim 1, which is characterized in that
The carbon nanotube loaded transition metal oxide material being prepared is used for the oxygen reduction catalyst of zinc-air battery cathode.
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| CN109786766A (en) * | 2018-12-27 | 2019-05-21 | 上海理工大学 | A kind of preparation method of porous carbon carrying transition metal oxide composite |
| CN110201695A (en) * | 2019-03-29 | 2019-09-06 | 上海理工大学 | A kind of preparation method of porous carbon materials carrying transition metal Fe, Co composite material |
| CN110508308A (en) * | 2019-08-13 | 2019-11-29 | 三峡大学 | A kind of preparation method and application of CoMn-P-NCNT multifunction catalyst |
| CN110514700A (en) * | 2019-09-27 | 2019-11-29 | 西安电子科技大学 | A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method |
| CN110743553A (en) * | 2019-10-10 | 2020-02-04 | 天津大学 | Preparation of metal element doped metal oxide ORR catalyst |
| CN113201746A (en) * | 2021-03-26 | 2021-08-03 | 广州费舍尔人工智能技术有限公司 | Fluorine modified nickel cobaltate modified carbon nanotube electrode catalyst |
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| CN113201746A (en) * | 2021-03-26 | 2021-08-03 | 广州费舍尔人工智能技术有限公司 | Fluorine modified nickel cobaltate modified carbon nanotube electrode catalyst |
| CN113913855A (en) * | 2021-06-30 | 2022-01-11 | 海信（山东）冰箱有限公司 | High-efficiency ethylene-removing electro-catalytic module and preparation method and application thereof |
| CN114890851A (en) * | 2022-05-26 | 2022-08-12 | 陕西师范大学 | Nano composite burning rate catalyst with carbon nano tube embedded transition metal compound |
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