CN105529474A - Graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst and preparation method thereof - Google Patents
Graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electro-catalysis hydrogen production, and particularly relates to a graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst and a preparation method thereof. The catalyst comprises 1-10 layers of graphene wrapped ultra-dispersed nano MoC (1-20 nano), and has very large specific surface area (100-300m2/g) and rich dual hole structure (3-4 and 20-500 nano). The preparation method comprises following step of with Mo3(BTC)2 as a hybridization precursor, carbonizing at 500-1000DEG C under the protection of argon so as to prepare the graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst, wherein the temperature rising rate of the carbonization is controlled at 1-80 DEG C per minute, and the carbonization time is 0.5-24 hours. The catalyst has very high electro-catalysis hydrogen producing activity and stability under the acid condition and the alkaline condition. The raw material used in preparation is cheap, the preparation method is mature and stable, is simple to operate, has high controllability, and is applicable to large scale production and hydrogen production through water electrolysis in industry.
Description
Technical field
The invention belongs to electro-catalysis hydrogen producing technology field, be specifically related to super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of a kind of Graphene parcel and preparation method thereof.
Background technology
Along with continuing to increase and social development constantly progress of world population, the demand of the mankind to the energy grows with each passing day.Nowadays, along with petering out of the traditional fossil energy such as oil, coal and going from bad to worse of environmental problem, traditional " the energy resource structure system based on fossil energy " is faced with unprecedented challenge and crisis.The highest energy density that hydrogen has, excellent to have good burning performance, green energy resource that the best that the advantage such as cleanliness without any pollution makes it to become traditional fossil energy is alternative.But, the development of hydrogen producing technology technique is depended in the utilization of Hydrogen Energy to a great extent, current industrial hydrogen production technique is Effect of Catalysis In Petrochemistry cracking and natural gas steam reformation hydrogen production mainly, and this technique is considered from the angle of environment and total energy approach and do not meet the energy development strategy of now current " Green Sustainable ".In recent years, along with the development of new-generation technology (as solar power generation, wind power generation, nuclear energy power generation, hydroelectric power generation, geothermal power generation etc.) and continuing to optimize and upgrading of network system, the advantage of water electrolysis hydrogen production technology is constantly amplified, even be described as " optimal Process of Hydrogen Production " by many scientists and enterprisers, and the most crucial problem of this technology is the exploitation of efficient, stable, honest hydrogen manufacturing eelctro-catalyst.
At present, the most effective eelctro-catalyst of electro-catalysis process for making hydrogen is platinum based catalyst, because such catalyst has minimum overpotential and very high stability in water electrolysis hydrogen production process.But the fancy price of platinum and low memory space seriously constrain the extensive use of such catalyst in water electrolysis hydrogen production and the tremendous development of this process for making hydrogen.Therefore, look for cheapness, replaceable high activity electro-catalysis catalyst for preparing hydrogen is the key problem developing this process for making hydrogen.Current research shows, early transition metal carbide shows higher catalytic activity and stability in electro-catalysis hydrogen production reaction.Wherein, molybdenum carbide (MoC
x) be one of alternative catalyst of the best be widely studied in recent years.But the multiple synthetic method that present stage is reported all has certain limitation, molybdenum carbide (MoC
x) building-up process all inevitably use high temperature (~ 900 DEG C), molybdenum carbide (MoC in building-up process can be caused
x) sintering of particle and reunion, be difficult to the Superfine powder structure realizing high uniformity dispersion; In addition, high synthesis temperature can cause subsiding of the pore structure of catalyst, makes this catalyst generally have less specific area (<50m
2/ g).Above-mentioned technical bottleneck seriously constrains molybdenum carbide (MoC
x) exposure of catalyst active sites in electro-catalysis hydrogen production process and the diffusion of product and reactant, have impact on activation plays and the extensive use of such eelctro-catalyst largely.
Summary of the invention
An object of the present invention is to provide the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of a kind of Graphene parcel.These catalyst raw material wide material sources, with low cost, and high electro-catalysis hydrogen production activity and stability is all shown under acid and alkali condition, the platinum based catalyst that present stage use is the widest can be replaced.
Two of object of the present invention is to provide the preparation method of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of above-mentioned Graphene parcel.The clear novelty of the method mentality of designing, mature preparation process is stable, simple to operate, controllability strong, is applicable to large-scale production.
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of Graphene parcel provided by the invention, by Mo
3(BTC)
2(Mo-MOFs) super-dispersed nano molybdenum carbide (MoC) (its particle diameter the is 1 ~ 20nm) composition of hydridization presoma 1 ~ 10 layer graphene parcel of generation in place in high temperature cabonization process, and there is very large specific area (100 ~ 300m
2/ g) and abundant double-pore structure (being respectively 3 ~ 4nm and 20 ~ 500nm); Prepared by following preparation method.
The preparation method of above-mentioned electro-catalysis catalyst for preparing hydrogen provided by the invention, concrete steps are:
Adopt Mo
3(BTC)
2(Mo-MOFs) be hydridization presoma; Under argon shield, above-mentioned hydridization presoma is warming up to 500 ~ 1000 DEG C, it is 1 ~ 80 DEG C/min that heating rate controls; Carbonization 0.5 ~ 24 hour at this temperature, i.e. the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
Wherein, carburizing temperature is preferably 700 DEG C ~ 900 DEG C, and heating rate is preferably 5 ~ 10 DEG C/min, and carbonization time is preferably 3 ~ 5 hours.
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of prepared Graphene parcel, can be used for the water electrolysis hydrogen production reaction under acidity and alkali condition, but does not limit this catalyst for other catalytic hydrogenations of catalysis and hydrogenolysis.
Know-why of the present invention is: utilize Mo
3(BTC)
2(Mo-MOFs) organic ligand abundant in " atomic level contact " in hydridization presoma between Mo atom and trimesic acid part and Mo-MOFs presoma and porosity, overcome the reunion in MoC activated centre in high―temperature nuclei process and subsiding of pore structure, the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of prepared above-mentioned Graphene parcel is made to have very distinct structure feature and advantage: super-dispersed nano MoC(1 ~ 20 nanometer of being wrapped up by 1 ~ 10 layer graphene) form, and there is very large specific area (100 ~ 300m simultaneously
2/ g) and abundant double-pore structure (3 ~ 4 and 20 ~ 500 nanometer).The nanometer MoC that oversubscription in this catalyst composition is loose can fully expose its catalytic active site; Graphene shell effectively can improve the conductivity of eelctro-catalyst, accelerates charge transfer rate in electrochemical process; The porosity that Large ratio surface sum is enriched is conducive to the hydrogen of generation and electrolytical diffusion, reduces the resistance to mass tranfer in electro-catalysis process.Above structure feature makes this catalyst all show high electro-catalysis hydrogen production activity and stability under acidity and alkali condition.
The present invention compared with prior art has following beneficial effect:
1, the present invention makes full use of Mo
3(BTC)
2(Mo-MOFs) organic ligand abundant in " atomic level contact " in hydridization presoma between Mo atom and trimesic acid part and Mo-MOFs presoma and porosity, overcome the reunion in MoC activated centre in high―temperature nuclei process and subsiding of pore structure, make super-dispersed nano MoC(1 ~ 20nm that the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of prepared above-mentioned Graphene parcel is wrapped up by 1 ~ 10 layer graphene) form, and there is very large specific area (100 ~ 300m simultaneously
2/ g) and abundant double-pore structure (3 ~ 4nm and 20 ~ 500nm).The MoC eelctro-catalyst that the method prepares is no matter from particle diameter and the dispersiveness in catalyst self structure and porosity and obtained MoC activated centre, and preparation method has advantage clearly all than ever;
2, the super-dispersed nano molybdenum carbide particles that the Graphene that prepared by the present invention wraps up assembles the electro-catalysis catalyst for preparing hydrogen of formation again, utilize its super-dispersed nano structure, Graphene shell and enrich the cooperative effect of porosity, greatly reduce the overpotential of this catalyst in water electrolysis hydrogen production reaction, drastically increase electro-catalysis hydrogen production activity and stability;
3, the present invention is by " Mo
3(BTC)
2(Mo-MOFs) high temperature cabonization method " the electro-catalysis catalyst for preparing hydrogen of super-dispersed nano molybdenum carbide of above-mentioned Graphene parcel can be prepared.The raw material sources of this preparation method is abundant, low price, and technical maturity is stable, simple to operate, controllability strong, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the pie graph of the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of Graphene parcel.Wherein, (a) is scanning electron microscope (SEM) photograph, and the domain size distribution that (b) is transmission electron microscope picture and MoC, (c) is transmission electron microscope picture, and (d) is high-resolution-ration transmission electric-lens figure.
Fig. 2 is the proterties figure of the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of Graphene parcel.Wherein, left figure is nitrogen adsorption desorption curve, and right figure is pore size distribution curve.
Fig. 3 is the polarization curve of the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of Graphene parcel.Wherein, left figure is at 0.5mol/LH
2sO
4polarization curve in electrolyte (acidity), right figure is the polarization curve in 1.0mol/LKOH electrolyte (alkalescence).
Fig. 4 is that the electro-catalysis catalyst for preparing hydrogen of the super-dispersed nano molybdenum carbide of described Graphene parcel is at 0.5mol/LH
2sO
4the polarization curve of circulation 3000 front and back in electrolyte.
Embodiment
Below by specific embodiment, the present invention is set forth further, but do not limit the present invention.
embodiment 1,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 700 DEG C carbonization 5 hours, heating rate controls at 5 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.Form as shown in Figure 1: prepared electro-catalysis catalyst for preparing hydrogen is by the super-dispersed nano MoC(~ 3nm wrapped up by 1 ~ 3 layer graphene); As shown in Figure 2: this catalyst has very large specific area (187m
2/ g) and abundant double-pore structure (3 ~ 4nm and 20 ~ 300nm).
The super-dispersed nano molybdenum carbide electricity of obtained Graphene parcel urges the electro-chemical test of catalyst for preparing hydrogen to carry out according to the following steps:
The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of a Graphene parcel that () takes described in 15mg is dispersed in the mixed solution of deionized water, the absolute ethyl alcohol of 250 μ L and the Nafion solution (5%) of 80 μ L including 750 μ L, and ultrasonic 1 hour to form uniform suspension.Then get the above-mentioned hanging drop of 4 μ L to be coated onto on the glass-carbon electrode (GC) that diameter is 3mm, natural drying can prepare work electrode;
The electrochemistry hydrogen manufacturing performance test of b work electrode that () prepares all adopts three-electrode system, and electrolyte is respectively the sulfuric acid solution (acidity) of 0.5mol/L and the potassium hydroxide solution (alkalescence) of 1mol/L.Be graphite rod to electrode; reference electrode is saturated calomel electrode (Saturatedcalomelelectrode; SCE); linear sweep voltammetry curve is at electrochemical workstation (CHI660E; Shanghai Hua Chen instrument company) on carry out, probe temperature is room temperature, and sweep speed is 5mV/s; sweep limits is 0.1 to-0.6V, and experimental data all carries out iR correction.Electrode potential is obtained by contrast saturated calomel electrode, and is converted into the electrode potential relative to reversible hydrogen electrode (Reversiblehydrogenelectrode, RHE), and conversion equation is as follows: E
rHE=E
sCE+ 0.059pH+0.241.
As shown in Figure 3, this eelctro-catalyst all shows high hydrogen evolution activity under acidity and alkali condition, and current density is-10mA/cm
2condition under overpotential be respectively 132 and 77mV; As shown in Figure 4, this eelctro-catalyst shows high liberation of hydrogen stability in acidity, after 3000 circulations, does not observe obvious activity decrease.
embodiment 2,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 800 DEG C carbonization 5 hours, heating rate controls at 5 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 159mV.
embodiment 3,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 900 DEG C carbonization 5 hours, heating rate controls at 5 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 185mV.
embodiment 4,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 700 DEG C carbonization 3 hours, heating rate controls at 10 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 144mV.
embodiment 5,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 800 DEG C carbonization 3 hours, heating rate controls at 10 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 164mV.
embodiment 6,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 900 DEG C carbonization 3 hours, heating rate controls at 10 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 200mV.
embodiment 7,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 600 DEG C carbonization 5 hours, heating rate controls at 5 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 117mV.
embodiment 8,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 1000 DEG C carbonization 5 hours, heating rate controls at 5 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 250mV.
embodiment 9,by Mo
3(BTC)
2(Mo-MOFs), as in tube furnace, under argon shield, temperature programming to 600 DEG C carbonization 5 hours, heating rate controls at 20 DEG C/min, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
The electro-chemical test of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of obtained Graphene parcel is with the step (a) of case study on implementation 1 and (b).
This eelctro-catalyst shows higher hydrogen evolution activity in acidity, and current density is-10mA/cm
2condition under overpotential be 168mV.
In sum, the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen that the Graphene that prepared by the present invention wraps up adopts Mo
3(BTC)
2(Mo-MOFs) as hydridization presoma, can be obtained by high temperature cabonization under argon shield.Its preparation method utilizes Mo
3(BTC)
2(Mo-MOFs) organic ligand abundant in " atomic level contact " in hydridization presoma between Mo atom and trimesic acid part and Mo-MOFs presoma and porosity, overcome the reunion in MoC activated centre in high―temperature nuclei process and subsiding of pore structure, the electro-catalysis catalyst for preparing hydrogen prepared is made to have very distinct structure feature and advantage: the super-dispersed nano MoC(1 ~ 20nm wrapped up by 1 ~ 10 layer graphene) form, and there is very large specific area (100 ~ 300m simultaneously
2/ g) and abundant double-pore structure (3 ~ 4nm and 20 ~ 500nm).This catalyst can expose catalytic active site better, improve the conductivity of eelctro-catalyst to accelerate charge transfer rate in electrochemical process, the hydrogen that acceleration generates and electrolytical diffusion, to reduce the resistance to mass tranfer in electro-catalysis process, all show high electro-catalysis hydrogen production activity and stability under acidity and alkali condition.This preparation method's needed raw material low price, technical maturity is stable, simple to operate, controllability strong, is applicable to large-scale production.
Foregoing be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (6)
1. a super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen for Graphene parcel, is characterized in that:
Described Graphene is Mo
3(BTC)
21 ~ 10 layer graphene of hydridization presoma generation in place in high temperature cabonization process;
The domain size distribution of described super-dispersed nano molybdenum carbide is 1 ~ 20 nanometer, and is wrapped in by above-mentioned Graphene shell;
Its specific area is 100 ~ 300m
2/ g, has abundant double-pore structure, is respectively 3 ~ 4 nanometers and 20 ~ 500 nanometers.
2. the preparation method of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of Graphene parcel as claimed in claim 1, is characterized in that concrete steps are:
Adopt Mo
3(BTC)
2for hydridization presoma; Under argon shield, above-mentioned hydridization presoma is warming up to carburizing temperature 500 ~ 1000 DEG C, it is 1 ~ 80 DEG C/min that heating rate controls; Carbonization 0.5 ~ 24 hour at this temperature, i.e. the nano silicon carbide molybdenum electro-catalysis catalyst for preparing hydrogen of obtained described Graphene parcel.
3. the preparation method of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of Graphene parcel as claimed in claim 2, is characterized in that described carburizing temperature is 700 DEG C ~ 900 DEG C.
4. the preparation method of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of Graphene parcel as claimed in claim 3, is characterized in that described heating rate is 5 ~ 10 DEG C/min.
5. the preparation method of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of Graphene parcel as claimed in claim 4, is characterized in that described carbonization time is 3 ~ 5 hours.
6. the application of the super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen of Graphene parcel as claimed in claim 1 under acid or alkaline conditions in water electrolysis hydrogen production reaction.
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| CN108940328A (en) * | 2018-06-28 | 2018-12-07 | 大连理工大学 | Nanometer sheet-modified molybdenum carbide electro-catalysis catalyst for preparing hydrogen of nanometer rods coupling three-dimensional composite material Ni-Co and preparation method thereof |
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| CN111359647A (en) * | 2020-03-17 | 2020-07-03 | 中国石油大学(北京) | Ultrathin carbon layer coated nitrogen-doped cross-linked hierarchical pore molybdenum carbide material and preparation thereof |
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Cited By (10)
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|---|---|---|---|---|
| CN106058193A (en) * | 2016-07-20 | 2016-10-26 | 华南理工大学 | Novel negative electrode material of sodium-ion battery as well as preparation method and application thereof |
| CN106637288A (en) * | 2016-12-27 | 2017-05-10 | 复旦大学 | Nitrogen-doped graphite-loaded phosphorus-doped molybdenum carbide nanowire electrocatalytic hydrogen production catalyst and preparation method thereof |
| CN108940328A (en) * | 2018-06-28 | 2018-12-07 | 大连理工大学 | Nanometer sheet-modified molybdenum carbide electro-catalysis catalyst for preparing hydrogen of nanometer rods coupling three-dimensional composite material Ni-Co and preparation method thereof |
| CN108940328B (en) * | 2018-06-28 | 2020-02-18 | 大连理工大学 | Nano sheet-nano rod coupled three-dimensional composite material Ni-Co modified molybdenum carbide electro-catalysis hydrogen production catalyst and preparation method thereof |
| CN109136973A (en) * | 2018-08-28 | 2019-01-04 | 南京工业大学 | A kind of base metal doping molybdenum carbide hydrogen-precipitating electrode and its preparation method and application |
| CN109136973B (en) * | 2018-08-28 | 2020-07-14 | 南京工业大学 | Non-noble metal doped molybdenum carbide hydrogen evolution electrode and preparation method and application thereof |
| CN111359647A (en) * | 2020-03-17 | 2020-07-03 | 中国石油大学(北京) | Ultrathin carbon layer coated nitrogen-doped cross-linked hierarchical pore molybdenum carbide material and preparation thereof |
| CN111359647B (en) * | 2020-03-17 | 2021-02-23 | 中国石油大学(北京) | Ultrathin carbon layer coated nitrogen-doped cross-linked hierarchical pore molybdenum carbide material and preparation thereof |
| CN111905783A (en) * | 2020-06-29 | 2020-11-10 | 复旦大学 | Molybdenum carbide/carbon nano hydrogen production catalyst synthesized by using ink |
| CN111905783B (en) * | 2020-06-29 | 2021-10-26 | 复旦大学 | Molybdenum carbide/carbon nano hydrogen production catalyst synthesized by using ink |
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