CN113089017B - Metal bismuth nanoparticle composite material and preparation method and application thereof - Google Patents
Metal bismuth nanoparticle composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a supported metal bismuth particle composite material, wherein metal bismuth particles are supported on a porous carbon carrier through a coupling agent with amino groups, and the particle size of the metal bismuth particles is 5-30nm. The invention is prepared by loading tetraaminophenyl porphyrin molecules on porous carbon to form a modified porous carbon composite material through simple two-step impregnation adsorption, and then carrying out second-step impregnation adsorption on the modified porous carbon composite material and bismuth metal salt under the condition of sodium borohydride reduction. The bismuth metal nano particles are fixed on the porous carbon carrier in a strong combination mode due to the domain-limiting effect of the porous carbon and the special stabilizing effect of the molecular coupling agent, the loading capacity is high, the activity is high, the molecular coupling agent plays a role in reinforcing the interaction between the metal bismuth nano particles and the carrier, and the structure of the molecular coupling agent cannot be changed under the reducing condition. The supported metal bismuth particle composite material provided by the invention has excellent catalytic activity and stability when used for preparing formic acid by carbon dioxide epoxy, and has obvious advantages in industry.
Description
Technical Field
The invention belongs to the field of inorganic composite material catalysts, and particularly relates to a metal bismuth nanoparticle composite material and a preparation method and application thereof.
Background
In order to advance the current human society, the carbon dioxide concentration in the atmosphere is increasing due to the large amount of mining and consumption of fossil fuels, and the increasing activity of human beings causes the carbon dioxide concentration to exceed the safety upper limit (350 ppm) early, which causes serious climate and environmental problems, especially global warming. The recovery and conversion of carbon dioxide in the atmosphere into useful chemical raw materials or small molecule fuels is one of the effective ways to simultaneously alleviate environmental problems and energy crisis, so that the preparation of high value-added chemical raw materials by electrocatalysis of carbon dioxide reduction is one of the hot spots of current research and the most potential technologies. However, carbon dioxide belongs to a compound with relatively stable thermodynamic properties, a relatively high energy barrier needs to be overcome in the activation process of a carbon-oxygen double bond, and then hydrogen protons exist in the aqueous electrolyte to induce the generation of a hydrogen evolution side reaction, so that the selectivity of the carbon dioxide reduction reaction is remarkably reduced. Meanwhile, most of carbon dioxide reduction electrocatalysts have poor selectivity and stability and are difficult to further apply due to the technical problems that products are difficult to separate and the like.
Among the reduction products, formic acid has the advantages of high volume energy density, easy storage and transportation and the like, and has more economic value than carbon monoxide which is also transferred by two electrons, so the formic acid is widely considered to have extremely high economic benefit and development potential. At present, carbon dioxide reduction catalysts with good formic acid selectivity mainly comprise metals or metal oxides such as tin, lead, indium, bismuth and the like, and compared with other heavy metals, the carbon dioxide reduction catalysts have low toxicity and rich earth crust reserves. In addition, the general bismuth-based material is complex in preparation method, extra electric energy input is needed, the cost is increased, the morphology is difficult to control, the stability is poor, and the practical application is not facilitated. Therefore, the construction of a low-cost, efficient and stable carbon dioxide reduction catalyst has important practical significance for alleviating energy and environment problems.
Some reports on supported bismuth nanoparticles as catalysts are disclosed in the prior art. Document 1 ("Selective Electrochemical Production of format from Carbon Dioxide with Bismuth-Based Catalysts in an Aqueous Electrolyte", ACS catalyst.2018, 8, 931-937) discloses a conductive Carbon black supported Bismuth oxide nanoparticle composite catalyst that exhibits 93.4% formic acid faradic efficiency in the range of-1.37V to-1.70V (relative to an Ag/AgCl reference), but suffers from reduced stability due to the catalyst material being a metal oxide that is susceptible to structural transformation at reducing potentials. At the same time, biO x Is less conductive so that its current density is also less. Document 2 ("efficiency CO 2 Reduction to HCOOH with High Selectivity and Energy Efficiency over Bi/rGO Catalyst ", small Methods,2020,1900846) discloses a reduced graphene oxide loaded bismuth nanoparticle with a formic acid faraday up to 98% and stability test performance remaining over 12 hours. However, since the force acting between the metal particles and the graphene support is weak, it is difficult to maintain the catalytic stability for a long time. It can be seen that a class of bismuth-based nanoparticles known in the artAlthough the composite catalyst has achieved good formic acid Faraday efficiency and high catalyst activity, the stability of the catalyst is also a limiting factor for limiting the catalyst to large-scale industrialization and commercialization.
Based on the method, the metal bismuth nanoparticle composite catalyst with high active sites, high conductivity, high specific surface area and high stability is prepared from the structural design and the cost of the catalyst, and the catalyst can keep high efficiency and stability for a long time under simple preparation conditions and shows good application prospects.
Disclosure of Invention
The invention aims to provide a method for constructing a high-efficiency stable bismuth nanoparticle composite material, a catalyst and application thereof, the bismuth nanoparticle composite material catalyst with uniform size can be used for preparing formic acid by carbon dioxide electroreduction, and has excellent catalytic performance and excellent electrochemical stability compared with other existing heavy metal materials; the invention has simple synthesis method, and the appearance does not need to be subjected to complicated electrochemical regulation and conversion. Compared with other preparation methods of nano-particle catalysts, the preparation method does not need high-temperature heating conditions and complex precursor design, and has the advantages of simple process, low cost and convenient operation.
The invention firstly provides a supported metal bismuth particle composite material, wherein metal bismuth particles are supported on a porous carbon carrier through a coupling agent with amino groups, and the particle size of the metal bismuth particles is 5-30nm.
Furthermore, the particle size of the metal bismuth particles is 7-10nm.
Further, the linking agent with amino groups is at least one selected from tetraaminophenyl porphyrin and tetraaminophthalocyanine.
The metal bismuth nanoparticle composite material provided by the invention is characterized in that the position of a Raman spectrum characteristic peak is positioned at 996 +/-1 cm -1 ，1236±1cm -1 ，1449±1cm -1 ，1486±1cm -1 Preferably, the Raman spectral characteristic peak position is located at 996 + -0.5 cm -1 ，1236±0.5cm -1 ，1449±0.5cm -1 ，1486±0.5cm -1
The metallic bismuth nanoparticle composite material is characterized in that the XPS spectrum of the metallic bismuth nanoparticle composite material contains 4f of Bi 7/2 The orbital binding energy position is 158.9 +/-0.2 eV, and the corresponding 1s orbital binding energy position of nitrogen is 400.4 +/-0.1 eV; preferably, the XPS spectrum thereof is Bi 4f 7/2 The orbital binding energy position is 158.9 +/-0.1 eV, and the corresponding 1s orbital binding energy position of nitrogen is 400.4 +/-0.05 eV
Because electron transfer interaction occurs between the coupling agent with amino and the metal, and pi interaction exists between the coupling agent and the carbon carrier, the integral composite material has good stability. After the metal bismuth nanoparticles provided by the invention are loaded on a porous carbon carrier, raman spectrum and XPS can shift to a certain degree. And thus can be judged by the characteristic peak positions of its raman spectrum and XPS spectrum. Specifically, the Raman spectrum is generated by 2-3 cm -1 The red shift from left to right indicates that the electron cloud density of the tetraaminophenylporphyrin molecule in the composite material is reduced, namely, the electron transfer occurs. In XPS Bi has a negative shift of 0.5eV for the 4f orbital binding energy and a positive shift of 0.25eV for the 1s orbital binding energy of N. The electron transfer process from the tetraaminophenylporphyrin molecule to the bismuth nanoparticle was demonstrated to occur in the composite.
The invention also provides a method for preparing the metal bismuth nanoparticle composite catalyst, which comprises the following steps:
(1) Dispersing a porous carbon carrier in a coupling agent solution, carrying out impregnation adsorption, washing, drying and baking to obtain a coupling agent-treated porous carbon composite material;
(2) Dispersing the porous carbon composite material treated by the coupling agent in a bismuth metal salt solution, dipping and adsorbing, then dropwise adding a solution of a reducing agent under stirring, and obtaining the load type metal bismuth particle composite material under the stirring condition.
In step (1), the porous carbon is not particularly limited, and may be any commercially available porous carbon material or porous carbon material prepared according to a conventional method, such as: activated carbon, ketjen black, activated carbon fiber, super-P, acetylene black, graphene, expanded graphite, carbon nanotube, mesoporous carbon, or carbonMolecular sieves, and the like, and in particular embodiments of the invention, the porous carbon may be ketjen black. The pore diameter and the specific surface area of the porous carbon are not limited, and in the specific embodiment of the invention, the pore diameter of the porous carbon is 0.5-20nm, preferably 5-10nm; the specific surface area is 1000-1600m 2 A/g, preferably from 1200 to 1500m 2 /g。
The concentration of the coupling agent solution can be 0.1-1mg/mL, preferably 0.25-0.5mg/mL. The solvent for the linking agent is not particularly limited, and may be any solvent capable of dissolving the linking agent, for example, a conventional organic solvent such as chloroform, dimethylformamide, tetrahydrofuran, ethanol, propanol, ethyl acetate, or benzene.
The impregnation time is not particularly limited, and may be sufficient for impregnation and adsorption, and is generally 6 to 24 hours.
In the step (2), the bismuth metal salt may be bismuth nitrate, bismuth trichloride, and preferably bismuth nitrate. The concentration of the bismuth metal salt may be 25-100mM, preferably 50-75mM. The reducing agent can be sodium borohydride, potassium borohydride and hydrazine hydrate; the concentration of the reducing agent is 50-150mM, preferably 70-100mM. The solvent of the bismuth metal salt solution and the reducing agent solution is not particularly limited, and may be dimethylformamide, ethanol, ethylene glycol, or methanol.
Further, the mass ratio of the composite porous carbon to the coupling agent to the bismuth metal salt to the reducing agent is 5-10:1-2:1-2:0.05-1.
The efficient and stable metal bismuth nanoparticle composite material prepared by the method is obtained by the steps of firstly loading tetraaminophenylporphyrin molecules on porous carbon to form a modified porous carbon composite material through simple two-step impregnation adsorption, then carrying out second-step impregnation adsorption with bismuth metal salt, and reducing with sodium borohydride. The bismuth metal nano particles are fixed on the porous carbon carrier in a strong combination mode due to the limited domain effect of the porous carbon and the special stabilizing effect of the molecular coupling agent, the loading capacity is high, the activity is high, the molecular coupling agent has the function of reinforcing the interaction between the metal bismuth nano particles and the carrier, and the structure of the molecular coupling agent cannot be changed under the reduction condition. In addition, the method for modifying the carbon carrier by the conjugated organic molecules can be expanded to other similar metal nano particles, has simple and easily repeated operation process, and has good reference significance and wide application prospect.
The invention also provides application of the metal bismuth nanoparticle composite catalyst in preparation of formic acid by reduction of carbon dioxide. The metal bismuth nanoparticle composite catalyst prepared by the invention has high catalytic activity and good stability, can keep the formic acid Faraday efficiency for a long time, and has obvious industrialization advantages.
Compared with other prior art, the invention has the following advantages:
1. the invention is based on the limited domain effect of porous carbon, the interaction between the molecular coupling agent and the metal bismuth nano-particles to prepare a high-efficiency stable bismuth metal nano-particle composite material, compared with other methods, the method has the advantages of low cost, simple process flow, remarkable effect improvement and suitability for the requirement of practical application; the porous carbon material has the characteristics of large specific surface area, high chemical stability, good electrical conductivity, good mechanical property, developed pores, wide sources, low cost and the like, and is widely applied to the fields of supercapacitors, fuel cells, water purification adsorption, electrocatalysis and the like; the high-efficiency stable bismuth metal nanoparticle composite material prepared by the invention has great potential application value in the fields of electrocatalysis, industrial catalysis, artificial nitrogen fixation and the like;
2. the carbon source selected by the invention is simple and easy to obtain, has a porous structure, a high specific surface area and a plurality of micro-mesopores, and can show excellent adsorption performance and confinement effect;
3. the preparation method adopts the organic micromolecules of the tetraaminophenylporphyrin as the molecular coupling agent for stabilizing the metal nanoparticles, has simple and convenient operation, safe preparation process, no pollution and easily controlled feeding amount;
4. the preparation method of the invention adopts a chemical reduction means, avoids the conditions of high-temperature heating and external reduction current, and saves the cost in the process flow;
5. the high-efficiency stable bismuth metal nano-particles obtained by the method can be used as a cathode catalyst for carbon dioxide reduction, and have high activity and ensure the long-term stability of the material;
6. the bismuth nanoparticles prepared by the method have uniform and controllable size, and have better shape retention degree and higher chemical robustness compared with other catalysts with sheet or layered shapes;
7. the organic micromolecules adopted in the invention can generate electron transfer interaction with the bismuth metal nanoparticles loaded on the porous carbon, so that the reduction current density of the composite catalyst for carbon dioxide reduction is greatly improved.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of the high-efficiency stable metal bismuth nanoparticle composite material prepared in example 1 of the invention.
Fig. 2 (a) is a transmission electron microscope photograph of the highly efficient and stable metal bismuth nanoparticle composite material prepared in example 1 of the present invention, and (b) is a corresponding size distribution and a fitted curve.
Fig. 3 is an energy spectrum of each element of the high-efficiency stable metal bismuth nanoparticle composite material prepared in example 1 of the invention.
Fig. 4 is a raman spectrum of the highly efficient and stable metal bismuth nanoparticle composite material prepared in example 1 and comparative example 1 of the present invention and the original tetraaminophenylporphyrin.
Fig. 5 is XPS spectra of bismuth as metal bismuth nanoparticle composites prepared in example 1 and comparative example 1 of the present invention, wherein fig. 5 (a) is a 4f orbital spectrum of Bi and fig. 5 (b) is a 1s orbital spectrum of N.
Fig. 6 is a graph showing experimental performance of carbon dioxide reduction of the high efficiency stable metal bismuth nanoparticle composite material prepared in example 1 of the present invention and comparative examples 1 and 2, wherein (a) is a polarization curve under saturated carbon dioxide and argon gas, and (b) is faradaic efficiency of the product.
Fig. 7 (a) shows the stability curve and the corresponding change of faradaic efficiency of the high efficiency stable metal bismuth nanoparticle composite material prepared in example 1 of the present invention, and (b) shows the stability curve and the corresponding change of faradaic efficiency of comparative example 1.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The methods described in the following examples are conventional methods unless otherwise specified.
The raw materials such as materials and reagents used in the following examples are commercially available from public unless otherwise specified.
Example 1
Dissolving 10mg of tetraaminophenylporphyrin in 20mL of a mixed solvent of chloroform and 20mL of dimethylformamide, subjecting to ultrasonication for 1 hour, and adding Ketjen black (model ECP-600JD, pore diameter of about 10nm, specific surface area of 1400m, obtained from LION, japan) to the mixed solution 2 /g) 60mg, continuing to perform ultrasonic treatment for 1 hour, performing immersion adsorption for 12 hours, centrifuging to collect a solid product, washing with ethanol for 2 times, and performing vacuum drying at 60 ℃ for 6 hours. The dried sample is taken out and placed in a double-temperature-zone tube furnace to be baked for 1 hour at 100 ℃. And (2) dispersing 60mg of baked porous carbon in 20mL of dimethylformamide solution dissolved with 1mmol of bismuth nitrate, performing ultrasonic treatment for 1 hour, then soaking for 12 hours, dropwise adding 10mL of dimethylformamide solution dissolved with 1mmol of sodium borohydride into the solution, stirring for 15 minutes, centrifuging, washing for 3 times by using ethanol, and performing vacuum drying at 60 ℃ for 6 hours to obtain the metal bismuth nanoparticle composite material.
The X-ray powder diffraction curve of the highly efficient and stable metal bismuth nanoparticle composite material prepared in this example is shown in fig. 1, and it can be seen from the graph that no peaks other than the diffraction peak of metal bismuth exist.
Fig. 2 (a) is a transmission electron microscope photograph of the high efficiency stable metallic bismuth nanoparticle composite prepared in example 1, and (b) is the corresponding size distribution and fitted curve. It can be seen that the average size of the metallic bismuth nanoparticles is about 7nm, the size is uniform, and no obvious aggregation phenomenon occurs.
Fig. 3 is an energy spectrum of each element of the high-efficiency stable metal bismuth nanoparticle composite material prepared in example 1 of the present invention. As can be seen from fig. 3, the carbon support of the composite catalyst prepared in this example uniformly distributed nitrogen and oxygen elements, which proves the uniform loading of the tetraaminophenylporphyrin molecules.
Fig. 4 is a raman spectrum of the highly efficient and stable metal bismuth nanoparticle composite material prepared in example 1 and comparative example 1 of the present invention and the original tetraaminophenylporphyrin. As can be seen from the figure, in the catalyst prepared in example 1, due to the existence of the linking agent tetraaminophenylporphyrin, the porous carbon carrier is firstly modified, then the metal bismuth nanoparticles are loaded on the recarbon carrier through reduction reaction, and the carbon carrier in comparative example 1 is not treated by tetraaminophenylporphyrin, so that the Raman spectrum of the catalyst is generated by 2-6cm -1 Negative shift.
Fig. 5 is XPS spectra of bismuth as metal bismuth nanoparticle composites prepared in example 1 and comparative example 1 of the present invention, wherein fig. 5 (a) is a 4f orbital spectrum of Bi and fig. 5 (b) is a 1s orbital spectrum of N. It can be seen that the valence of bismuth of the composite material obtained in example 1 is zero, and the characteristic peak of bismuth element is shifted by 0.5 electron volts toward a low energy direction compared to comparative example 1, demonstrating the transfer of electrons from the tetraaminophenylporphyrin molecule to the metal particles. Meanwhile, fig. 5 (b) shows that the obtained composite material contains two types of nitrogen elements, pyrrole nitrogen corresponds to nitrogen in a porphyrin ring, and amino nitrogen corresponds to amino group in tetraaminophenylporphyrin, which indicates that the tetraaminophenylporphyrin successfully modifies a carbon carrier.
In conclusion, it can be confirmed that example 1 successfully prepares a metal bismuth nanoparticle composite material with uniform size, and electron transfer interaction exists between the supported tetraaminophenylporphyrin molecule and the metal bismuth nanoparticle.
Fig. 6 is graphs of experimental performance of the high efficiency stable metallic bismuth nanoparticle composite prepared in example 1 of the present invention and reduction of carbon dioxide in comparative example 1 and comparative example 2, in which fig. 6 (a) is a polarization curve under saturated carbon dioxide and argon, and fig. 6 (b) is faradaic efficiency of the composite of example 1 as a catalyst for reduction reaction of carbon dioxide.
The specific experimental steps are as follows: the obtained composite material of the metal bismuth nano-particles (the loading amount is 1 mg/cm) 2 ) Supported on a cut carbon cloth, tested in 0.5M potassium bicarbonate solution, the composition of the reactants was measured by gas chromatography and liquid nuclear magnetic resonance, and the faradaic efficiency was calculated. To be provided withThe faraday efficiency tests in the other examples below were all tested under the same operation and conditions.
The catalyst prepared in example 1 above had a current density of 55.6mA/cm at-1.0V in a carbon dioxide reduction experiment 2 . According to a Faraday efficiency calculation formula:
n represents the amount of the substance of the product, F represents a Faraday constant, Q represents the total amount of passed electric charge, and the formic acid Faraday efficiency can reach 92.1 percent by calculation; comparative example 1 Current Density of 38.5mA/cm at-1.0 volts 2 The formic acid Faraday efficiency is 91.2%; the comparative example 2 has almost no carbon dioxide reduction catalytic activity, which shows that the high-efficiency stable metal bismuth nanoparticle composite material prepared by the invention has excellent carbon dioxide electrocatalytic activity, and the performance of the catalyst is improved after the tetraaminophenylporphyrin molecule is loaded.
Fig. 7 is a stability curve of a metal bismuth nanoparticle composite material, in which fig. 7 (a) corresponds to example 1 and fig. 7 (b) corresponds to comparative example 1. The specific experimental steps are as follows: the catalyst was supported on a surface of 0.5cm 2 The constant potential curve measurement is carried out on the carbon cloth in 0.5M potassium bicarbonate, the measurement is continuously carried out for more than 20 hours under the constant potential of-0.9V, and the distribution condition of the product is analyzed at regular time. From the above curves, it can be seen that the catalyst prepared in example 1 has excellent stability, the faraday efficiency can still be maintained at 80.8% after 20 hours, while the faraday efficiency of the catalyst in comparative example 1 is already reduced to about 30% after 10 hours, which further illustrates that in the technical scheme of the present invention, the carbon carrier treated by tetraaminophenylporphyrin molecules results in improved performance.
Example 2
Prepared in the same manner as in example 1 except that the mass of tetraaminophenylporphyrin added in example 1 was changed from 10mg to 5mg, so that there was no significant change in the size of metallic bismuth nanoparticles supported on porous carbon, and the resulting composite catalyst was tested in 0.5M potassium bicarbonate solution at a potential of-1.0V and a current density of 43.5mA/cm 2 The faradaic efficiency of formic acid was 86.2%. The stability test duration was 15 hours at a constant potential of-0.9 volts with a faraday efficiency of at least 80%.
Example 3
Prepared according to the same manner as in example 1 except that the mass of the tetraaminophenylporphyrin added in example 1 was changed from 10mg to 15mg, as a result, there was no significant change in the size of the metallic bismuth nanoparticles supported on the porous carbon, and the resulting composite catalyst was then tested in 0.5M potassium bicarbonate solution at a potential of-1.0V and a current density of 40.6mA/cm 2 The formic acid faradaic efficiency was 88.4%. The stability test duration was 14 hours at a potentiostatic potential of-0.9 volts with a faraday efficiency of at least 80%.
Example 4
Prepared in the same manner as in example 1 except that the mass of tetraaminophenylporphyrin added in example 1 was changed from 10mg to 20mg, so that there was no significant change in the size of metallic bismuth nanoparticles supported on porous carbon, and the resulting composite catalyst was tested in 0.5M potassium bicarbonate solution at a potential of-1.0V and a current density of 34.2mA/cm 2 The formic acid faradaic efficiency was 82.2%. The stability test duration was 12 hours at a constant potential of-0.9 volts with a faraday efficiency maintained at least 80%.
Example 5
Prepared in the same manner as in example 1 except that the concentration of bismuth nitrate used in example 1 was changed from 50mM to 25mM, so that the size of metallic bismuth nanoparticles supported on porous carbon became 5 nm, and the resulting composite catalyst was then tested in a 0.5M potassium hydrogencarbonate solution at a potential of-1.0V and a current density of 35.1mA/cm 2 The formic acid faradaic efficiency was 88.1%. The stability test duration was 16 hours at a constant potential of-0.9 volts with a faraday efficiency maintained at least 80%.
Example 6
Preparation was carried out in the same manner as in example 1 except that the concentration of bismuth nitrate used in example 1 was changed from 50mM to 75mM, resulting in metallic bismuth nanoparticles supported on porous carbonThe particle size was changed to 10nm, and then the obtained composite catalyst was tested in a 0.5M potassium hydrogen carbonate solution at a potential of-1.0V and a current density of 38.7mA/cm 2 The formic acid faradaic efficiency was 87.7%. The stability test duration was 17 hours at a constant potential of-0.9 volts with a faraday efficiency of at least 80%.
Example 7
Prepared in the same manner as in example 1 except that the concentration of bismuth nitrate used in example 1 was changed from 50mM to 100mM, so that the size of metallic bismuth nanoparticles supported on porous carbon became 15 nm, and the resulting composite catalyst was then tested in 0.5M potassium hydrogencarbonate solution at a potential of-1.0V and a current density of 37.9mA/cm 2 The formic acid faradaic efficiency was 81.3%. The stability test duration was 11 hours at a constant potential of-0.9 volts with a faraday efficiency of at least 80%.
Example 8
Prepared according to the same manner as in example 1 except that the concentration of sodium borohydride added in example 1 was changed from 100mM to 50mM, as a result, crystallinity of metallic bismuth nanoparticles supported on porous carbon was deteriorated and the supported amount was decreased, and then the resulting composite catalyst was tested in 0.5M potassium hydrogencarbonate solution at a potential of-1.0V and a current density of 35.6mA/cm 2 The formic acid faradaic efficiency was 80.6%. The stability test duration was 8 hours at a constant potential of-0.9 volts with a faraday efficiency of at least 80%.
Example 9
Prepared according to the same method as example 1, except that the concentration of sodium borohydride added in example 1 is changed from 100mM to 150mM, so that metallic bismuth nanoparticles loaded on porous carbon are agglomerated, and small particles on the morphology have the tendency of local agglomeration to nano-sheets, and then the obtained composite catalyst is tested in 0.5M potassium bicarbonate solution, and the current density is 38.8mA/cm at the potential of-1.0V 2 The formic acid faradaic efficiency was 80.9%. The stability test duration was 9 hours at a constant potential of-0.9 volts with at least 80% maintenance of faraday efficiency.
Comparative example 1
Prepared substantially in the same manner as in example 1, except that the starting porous carbon in example 1 was used directly as an adsorbent for bismuth metal salt, which was not modified with tetraaminophenylporphyrin molecules. The resulting bismuth metal nanoparticle composite had a particle size and formic acid faradaic efficiency close to that of example 1, 91.2%. But the current density and the stability are reduced, and the current density is 38.5mA/cm at-1.0 volt 2 And the stability test shows that the faradaic efficiency of formic acid is reduced to 32.3% at 4 hours, which obviously shows that the tetraaminophenylporphyrin plays a crucial stabilizing role on the bismuth metal nanoparticles.
Comparative example 2
Prepared essentially as in example 1, except that the tetraaminophenylporphyrin is supported on porous carbon and then no subsequent adsorption and chemical reduction of the bismuth metal salt is carried out. The obtained composite material hardly shows activity in a carbon dioxide reduction performance test, and no formic acid product is generated. This indicates that the tetraaminophenylporphyrin itself has no catalytic activity for carbon dioxide reduction, i.e., no performance contribution to the composite obtained in example 1.
Claims (10)
1. A loaded metal bismuth particle composite material is characterized in that metal bismuth particles are loaded on a porous carbon carrier through a coupling agent with amino groups, and the particle size of the metal bismuth particles is 5-30nm;
the coupling agent with amino is at least one of tetraaminophenyl porphyrin and tetraaminophthalocyanine;
the preparation method of the metal bismuth nanoparticle composite catalyst comprises the following steps:
(1) Dispersing a porous carbon carrier in a coupling agent solution, carrying out impregnation adsorption, washing, drying and baking to obtain a coupling agent-treated porous carbon composite material;
(2) Dispersing the porous carbon composite material treated by the coupling agent in a bismuth metal salt solution, dipping and adsorbing, then dropwise adding a solution of a reducing agent under stirring, and obtaining the load type metal bismuth particle composite material under the stirring condition.
2. A supported metallic bismuth particle composite material as claimed in claim 1 wherein the metallic bismuth particles have a particle size in the range of 7 to 10nm.
3. The supported metallic bismuth particle composite of claim 1, wherein the raman spectral peak position is 996 ± 1cm -1 ，1236±1cm -1 ，1449±1cm -1 ，1486±1cm -1 。
4. A supported metallic bismuth particle composite material as claimed in claim 1 wherein the XPS spectrum of the composite material is Bi at 4f 7/2 The orbital binding energy position is 158.9e + -0.2V, and the corresponding 1s orbital binding energy position of nitrogen is 400.4 + -0.1 eV.
5. The supported metallic bismuth particle composite material according to claim 1, wherein in the step (1), the concentration of the coupling agent solution is 0.1 to 1mg/mL.
6. The supported metallic bismuth particle composite material according to claim 5, wherein in the step (1), the concentration of the coupling agent solution is 0.25 to 0.5mg/mL.
7. The supported metallic bismuth particle composite material according to claim 1, wherein in the step (2), the bismuth metal salt is bismuth nitrate or bismuth trichloride; the concentration of the metal bismuth salt is 25-100 mM; the reducing agent is sodium borohydride, potassium borohydride or hydrazine hydrate; the concentration of the reducing agent is 50-150 mM.
8. The supported metal bismuth particle composite material as claimed in claim 7, wherein the concentration of the metal bismuth salt is 50 to 75mM and the concentration of the reducing agent is 70 to 100mM.
9. The supported metallic bismuth particle composite material as claimed in claim 1, wherein the mass ratio of the composite porous carbon, the coupling agent, the bismuth metal salt and the reducing agent is 5 to 10:1-2:1-2:0.05-1.
10. Use of the supported metallic bismuth nanoparticle composite material of any one of claims 1 to 9 for the preparation of formic acid by reduction with carbon dioxide.
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