技术领域technical field
本发明涉及催化剂技术以及能源可持续发展领域，具体是一种氧化铈负载铋纳米催化剂及其制备方法和应用。The invention relates to the field of catalyst technology and energy sustainable development, in particular to a cerium oxide-supported bismuth nanocatalyst and a preparation method and application thereof.
背景技术Background technique
随着对能源需求量的增加，大气内急剧升高的CO2含量所引发的气候变暖及生态问题成为了人类可持续发展的严峻挑战。因此，对CO2进行有效利用，使其转化为绿色资源，具有极其重要的意义。其中，电催化还原CO2，可以有效地利用可再生的电能(太阳能、风能等)，从而受到研究人员的广泛关注。在众多的CO2还原产物中，甲酸作为具有较高附加值的产物，不仅可以应用于医药、制革和纺织工业中，而且是燃料电池的氢载体，因此甲酸被认为是极具吸引力的CO2还原产物。另外，通过传统方法合成甲酸复杂且不环保，因此，通过电催化还原CO2产甲酸是一种非常有前景的方法。With the increasing demand for energy, the climate warming and ecological problems caused by the rapidly rising CO2 content in the atmosphere have become severe challenges to the sustainable development of human beings. Therefore, it is extremely important to effectively utilize CO2 and convert it into green resources. Among them, the electrocatalytic reduction of CO2 can effectively utilize renewable electric energy (solar energy, wind energy, etc.), and thus has attracted extensive attention of researchers. Among the numerousCO2 reduction products, formic acid, as a product with higher added value, can not only be used in medicine, tanning and textile industries, but also be a hydrogen carrier for fuel cells, so formic acid is considered to be very attractiveCO2 reduction products. In addition, the synthesis of formic acid by traditional methods is complex and not environmentally friendly, thus, the production of formic acid by electrocatalytic reduction ofCO2 is a very promising approach.
目前，尽管某些催化剂在电还原CO2产甲酸上取得了较高的选择性，得到了较高的法拉第效率(Faradaic efficiency，FE)，但甲酸的FE对外加电流密度很敏感，这导致甲酸的生成速率受到限制。通常情况下，在较高电流密度(>60mA/cm2)下，甲酸的FE就会由于析氢反应而大幅下降。因此，目前急需开发一种高选择性、高活性的高性能电还原CO2产甲酸的催化剂，以保证在提升CO2还原产甲酸速率的同时，还能够保持较高的甲酸FE。At present, although some catalysts have achieved high selectivity and high Faradaic efficiency (FE) in the electroreduction ofCO2 to produce formic acid, the FE of formic acid is sensitive to the applied current density, which leads to formic acid The generation rate of is limited. Normally, at a higher current density (>60mA/cm2 ), the FE of formic acid will drop significantly due to the hydrogen evolution reaction. Therefore, there is an urgent need to develop a high-selectivity, high-activity high-performance catalyst for electroreduction of CO2 to produce formic acid, so as to ensure that while increasing the rate of CO2 reduction to produce formic acid, it can also maintain a high FE of formic acid.
发明内容Contents of the invention
本发明的目的在于提供一种氧化铈负载铋纳米催化剂及其制备方法和应用，以解决上述背景技术中提出的问题。The purpose of the present invention is to provide a cerium oxide-supported bismuth nanocatalyst and its preparation method and application, so as to solve the problems raised in the above-mentioned background technology.
为实现上述目的，本发明实施例提供如下技术方案：In order to achieve the above purpose, embodiments of the present invention provide the following technical solutions:
一种氧化铈负载铋纳米催化剂的制备方法，包括以下步骤：A preparation method of cerium oxide supported bismuth nano catalyst, comprising the following steps:
S01、将载体氧化铈置于水中，搅拌均匀，得到溶液C；S01, placing the carrier cerium oxide in water, stirring evenly to obtain solution C;
S02、往溶液C中添加Bi(NO3)3·5H2O，搅拌均匀，得到溶液D；所述Bi(NO3)3·5H2O的添加质量为载体氧化铈质量的2-5倍；S02. Add Bi(NO3 )3 5H2 O to solution C, and stir evenly to obtain solution D; the added mass of Bi(NO3 )3 5H2 O is 2-5 times the mass of the carrier cerium oxide ;
S03、将Na2CO3溶液缓慢添加到溶液D中，搅拌均匀，得到溶液E；S03. Slowly add the Na2 CO3 solution to the solution D, and stir evenly to obtain the solution E;
S04、将溶液E依次进行离心、水洗、醇洗和真空干燥处理后，得到前驱体；S04, after the solution E is centrifuged, washed with water, washed with alcohol and vacuum-dried in sequence, the precursor is obtained;
S05、将前驱体置于惰性气体/H2混合气体中进行煅烧，得到氧化铈负载铋纳米催化剂。S05. Calcining the precursor in an inert gas/H2 mixed gas to obtain a bismuth nanocatalyst supported on cerium oxide.
本发明实施例采用的一种优选方案，所述步骤S03中，Na2CO3溶液中溶质的质量为载体氧化铈质量的0.8-1.2倍。A preferred scheme adopted in the embodiment of the present invention, in the step S03, the mass of the solute in the Na2 CO3 solution is 0.8-1.2 times the mass of the carrier cerium oxide.
本发明实施例采用的另一种优选方案，所述的步骤S04中，真空干燥的温度为35-50℃。Another preferred solution adopted in the embodiment of the present invention, in the step S04, the vacuum drying temperature is 35-50°C.
本发明实施例采用的另一种优选方案，所述的步骤S05中，惰性气体/H2混合气体中H2的体积浓度为8-12％，煅烧的温度为100-200℃，煅烧的时间为0.5-2h。Another preferred scheme adopted in the embodiment of the present invention, in the step S05, the volume concentration ofH2 in the inert gas/H2 mixed gas is 8-12%, the temperature of calcination is 100-200°C, and the time of calcination is 0.5-2h.
本发明实施例采用的另一种优选方案，所述载体氧化铈的制备方法包括以下步骤：Another preferred solution adopted in the embodiment of the present invention, the preparation method of the carrier cerium oxide includes the following steps:
S11、将Ce(NO3)3·6H2O溶于水中，得到溶液A；S11. Dissolving Ce(NO3 )3 ·6H2 O in water to obtain solution A;
S12、往溶液A中添加NaBH4，搅拌均匀，得到溶液B；所述NaBH4的添加质量为Ce(NO3)3·6H2O质量的0.1-0.4倍；S12. Add NaBH4 to solution A and stir evenly to obtain solution B; the added mass of NaBH4 is 0.1-0.4 times the mass of Ce(NO3 )3 ·6H2 O;
S13、将溶液B依次进行离心、水洗、醇洗和干燥处理后，得到所述的载体氧化铈。S13. After the solution B is centrifuged, washed with water, washed with alcohol and dried in sequence, the carrier cerium oxide is obtained.
本发明实施例采用的另一种优选方案，所述的步骤S13中，干燥的温度为50-70℃。Another preferred solution adopted in the embodiment of the present invention, in the step S13, the drying temperature is 50-70°C.
本发明实施例还提供了一种利用上述制备方法制得的氧化铈负载铋纳米催化剂。The embodiment of the present invention also provides a bismuth nanocatalyst supported on cerium oxide prepared by the above preparation method.
本发明实施例还提供了一种上述氧化铈负载铋纳米催化剂在电催化还原CO2产甲酸中的应用。The embodiment of the present invention also provides an application of the above cerium oxide-supported bismuth nanocatalyst in electrocatalytic reduction of CO2 to produce formic acid.
本发明实施例采用的另一种优选方案，所述电催化还原CO2产甲酸的方法包括以下步骤：将氧化铈负载铋纳米催化剂和导电炭黑分散在水/乙醇混合溶液中后，再添加全氟磺酸型聚合物进行混合，得到分散液；接着，将分散液滴加到碳布上形成工作电极，将Ag/AgCl和Pt网分别作为参比电极和对电极，将NaSO4溶液作为电解液；然后，在-1.4～-1.9Vvs.Ag/AgCl的电解电压下对CO2进行电解还原，得到甲酸。Another preferred scheme adopted in the embodiment of the present invention, the method for the electrocatalytic reduction ofCO to produce formic acid comprises the following steps: after dispersing the cerium oxide-supported bismuth nanocatalyst and conductive carbon black in the water/ethanol mixed solution, adding The perfluorosulfonic acid polymers were mixed to obtain a dispersion; then, the dispersion was added dropwise on the carbon cloth to form a working electrode, the Ag/AgCl and Pt mesh were used as the reference electrode and the counter electrode, respectively, and theNaSO solution was used as the Electrolyte; Then,CO2 is electrolytically reduced under the electrolytic voltage of -1.4～-1.9Vvs.Ag/AgCl to obtain formic acid.
本发明实施例采用的另一种优选方案，所述的氧化铈负载铋纳米催化剂与导电炭黑的质量为(4-6):1；所述水/乙醇混合溶液中水与乙醇的体积比为(0.8-1.2):1；所述的氧化铈负载铋纳米催化剂与全氟磺酸型聚合物的质量体积比按照mg/μL计为1:(8-12)；所述NaSO4溶液的摩尔浓度为0.1-0.3M。Another preferred scheme adopted in the embodiments of the present invention, the quality of the cerium oxide-supported bismuth nanocatalyst and conductive carbon black is (4-6): 1; the volume ratio of water and ethanol in the water/ethanol mixed solution Be (0.8-1.2): 1; The mass volume ratio of described cerium oxide supported bismuth nanocatalyst and perfluorosulfonic acid type polymer is 1:(8-12) according to mg/μL; Described NaSOThe solution The molar concentration is 0.1-0.3M.
与现有技术相比，本发明实施例的有益效果是：Compared with the prior art, the beneficial effects of the embodiments of the present invention are:
(1)本发明实施例提供的氧化铈负载铋纳米催化剂的制备方法，采用一步还原法，在室温下即可制备载体氧化铈，其具有合成时间短，操作简便等优点。另外，本发明实施例通过采用非晶氧化铈作为载体，可以充分利用氧化铈内部的大量缺陷，与铋纳米颗粒结合，从而可以增加活性位点数量，以显著提高催化剂的活性。(1) The preparation method of cerium oxide-supported bismuth nanocatalyst provided in the embodiment of the present invention adopts a one-step reduction method, and the carrier cerium oxide can be prepared at room temperature, which has the advantages of short synthesis time and simple operation. In addition, the embodiment of the present invention uses amorphous cerium oxide as a carrier, which can make full use of a large number of defects inside cerium oxide and combine with bismuth nanoparticles, thereby increasing the number of active sites and significantly improving the activity of the catalyst.
(2)本发明实施例将合成的载体氧化铈负载铋纳米催化剂具有高选择性，且该催化剂在硫酸钠电解液中用于常温常压下CO2电化学还原，对甲酸的生成具有极好的催化活性以及优异的稳定性。(2) The carrier cerium oxide supported bismuth nano-catalyst synthesized by the embodiment of the present invention has high selectivity, and the catalyst is used in sodium sulfate electrolyte forCO under normal temperature and pressure Electrochemical reduction has excellent properties for the generation of formic acid catalytic activity and excellent stability.
附图说明Description of drawings
图1为对比例1制得的CeOx以及实施例1制得的Bi/CeOx催化剂的X射线衍射谱图。Fig. 1 is the X-ray diffraction spectrogram of the CeOx prepared in Comparative Example1 and the Bi/CeOx catalyst prepared in Example 1.
图2为实施例1制得的Bi/CeOx催化剂分别在惰性气体以及CO2饱和的Na2SO4电解液中的线性伏安曲线图。Fig. 2 is the linear voltammetry curves of the Bi/CeOx catalyst prepared in Example 1 respectively in inert gas and CO2 saturated Na2 SO4 electrolyte.
图3为对比例2制得的纯铋催化剂分别在惰性气体以及CO2饱和的Na2SO4电解液中的线性伏安曲线图。3 is a linear voltammetry curve of the pure bismuth catalyst prepared in Comparative Example 2 in inert gas and CO2 -saturated Na2 SO4 electrolyte.
图4为实施例1制得的Bi/CeOx催化剂在常温常压CO2气氛下的Na2SO4电解液中不同电解电压下的电流-时间曲线图。Fig. 4 is the current-time curves of the Bi/CeOx catalyst prepared in Example 1 in Na2 SO4 electrolyte solution under normal temperature and pressure CO2 atmosphere under different electrolysis voltages.
图5为对比例2制得的pure Bi催化剂在常温常压CO2气氛下的Na2SO4电解液中不同电压下的电流-时间曲线图。Fig. 5 is the current-time curves of the pure Bi catalyst prepared in Comparative Example 2 in the Na2 SO4 electrolyte under the normal temperature and pressure CO2 atmosphere under different voltages.
图6为实施例1制得的Bi/CeOx催化剂、对比例2制得的pure Bi催化剂以及对比例3制得的Bi/CeO2催化剂在常温常压不同电解电压下的甲酸的法拉第效率对比曲线图。Fig. 6 is that the Bi/CeOx catalyst that embodiment 1 makes, the pure Bi catalyst that comparative example 2 makes and the Bi/CeO that comparative example3 makes catalyzer is at normal temperature and pressure different electrolysis voltages Faradaic efficiency comparison of formic acid Graph.
图7为实施例1制得的Bi/CeOx催化剂、对比例2制得的pure Bi催化剂以及对比例3制得的Bi/CeO2催化剂在常温常压不同电解电压下的甲酸的生产速率对比曲线图。Fig. 7 is the Bi/CeOx catalyst that embodiment 1 makes, the pure Bi catalyst that comparative example2 makes and the Bi/CeO that comparative example 3 makes The production rate comparison of the formic acid under normal temperature and pressure different electrolysis voltage of catalyst Graph.
图8为实施例1制得的Bi/CeOx催化剂在常温常压CO2气氛下的Na2SO4电解液中-1.7V vs.Ag/AgCl处的长时间稳定性曲线图。Fig. 8 is a long-term stability curve at -1.7V vs. Ag/AgCl of the Bi/CeOx catalyst prepared in Example 1 in a Na2 SO4 electrolyte under a CO2 atmosphere at normal temperature and pressure.
图9为对比例3制得的二氧化铈负载铋纳米催化剂(Bi/CeO2)分别在惰性气体以及CO2饱和的Na2SO4电解液中的线性伏安曲线。9 is the linear voltammetry curves of the ceria-supported bismuth nanocatalyst (Bi/CeO2 ) prepared in Comparative Example 3 in inert gas and CO2 saturated Na2 SO4 electrolyte.
图10为对比例3中Bi/CeO2催化剂在常温常压CO2气氛下的Na2SO4电解液中不同电压下的电流-时间曲线。Fig. 10 is the current-time curves of the Bi/CeO2 catalyst in Comparative Example 3 under different voltages in the Na2 SO4 electrolyte under the normal temperature and pressure CO2 atmosphere.
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
该实施例提供了一种氧化铈负载铋纳米催化剂及其制备方法，具体的，该氧化铈负载铋纳米催化剂的制备方法包括以下步骤：This embodiment provides a cerium oxide-supported bismuth nanocatalyst and a preparation method thereof. Specifically, the preparation method of the cerium oxide-supported bismuth nanocatalyst includes the following steps:
(1)将1.5g的Ce(NO3)3·6H2O溶于超纯水中，利用超声波搅拌均匀，得到溶液A；(1) Dissolve 1.5 g of Ce(NO3 )3 6H2 O in ultrapure water, and stir evenly with ultrasonic waves to obtain solution A;
(2)往溶液A中添加400mg的NaBH4，搅拌均匀，进行还原反应40min，得到溶液B；(2) Add 400 mg of NaBH4 to solution A, stir evenly, and carry out reduction reaction for 40 minutes to obtain solution B;
(3)将溶液B依次进行离心、水洗、醇洗处理后，再置于60℃的温度下进行干燥处理，便可得到载体氧化铈(CeOx)；(3) After the solution B is centrifuged, washed with water, and washed with alcohol in sequence, and then dried at a temperature of 60° C., the carrier cerium oxide (CeOx ) can be obtained;
(4)将400mg的载体氧化铈置于超纯水中，利用超声波搅拌均匀，得到溶液C，其中，超声频率为40kHz；(4) Place 400 mg of carrier cerium oxide in ultrapure water, and stir evenly with ultrasonic waves to obtain solution C, wherein the ultrasonic frequency is 40 kHz;
(5)往溶液C中添加1.5g的Bi(NO3)3·5H2O，利用超声波搅拌均匀，得到溶液D，其中，超声频率为40kHz；(5) Add 1.5 g of Bi(NO3 )3 ·5H2 O to solution C, and stir evenly with ultrasonic waves to obtain solution D, wherein the ultrasonic frequency is 40 kHz;
(6)将400mg的Na2CO3溶于超纯水中，利用超声波搅拌均匀，得到Na2CO3溶液，其中，超声频率为40kHz；然后将Na2CO3溶液缓慢滴加到溶液D中，搅拌均匀，得到溶液E；其中，搅拌在室温下进行，搅拌的时间为90min；(6) Dissolve 400mg of Na2 CO3 in ultrapure water, and stir evenly with ultrasonic waves to obtain a Na2 CO3 solution, wherein the ultrasonic frequency is 40kHz; then slowly add the Na2 CO3 solution dropwise into solution D , stirred evenly to obtain solution E; wherein, the stirring was carried out at room temperature, and the stirring time was 90min;
(7)将溶液E依次进行离心、水洗、醇洗处理后，再置于40℃的温度下进行真空干燥处理后，得到前驱体；(7) After the solution E is centrifuged, washed with water, and washed with alcohol in sequence, and then placed at a temperature of 40° C. for vacuum drying, the precursor is obtained;
(8)将前驱体置于惰性气体/H2混合气体中进行煅烧，即可得到氧化铈负载铋纳米催化剂(Bi/CeOx)。其中，惰性气体/H2混合气体中H2的体积浓度为10％，煅烧的温度为150℃，煅烧(保温)的时间为1h，惰性气体可选用氩气(Ar)。(8) Calcining the precursor in an inert gas/H2 mixed gas to obtain a cerium oxide-supported bismuth nanocatalyst (Bi/CeOx ). Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 10%, the temperature of calcination is 150° C., the time of calcination (insulation) is 1 h, and the inert gas can be argon (Ar).
实施例2Example 2
该实施例提供了一种氧化铈负载铋纳米催化剂及其制备方法，具体的，该氧化铈负载铋纳米催化剂的制备方法包括以下步骤：This embodiment provides a cerium oxide-supported bismuth nanocatalyst and a preparation method thereof. Specifically, the preparation method of the cerium oxide-supported bismuth nanocatalyst includes the following steps:
(1)将1g的Ce(NO3)3·6H2O溶于超纯水中，利用超声波搅拌均匀，得到溶液A；(1) Dissolve 1 g of Ce(NO3 )3 6H2 O in ultrapure water and stir evenly with ultrasonic waves to obtain solution A;
(2)往溶液A中添加100mg的NaBH4，搅拌均匀，进行还原反应10min，得到溶液B；(2) Add 100 mg of NaBH4 to solution A, stir evenly, and carry out reduction reaction for 10 minutes to obtain solution B;
(3)将溶液B依次进行离心、水洗、醇洗处理后，再置于50℃的温度下进行干燥处理，便可得到载体氧化铈(CeOx)；(3) After the solution B is centrifuged, washed with water and washed with alcohol in sequence, and then dried at a temperature of 50° C., the carrier cerium oxide (CeOx ) can be obtained;
(4)将100mg的载体氧化铈置于超纯水中，利用超声波搅拌均匀，得到溶液C；(4) Place 100 mg of carrier cerium oxide in ultrapure water, and stir evenly with ultrasonic waves to obtain solution C;
(5)往溶液C中添加0.5g的Bi(NO3)3·5H2O，利用超声波搅拌均匀，得到溶液D；(5) Add 0.5 g of Bi(NO3 )3 5H2 O to solution C, and stir evenly with ultrasonic waves to obtain solution D;
(6)将120mg的Na2CO3溶于超纯水中，利用超声波搅拌均匀，得到Na2CO3溶液；然后将Na2CO3溶液缓慢滴加到溶液D中，搅拌均匀，得到溶液E；其中，搅拌在室温下进行，搅拌的时间为30min；(6) Dissolve 120mg of Na2 CO3 in ultrapure water, and stir evenly with ultrasonic waves to obtain a Na2 CO3 solution; then slowly add the Na2 CO3 solution dropwise into solution D, and stir evenly to obtain solution E ; Wherein, stirring is carried out at room temperature, and the time of stirring is 30min;
(7)将溶液E依次进行离心、水洗、醇洗处理后，再置于35℃的温度下进行真空干燥处理后，得到前驱体；(7) After the solution E is centrifuged, washed with water, and washed with alcohol in sequence, and then placed at a temperature of 35°C for vacuum drying, the precursor is obtained;
(8)将前驱体置于惰性气体/H2混合气体中进行煅烧，即可得到氧化铈负载铋纳米催化剂。其中，惰性气体/H2混合气体中H2的体积浓度为8％，煅烧的温度为100℃，煅烧(保温)的时间为0.5h，惰性气体可选用氩气(Ar)。(8) The precursor is placed in an inert gas/H2 mixed gas for calcination to obtain a ceria-supported bismuth nanocatalyst. Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 8%, the temperature of calcination is 100° C., the time of calcination (insulation) is 0.5 h, and the inert gas can be argon (Ar).
实施例3Example 3
该实施例提供了一种氧化铈负载铋纳米催化剂及其制备方法，具体的，该氧化铈负载铋纳米催化剂的制备方法包括以下步骤：This embodiment provides a cerium oxide-supported bismuth nanocatalyst and a preparation method thereof. Specifically, the preparation method of the cerium oxide-supported bismuth nanocatalyst includes the following steps:
(1)将2g的Ce(NO3)3·6H2O溶于超纯水中，利用超声波搅拌均匀，得到溶液A；(1) Dissolve 2g of Ce(NO3 )3 6H2 O in ultrapure water and stir evenly with ultrasonic waves to obtain solution A;
(2)往溶液A中添加800mg的NaBH4，搅拌均匀，进行还原反应60min，得到溶液B；(2) Add 800 mg of NaBH4 to solution A, stir evenly, and carry out reduction reaction for 60 minutes to obtain solution B;
(3)将溶液B依次进行离心、水洗、醇洗处理后，再置于70℃的温度下进行干燥处理，便可得到载体氧化铈(CeOx)；(3) The solution B is centrifuged, washed with water and washed with alcohol in sequence, and then dried at a temperature of 70° C. to obtain the carrier cerium oxide (CeOx );
(4)将800mg的载体氧化铈置于超纯水中，利用超声波搅拌均匀，得到溶液C；(4) Place 800 mg of carrier cerium oxide in ultrapure water, and stir evenly with ultrasonic waves to obtain solution C;
(5)往溶液C中添加1.6g的Bi(NO3)3·5H2O，利用超声波搅拌均匀，得到溶液D；(5) Add 1.6 g of Bi(NO3 )3 5H2 O to solution C, and stir evenly with ultrasonic waves to obtain solution D;
(6)将640mg的Na2CO3溶于超纯水中，利用超声波搅拌均匀，得到Na2CO3溶液；然后将Na2CO3溶液缓慢滴加到溶液D中，搅拌均匀，得到溶液E；其中，搅拌在室温下进行，搅拌的时间为120min；(6) Dissolve 640 mg of Na2 CO3 in ultrapure water, and stir evenly with ultrasonic waves to obtain a Na2 CO3 solution; then slowly add the Na2 CO3 solution dropwise into solution D, and stir evenly to obtain solution E ; Wherein, stirring is carried out at room temperature, and the time of stirring is 120min;
(7)将溶液E依次进行离心、水洗、醇洗处理后，再置于50℃的温度下进行真空干燥处理后，得到前驱体；(7) After the solution E is centrifuged, washed with water, and washed with alcohol in sequence, and then placed at a temperature of 50° C. for vacuum drying, the precursor is obtained;
(8)将前驱体置于惰性气体/H2混合气体中进行煅烧，即可得到氧化铈负载铋纳米催化剂。其中，惰性气体/H2混合气体中H2的体积浓度为12％，煅烧的温度为200℃，煅烧(保温)的时间为2h，惰性气体可选用氩气(Ar)。(8) The precursor is placed in an inert gas/H2 mixed gas for calcination to obtain a ceria-supported bismuth nanocatalyst. Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 12%, the temperature of calcination is 200° C., the time of calcination (insulation) is 2 h, and the inert gas can be argon (Ar).
实施例4Example 4
该实施例提供了一种上述实施例1制得的氧化铈负载铋纳米催化剂在电催化还原CO2产甲酸中的应用。具体的，该电催化还原CO2产甲酸的方法包括以下步骤：将实施例1制得的氧化铈负载铋纳米催化剂和导电炭黑(市售的XC-72炭黑)分散在水/乙醇混合溶液中后，再添加全氟磺酸型聚合物(市售的Nafion)进行混合，得到分散液；接着，将分散液滴加到碳布上形成工作电极，将Ag/AgCl和Pt网分别作为参比电极和对电极，将NaSO4溶液作为电解液；然后，在-1.4～-1.9Vvs.Ag/AgCl的电解电压下对CO2进行电解还原，得到甲酸。其中，所述的氧化铈负载铋纳米催化剂与导电炭黑的质量为5:1；所述水/乙醇混合溶液中水与乙醇的体积比为1:1；所述的氧化铈负载铋纳米催化剂与全氟磺酸型聚合物的质量体积比按照mg/μL计为1:10；所述NaSO4溶液的摩尔浓度为0.3M。制得的甲酸可以通过液相核磁共振进行检测，具体的，取1mL电解后的电解液，加入200μL D2O(含0.1μL DMSO)，摇匀，便可通过液相核磁共振对甲酸的含量进行检测。This embodiment provides an application of the cerium oxide-supported bismuth nanocatalyst prepared in the above-mentioned embodiment 1 in the production of formic acid by electrocatalytic reduction ofCO . Concrete, this electrocatalytic reduction COThe method for producing formic acid comprises the following steps: the cerium oxide supported bismuth nanocatalyst that embodiment 1 makes and conductive carbon black (commercially available XC-72 carbon black) are dispersed in water/ethanol mixing After entering the solution, add a perfluorosulfonic acid polymer (commercially available Nafion) and mix to obtain a dispersion; then, add the dispersion to the carbon cloth to form a working electrode, and use Ag/AgCl and Pt mesh as The reference electrode and the counter electrode use NaSO4 solution as the electrolyte; then, CO2 is electrolytically reduced at the electrolytic voltage of -1.4~-1.9Vvs.Ag/AgCl to obtain formic acid. Wherein, the quality of described cerium oxide-supported bismuth nanocatalyst and conductive carbon black is 5:1; The volume ratio of water and ethanol in the described water/ethanol mixed solution is 1:1; Described cerium oxide-supported bismuth nanocatalyst The mass volume ratio to the perfluorosulfonic acid polymer is 1:10 in mg/μL; the molar concentration of the NaSO4 solution is 0.3M. The prepared formic acid can be detected by liquid phase nuclear magnetic resonance. Specifically, take 1 mL of electrolyzed electrolyte, add 200 μL D2 O (containing 0.1 μL DMSO), shake well, and the content of formic acid can be determined by liquid phase nuclear magnetic resonance. to test.
实施例5Example 5
该实施例提供了一种上述实施例1制得的氧化铈负载铋纳米催化剂在电催化还原CO2产甲酸中的应用。具体的，该电催化还原CO2产甲酸的方法包括以下步骤：将实施例1制得的氧化铈负载铋纳米催化剂和导电炭黑(市售的XC-72炭黑)分散在水/乙醇混合溶液中后，再添加全氟磺酸型聚合物(市售的Nafion)进行混合，得到分散液；接着，将分散液滴加到碳布上形成工作电极，将Ag/AgCl和Pt网分别作为参比电极和对电极，将NaSO4溶液作为电解液；然后，在-1.4～-1.9V vs.Ag/AgCl的电解电压下对CO2进行电解还原，得到甲酸。其中，所述的氧化铈负载铋纳米催化剂与导电炭黑的质量为4:1；所述水/乙醇混合溶液中水与乙醇的体积比为0.8:1；所述的氧化铈负载铋纳米催化剂与全氟磺酸型聚合物的质量体积比按照mg/μL计为1:8；所述NaSO4溶液的摩尔浓度为0.1M。This embodiment provides an application of the cerium oxide-supported bismuth nanocatalyst prepared in the above-mentioned embodiment 1 in the production of formic acid by electrocatalytic reduction ofCO . Concrete, this electrocatalytic reduction COThe method for producing formic acid comprises the following steps: the cerium oxide supported bismuth nanocatalyst that embodiment 1 makes and conductive carbon black (commercially available XC-72 carbon black) are dispersed in water/ethanol mixing After entering the solution, add a perfluorosulfonic acid polymer (commercially available Nafion) and mix to obtain a dispersion; then, add the dispersion to the carbon cloth to form a working electrode, and use Ag/AgCl and Pt mesh as The reference electrode and the counter electrode use NaSO4 solution as the electrolyte; then, CO2 is electrolytically reduced under the electrolysis voltage of -1.4~-1.9V vs. Ag/AgCl to obtain formic acid. Wherein, the quality of described cerium oxide-supported bismuth nanocatalyst and conductive carbon black is 4:1; The volume ratio of water and ethanol in the described water/ethanol mixed solution is 0.8:1; Described cerium oxide-supported bismuth nanocatalyst The mass volume ratio to the perfluorosulfonic acid polymer is 1:8 in terms of mg/μL; the molar concentration of the NaSO4 solution is 0.1M.
实施例6Example 6
该实施例提供了一种上述实施例1制得的氧化铈负载铋纳米催化剂在电催化还原CO2产甲酸中的应用。具体的，该电催化还原CO2产甲酸的方法包括以下步骤：将实施例1制得的氧化铈负载铋纳米催化剂和导电炭黑(市售的XC-72炭黑)分散在水/乙醇混合溶液中后，再添加全氟磺酸型聚合物(市售的Nafion)进行混合，得到分散液；接着，将分散液滴加到碳布上形成工作电极，将Ag/AgCl和Pt网分别作为参比电极和对电极，将NaSO4溶液作为电解液；然后，在-1.4～-1.9V vs.Ag/AgCl的电解电压下对CO2进行电解还原，得到甲酸。其中，所述的氧化铈负载铋纳米催化剂与导电炭黑的质量为6:1；所述水/乙醇混合溶液中水与乙醇的体积比为1.2:1；所述的氧化铈负载铋纳米催化剂与全氟磺酸型聚合物的质量体积比按照mg/μL计为1:12；所述NaSO4溶液的摩尔浓度为0.3M。This embodiment provides an application of the cerium oxide-supported bismuth nanocatalyst prepared in the above-mentioned embodiment 1 in the production of formic acid by electrocatalytic reduction ofCO . Concrete, this electrocatalytic reduction COThe method for producing formic acid comprises the following steps: the cerium oxide supported bismuth nanocatalyst that embodiment 1 makes and conductive carbon black (commercially available XC-72 carbon black) are dispersed in water/ethanol mixing After entering the solution, add a perfluorosulfonic acid polymer (commercially available Nafion) and mix to obtain a dispersion; then, add the dispersion to the carbon cloth to form a working electrode, and use Ag/AgCl and Pt mesh as The reference electrode and the counter electrode use NaSO4 solution as the electrolyte; then, CO2 is electrolytically reduced under the electrolysis voltage of -1.4~-1.9V vs. Ag/AgCl to obtain formic acid. Wherein, the quality of described cerium oxide-supported bismuth nano-catalyst and conductive carbon black is 6:1; The volume ratio of water and ethanol in the described water/ethanol mixed solution is 1.2:1; Described cerium oxide-supported bismuth nano-catalyst The mass volume ratio to the perfluorosulfonic acid polymer is 1:12 in mg/μL; the molar concentration of the NaSO4 solution is 0.3M.
对比例1Comparative example 1
该对比例提供了一种载体氧化铈(CeOx)，该载体氧化铈的制备方法包括以下步骤：This comparative example provides a kind of support cerium oxide (CeOx ), the preparation method of this support cerium oxide comprises the following steps:
(1)将1.5g的Ce(NO3)3·6H2O溶于超纯水中，利用超声波搅拌均匀，得到溶液A；(1) Dissolve 1.5 g of Ce(NO3 )3 6H2 O in ultrapure water, and stir evenly with ultrasonic waves to obtain solution A;
(2)往溶液A中添加400mg的NaBH4，搅拌均匀，进行还原反应40min，得到溶液B；(2) Add 400 mg of NaBH4 to solution A, stir evenly, and carry out reduction reaction for 40 minutes to obtain solution B;
(3)将溶液B依次进行离心、水洗、醇洗处理后，再置于60℃的温度下进行干燥处理，便可得到载体氧化铈(CeOx)。(3) The solution B is centrifuged, washed with water and washed with alcohol in sequence, and then dried at a temperature of 60° C. to obtain the carrier cerium oxide (CeOx ).
利用X射线粉末衍射对上述对比例1制得的载体氧化铈(CeOx)以及实施例1制得的氧化铈负载铋纳米催化剂(Bi/CeOx)的结晶性进行检测，检测结果如附图1所示。其中，载体氧化铈为低结晶性的结构，负载铋之后得到的氧化铈负载铋纳米催化剂仍保持较弱的结晶性。Utilize X-ray powder diffraction to detect the crystallinity of the carrier cerium oxide (CeOx ) and the cerium oxide-supported bismuth nanocatalyst (Bi/CeOx ) prepared in the above-mentioned comparative example 1 made in Example 1, and the detection results are shown in the accompanying drawings 1. Wherein, the carrier cerium oxide has a structure of low crystallinity, and the cerium oxide-supported bismuth nanocatalyst obtained after loading bismuth still maintains relatively weak crystallinity.
对比例2Comparative example 2
该对比例提供了一种纯铋催化剂(pure Bi)，该纯铋催化剂的制备方法包括以下步骤：This comparative example provides a kind of pure bismuth catalyst (pure Bi), the preparation method of this pure bismuth catalyst comprises the following steps:
(1)将1.5g的Bi(NO3)3·5H2O溶于超纯水中，利用超声波搅拌均匀，得到溶液F；(1) Dissolve 1.5g of Bi(NO3 )3 ·5H2 O in ultrapure water and stir evenly with ultrasonic waves to obtain solution F;
(2)将400mg的Na2CO3溶于超纯水中，利用超声波搅拌均匀，得到Na2CO3溶液；然后将Na2CO3溶液缓慢滴加到溶液F中，搅拌均匀，得到溶液G；其中，搅拌在室温下进行，搅拌的时间为90min；(2) Dissolve 400mg of Na2 CO3 in ultrapure water, and stir evenly with ultrasonic waves to obtain a Na2 CO3 solution; then slowly add the Na2 CO3 solution dropwise into solution F, and stir evenly to obtain solution G ; Wherein, stirring is carried out at room temperature, and the time of stirring is 90min;
(3)将溶液G依次进行离心、水洗、醇洗处理后，再置于40℃的温度下进行真空干燥处理后，得到前驱体；(3) After the solution G is centrifuged, washed with water, and washed with alcohol in sequence, and then placed at a temperature of 40° C. for vacuum drying, the precursor is obtained;
(4)将前驱体置于惰性气体/H2混合气体中进行煅烧，即可得到纯铋催化剂(pureBi)。其中，惰性气体/H2混合气体中H2的体积浓度为10％，煅烧的温度为150℃，煅烧(保温)的时间为1h，惰性气体可选用氩气(Ar)。(4) The precursor is placed in an inert gas/H2 mixed gas for calcination to obtain a pure bismuth catalyst (pureBi). Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 10%, the temperature of calcination is 150° C., the time of calcination (insulation) is 1 h, and the inert gas can be argon (Ar).
对比例3Comparative example 3
该对比例提供了一种二氧化铈负载的铋纳米催化剂(Bi/CeO2)，该催化剂的制备方法包括以下步骤：This comparative example provides a bismuth nanocatalyst (Bi/CeO2 ) supported by ceria, and the preparation method of the catalyst comprises the following steps:
(1)将1g的Ce(NO3)3·6H2O溶于超纯水中，利用超声波搅拌均匀，得到溶液H，其中，超声频率为40kHz；(1) Dissolve 1 g of Ce(NO3 )3 ·6H2 O in ultrapure water, and stir evenly with ultrasonic waves to obtain solution H, wherein the ultrasonic frequency is 40 kHz;
(2)将溶液H缓慢加入到NaOH溶液中，搅拌均匀，得到得到溶液I；其中，NaOH溶液浓度为6mol/L，搅拌在室温下进行，搅拌的时间为30min；(2) Solution H is slowly added to the NaOH solution, stirred evenly to obtain solution I; wherein, the concentration of the NaOH solution is 6mol/L, and the stirring is carried out at room temperature, and the stirring time is 30min;
(3)将溶液I转移至高温高压反应釜中，经过水热反应，得到溶液J；其中，保温温度为100℃，保温时间为24h；(3) Transfer the solution I to a high-temperature and high-pressure reaction kettle, and undergo a hydrothermal reaction to obtain a solution J; wherein, the holding temperature is 100° C., and the holding time is 24 hours;
(4)将溶液J依次进行离心、水洗、醇洗处理后，再置于40℃的温度下进行干燥处理，便可得到载体二氧化铈(CeO2)；(4) The solution J is centrifuged, washed with water and washed with alcohol in sequence, and then dried at a temperature of 40°C to obtain the carrier cerium oxide (CeO2 );
(5)将400mg的CeO2置于超纯水中，利用超声波搅拌均匀，得到溶液K；(5 ) 400mg of CeO2 is placed in ultrapure water, and stirred evenly by ultrasonic waves to obtain solution K;
(6)往溶液K中添加1.5g的Bi(NO3)3·5H2O，利用超声波搅拌均匀，得到溶液L；(6) Add 1.5 g of Bi(NO3 )3 5H2 O to solution K, and stir evenly with ultrasonic waves to obtain solution L;
(7)将400mg的Na2CO3溶于超纯水中，利用超声波搅拌均匀，得到Na2CO3溶液；然后将Na2CO3溶液缓慢滴加到溶液L中，搅拌均匀，得到溶液M；其中，搅拌在室温下进行，搅拌的时间为90min；(7) Dissolve 400mg of Na2 CO3 in ultrapure water, and stir evenly with ultrasonic waves to obtain a Na2 CO3 solution; then slowly add the Na2 CO3 solution dropwise into solution L, and stir evenly to obtain solution M ; Wherein, stirring is carried out at room temperature, and the time of stirring is 90min;
(8)将溶液M依次进行离心、水洗、醇洗处理后，再置于40℃的温度下进行真空干燥处理后，得到前驱体；(8) The solution M is sequentially centrifuged, washed with water, and washed with alcohol, and then placed at a temperature of 40° C. for vacuum drying to obtain a precursor;
(9)将前驱体置于惰性气体/H2混合气体中进行煅烧，即可得到二氧化铈负载铋纳米催化剂(Bi/CeO2)。其中，惰性气体/H2混合气体中H2的体积浓度为10％，煅烧的温度为150℃，煅烧(保温)的时间为1h，惰性气体可选用氩气(Ar)。(9) Calcining the precursor in an inert gas/H2 mixed gas to obtain a ceria-supported bismuth nanocatalyst (Bi/CeO2 ). Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 10%, the temperature of calcination is 150° C., the time of calcination (insulation) is 1 h, and the inert gas can be argon (Ar).
另外，按照实施例4提供的电催化还原CO2产甲酸的方法，分别用上述对比例2得到纯铋催化剂(pure Bi)以及对比例3得到的二氧化铈负载铋纳米催化剂(Bi/CeO2)代替氧化铈负载铋纳米催化剂对CO2进行电解还原制得甲酸。In addition, according to the electrocatalytic reduction of CO provided in Example4 The method for generating formic acid, respectively using the above comparative example 2 to obtain a pure bismuth catalyst (pure Bi) and the ceria-supported bismuth nanocatalyst (Bi/CeO ) obtained in comparative example3 ) instead of ceria-supported bismuth nanocatalysts for the electrolytic reduction ofCO2 to produce formic acid.
参考附图2、3、9，图2为实施例1制得的氧化铈负载铋纳米催化剂分别在惰性气体以及CO2饱和的Na2SO4电解液中的线性伏安曲线；图3为对比例2制得的纯铋催化剂分别在惰性气体以及CO2饱和的Na2SO4电解液中的线性伏安曲线；图9为对比例3制得的Bi/CeO2催化剂分别在惰性气体以及CO2饱和的Na2SO4电解液中的线性伏安曲线。从图中可以看出，实施例1制得的氧化铈负载铋纳米催化剂对CO2具有更强的还原作用。With reference to accompanying drawing 2,3,9, Fig. 2 is that the cerium oxide supported bismuth nanocatalyst that embodiment 1 makes is respectively in inert gas and CO2 saturated Na2 SO4 linear voltammetry curves in electrolytic solution; Fig. 3 is for The linear voltammetry curves of the pure bismuth catalyst prepared in ratio 2 in inert gas and CO2 saturated Na2 SO4 electrolyte; Fig. 9 shows the Bi/CeO2 catalyst prepared in comparative example 3 in inert gas and CO2 Linear voltammetry curves in saturatedNa2SO4 electrolyte. It can be seen from the figure that the ceria-supported bismuth nanocatalyst prepared in Example1 has a stronger reduction effect on CO.
参照附图4、5、10，图4为实施例1制得的氧化铈负载铋纳米催化剂(Bi/CeOx)在常温常压CO2气氛下的Na2SO4电解液中不同电解电压下的电流(Current density)-时间(Time)曲线；图5为对比例2中pure Bi催化剂在常温常压CO2气氛下的Na2SO4电解液中不同电压下的电流-时间曲线；图10为对比例3中Bi/CeO2催化剂在常温常压CO2气氛下的Na2SO4电解液中不同电压下的电流-时间曲线；电流-时间(I-t)曲线结果表明，在各个电解电压(Potential)下，相对于对比例2得到的pure Bi催化剂以及对比例3制得的Bi/CeO2催化剂，实施例1制得的Bi/CeOx催化剂所显示的电流都更大，具有明显的优势，其对CO2具有更强的还原作用。With reference to accompanying drawing 4,5,10, Fig. 4 is the cerium oxide supported bismuth nano-catalyst (Bi/CeOx ) that embodiment 1 makes under normal temperature and pressure CO2 in Na2 SO4 electrolyte under different electrolytic voltages The current (Current density)-time (Time) curve; Fig. 5 is the current-time curve under different voltages in the Na2 SO4 electrolyte of pure Bi catalyst in the comparative example 2 under normal temperature and pressure CO2 atmosphere; Fig. 10 Be Bi/CeO in the comparative example3 Catalyst is at normal temperature and pressureCO Under the Na SO under the atmosphere Under the current- time curve of different voltages in the electrolytic solution; Current- time (It) curve result shows, at each electrolysis voltage ( Potential), compared with the pure Bi catalyst obtained in Comparative Example2 and the Bi/CeO catalyst obtained in Comparative Example 3, the Bi/CeO catalyst obtained in Example1 has a larger electric current, which has obvious advantages , which has a stronger reducing effect onCO2 .
参照附图6-7，图6为实施例1制得的Bi/CeOx催化剂、对比例2制得的pure Bi催化剂以及对比例3制得的Bi/CeO2催化剂在常温常压不同电解电压下的甲酸的法拉第效率(FE)对比结果；图7为实施例1制得的Bi/CeOx催化剂、对比例2制得的pure Bi催化剂以及对比例3制得的Bi/CeO2催化剂在常温常压不同电解电压下的甲酸的生产速率(Productrate)的对比结果。从中可以看出，在各个电解电压(Potential)下，相对于对比例2得到的pure Bi催化剂以及对比例3制得的Bi/CeO2催化剂，实施例1制得的Bi/CeOx催化剂不仅具有极高的生产速率，并且还能保持较高的法拉第效率。其中，在-1.7V vs.Ag/AgCl处，实施例4的电催化还原CO2产甲酸的法拉第效率(FE)为98％，达到最高，甲酸生产速率达到1800μmol·h-1·cm-2；在-1.8V vs.Ag/AgCl处，实施例4的电催化还原CO2产甲酸的生产速率为2600μmol·h-1·cm-2，达到最大值，甲酸的FE为92％。由此可以知道，本发明实施例提供的氧化铈负载铋纳米催化剂的催化活性远高于目前已经报道的S-In2O3derived In(生产速率：生产速率：1449μmol·h-1·cm-2，FE：93％)、Sn(S)/Au needles(生产速率：957μmol·h-1·cm-2，FE：93％)、porous SnO2(生产速率：811μmol·h-1·cm-2，FE：87％)、Pd nanop惰性气体ticles(生产速率：398μmol·h-1·cm-2，FE：97％)等催化剂。With reference to accompanying drawing 6-7, Fig. 6 is the Bi/CeOx catalyst that embodiment 1 makes, the pure Bi catalyst that comparative example 2 makes and the Bi/CeO that comparative example3 makes catalyzer at normal temperature and pressure Different electrolysis voltage The Faraday efficiency (FE) contrast result of formic acid under; Fig. 7 is the Bi/CeOx catalyst that embodiment 1 makes, the pure Bi catalyst that comparative example 2 makes and the Bi/CeO that comparative example3 makes catalyzer at normal temperature Comparison results of formic acid production rate (Productrate) under different electrolysis voltages at normal pressure. It can be seen that, at each electrolysis voltage (Potential), compared to the pure Bi catalyst obtained in Comparative Example2 and the Bi/CeO catalyst obtained in Comparative Example 3, the Bi/CeO catalyst obtained in Example1 not only has Extremely high production rates, while maintaining high Faradaic efficiency. Among them, at -1.7V vs.Ag/AgCl, the faradaic efficiency (FE) of the electrocatalytic reduction ofCO2 to produce formic acid in Example 4 was 98%, reaching the highest, and the production rate of formic acid reached 1800μmol·h-1 ·cm-2 ; At -1.8V vs. Ag/AgCl, the production rate of formic acid produced by the electrocatalytic reduction of CO2 in Example 4 was 2600 μmol·h-1 ·cm-2 , reaching the maximum value, and the FE of formic acid was 92%. It can be seen from this that the catalytic activity of the cerium oxide-supported bismuth nanocatalyst provided by the embodiment of the present invention is much higher than that of the S-In2 O3 derived In that has been reported so far (production rate: production rate: 1449 μmol h-1 cm- 2 , FE: 93%), Sn(S)/Au needles (production rate: 957μmol·h-1 ·cm-2 , FE: 93%), porous SnO2 (production rate: 811μmol·h-1 ·cm- 2 , FE: 87%), Pd nanop inert gas ticles (production rate: 398 μmol·h-1 ·cm-2 , FE: 97%) and other catalysts.
此外，参照附图8，实施例1制得的Bi/CeOx催化剂在常温常压CO2气氛下的Na2SO4电解液中-1.7V vs.Ag/AgCl处的长时间稳定性曲线；从中可以知道，在电催化过程的37h内均维持电流稳定，并且甲酸的FE可在34h内保持在97％左右，具有优异的稳定性。In addition, referring to accompanying drawing 8, the Bi/CeOx catalyst prepared in Example 1 is in the Na2 SO4 electrolytic solution under normal temperature and pressure CO2 atmosphere -1.7V vs.Ag/AgCl long-term stability curve; It can be seen that the current is stable within 37 hours of the electrocatalytic process, and the FE of formic acid can be maintained at about 97% within 34 hours, which has excellent stability.
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.
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| CN201910836526.6ACN110538650B (en) | 2019-09-05 | 2019-09-05 | A kind of cerium oxide supported bismuth nano-catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111564641A (en)* | 2020-05-25 | 2020-08-21 | 中自环保科技股份有限公司 | Preparation method of catalyst layer in membrane electrode |
| CN113463119A (en)* | 2021-06-15 | 2021-10-01 | 华东理工大学 | Bismuth-based-silver-based composite material and preparation method and application thereof |
| CN113755878A (en)* | 2021-08-31 | 2021-12-07 | 北京大学深圳研究生院 | A kind of preparation method and application of bismuth-based catalyst |
| CN114717583A (en)* | 2022-04-19 | 2022-07-08 | 浙江师范大学 | A kind of preparation method and application of bismuth nanosheet supported palladium bimetallic catalyst |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150057149A1 (en)* | 2013-08-23 | 2015-02-26 | Basf Corporation | Catalysts for Oxidation of Carbon Monoxide and/or Volatile Organic Compounds |
| CN109482172A (en)* | 2018-12-29 | 2019-03-19 | 陕西师范大学 | A kind of degradation NOxBi/CeO2Composite photo-catalyst and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150057149A1 (en)* | 2013-08-23 | 2015-02-26 | Basf Corporation | Catalysts for Oxidation of Carbon Monoxide and/or Volatile Organic Compounds |
| CN109482172A (en)* | 2018-12-29 | 2019-03-19 | 陕西师范大学 | A kind of degradation NOxBi/CeO2Composite photo-catalyst and preparation method thereof |
| Title |
|---|
| ADHIDESH S.KUMAWAT ET AL.: ""Comparative study of carbon supported Pb,Bi and Sn catalysts for electroreduction of carbon dioxide in alkaline medium"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》* |
| CONGYI WU ET AL.: ""Highly efficient hydrogenation of carbon dioxide to methyl formate over supported gold catalysts"", 《GREEN CHEMISTRY》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111564641A (en)* | 2020-05-25 | 2020-08-21 | 中自环保科技股份有限公司 | Preparation method of catalyst layer in membrane electrode |
| CN113463119A (en)* | 2021-06-15 | 2021-10-01 | 华东理工大学 | Bismuth-based-silver-based composite material and preparation method and application thereof |
| CN113463119B (en)* | 2021-06-15 | 2022-09-09 | 华东理工大学 | Bismuth-based-silver-based composite material and preparation method and application thereof |
| CN113755878A (en)* | 2021-08-31 | 2021-12-07 | 北京大学深圳研究生院 | A kind of preparation method and application of bismuth-based catalyst |
| CN114717583A (en)* | 2022-04-19 | 2022-07-08 | 浙江师范大学 | A kind of preparation method and application of bismuth nanosheet supported palladium bimetallic catalyst |
| Publication number | Publication date |
|---|---|
| CN110538650B (en) | 2020-08-14 |
| Publication | Publication Date | Title |
|---|---|---|
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