技术领域Technical Field
本发明涉及贵金属纳米催化剂技术领域，具体涉及一种利用氢溢流原位合成PtCo双金属磁性纳米催化剂高效催化氨硼烷水解产氢的方法。The invention relates to the technical field of precious metal nanocatalysts, and in particular to a method for in-situ synthesizing a PtCo bimetallic magnetic nanocatalyst by hydrogen overflow to efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen.
背景技术Background Art
近年来，氢能源作为一种二次清洁能源，以其来源广泛、对环境零污染、燃烧值高等优势成为首选的新型清洁能源，高效的氢气储运技术是实现氢能源大规模应用的关键。在众多储氢材料中，氨硼烷以储氢含量较高(19.6wt％)、无毒、室温下稳定以及对环境友好等优点而备受关注。开发高效的脱氢催化剂是促进氨硼烷大规模应用的关键因素。In recent years, hydrogen energy, as a secondary clean energy, has become the preferred new clean energy due to its wide sources, zero pollution to the environment, and high calorific value. Efficient hydrogen storage and transportation technology is the key to realizing large-scale application of hydrogen energy. Among many hydrogen storage materials, ammonia borane has attracted much attention due to its high hydrogen storage content (19.6wt%), non-toxicity, stability at room temperature, and environmental friendliness. The development of efficient dehydrogenation catalysts is a key factor in promoting the large-scale application of ammonia borane.
目前，在利用催化剂催化氨硼烷产氢时，常用的催化剂主要是贵金属-非贵金属复合催化剂，然而在合成这类双金属催化剂过程中，非贵金属在合成过程中极易被空气所氧化，从而严重影响催化剂催化性能。因此，亟需开发一种能够有效规避合成贵金属-非贵金属复合催化剂过程中非贵金属氧化问题的催化剂及制备方法。At present, when using catalysts to catalyze the production of hydrogen from ammonia borane, the commonly used catalysts are mainly precious metal-non-precious metal composite catalysts. However, in the process of synthesizing such bimetallic catalysts, the non-precious metals are easily oxidized by air during the synthesis process, which seriously affects the catalytic performance of the catalyst. Therefore, it is urgent to develop a catalyst and preparation method that can effectively avoid the problem of non-precious metal oxidation during the synthesis of precious metal-non-precious metal composite catalysts.
发明内容Summary of the invention
本发明意在提供一种利用氢溢流原位合成PtCo双金属磁性纳米催化剂高效催化氨硼烷水解产氢的方法，以解决现有技术中催化氨硼烷产氢催化剂合成过程中非贵金属易被氧化的问题。The present invention aims to provide a method for in-situ synthesizing PtCo bimetallic magnetic nanocatalysts by hydrogen overflow to efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen, so as to solve the problem that non-precious metals are easily oxidized during the synthesis of catalysts for catalyzing hydrogen production from ammonia borane in the prior art.
为达到上述目的，本发明采用如下技术方案：一种利用氢溢流原位合成PtCo双金属磁性纳米催化剂高效催化氨硼烷水解产氢的方法，双金属磁性纳米催化剂为Pt/Co-MOF原位衍生的PtCo/C。To achieve the above object, the present invention adopts the following technical scheme: a method for in-situ synthesis of PtCo bimetallic magnetic nanocatalyst using hydrogen overflow to efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen, wherein the bimetallic magnetic nanocatalyst is PtCo/C derived in-situ from Pt/Co-MOF.
优选的，作为一种改进，Pt/Co-MOF纳米催化剂的制备方法，包括如下步骤：Preferably, as an improvement, the preparation method of Pt/Co-MOF nanocatalyst comprises the following steps:
步骤一、对苯二甲酸与Co(NO3)2·6H2O在室温下超声合成Co-MOF；Step 1, terephthalic acid and Co(NO3 )2 ·6H2 O are ultrasonically synthesized Co-MOF at room temperature;
步骤二、Co-MOF与H2PtCl6反应得到Pt/Co-MOF。Step 2: Co-MOF reacts with H2 PtCl6 to obtain Pt/Co-MOF.
优选的，作为一种改进，步骤一中，将苯二甲酸溶解在DMF、去离子水和乙醇的混合溶剂中，而后加入Co(NO3)2·6H2O，搅拌条件下加入TEA形成胶体悬浮液，然后室温下密封超声处理。Preferably, as an improvement, in step 1, phthalic acid is dissolved in a mixed solvent of DMF, deionized water and ethanol, and then Co(NO3 )2 ·6H2 O is added, and TEA is added under stirring to form a colloidal suspension, which is then sealed and ultrasonically treated at room temperature.
优选的，作为一种改进，步骤一中，混合溶剂中，DMF、去离子水和乙醇的质量比为10～30:1～3:1～3。Preferably, as an improvement, in step 1, in the mixed solvent, the mass ratio of DMF, deionized water and ethanol is 10-30:1-3:1-3.
优选的，作为一种改进，步骤一中，超声处理时间为4～8h。Preferably, as an improvement, in step 1, the ultrasonic treatment time is 4 to 8 hours.
优选的，作为一种改进，步骤一中，超声处理结束后，用乙醇洗涤离心并烘干得到Co-MOF。Preferably, as an improvement, in step 1, after the ultrasonic treatment, the Co-MOF is obtained by washing with ethanol, centrifuging and drying.
优选的，作为一种改进，步骤二中，将Co-MOF分散乙醇中，加入H2PtCl6溶液后，60～70℃下加热搅拌4～8h，最后用乙醇洗涤离心并烘干得到Pt/Co-MOF。Preferably, as an improvement, in step 2, the Co-MOF is dispersed in ethanol, H2 PtCl6 solution is added, and then heated and stirred at 60-70° C. for 4-8 hours, and finally washed with ethanol, centrifuged and dried to obtain Pt/Co-MOF.
优选的，作为一种改进，步骤二中，Co-MOF与乙醇的质量比为0.2～2:1。Preferably, as an improvement, in step 2, the mass ratio of Co-MOF to ethanol is 0.2 to 2:1.
优选的，作为一种改进，步骤一、步骤二中，洗涤离心的次数均为三次，离心的转速均为8000～14000r/min。Preferably, as an improvement, in step 1 and step 2, the washing centrifugation is performed three times, and the centrifugal speed is 8000-14000 r/min.
优选的，作为一种改进，步骤一、步骤二中，烘干至催化剂成片状。Preferably, as an improvement, in step one and step two, the catalyst is dried until it becomes flakes.
本方案的原理及优点是：实际应用时，本技术方案中，针对非贵金属在合成过程中容易被氧化，提出了一种利用氢溢流原位合成PtCo双金属磁性纳米催化剂提高氨硼烷水解产氢性能的新方法：利用乙醇的弱还原性在二维Co-MOF上负载金属Pt形成Pt/Co-MOF纳米催化剂，不会破坏Co-MOF的结构；在利用Pt/Co-MOF催化氨硼烷水解产氢时，利用贵金属Pt解离氨硼烷产生活性氢物种可以溢流到Co-MOF上，破坏MOF结构的同时将MOF结构中的Co2+物种还原为金属Co，产生新的PtCo/C双金属磁性纳米催化剂，催化氨硼烷高效产氢。通过原位还原获得PtCo双金属催化剂的方法可以有效避免非贵金属在合成过程中被空气氧化，通过原位合成的手法简化催化剂合成步骤，实现合成催化剂的同时高效催化氨硼烷产氢，解决了合成金属催化剂过程中依赖于惰性气体保护的问题。The principle and advantages of this scheme are: in practical application, in this technical scheme, in view of the fact that non-precious metals are easily oxidized during the synthesis process, a new method for in-situ synthesis of PtCo bimetallic magnetic nanocatalysts using hydrogen overflow to improve the performance of hydrogen production by hydrolysis of ammonia borane is proposed: the weak reducibility of ethanol is used to load metal Pt on the two-dimensional Co-MOF to form a Pt/Co-MOF nanocatalyst, which will not destroy the structure of Co-MOF; when using Pt/Co-MOF to catalyze the hydrolysis of ammonia borane to produce hydrogen, the noble metal Pt is used to dissociate ammonia borane to produce active hydrogen species, which can overflow onto Co-MOF, destroying the MOF structure while reducing the Co2+ species in the MOF structure to metal Co, producing a new PtCo/C bimetallic magnetic nanocatalyst, catalyzing ammonia borane to produce hydrogen efficiently. The method of obtaining a PtCo bimetallic catalyst by in-situ reduction can effectively avoid the oxidation of non-precious metals by air during the synthesis process, simplify the catalyst synthesis steps by in-situ synthesis techniques, and achieve the synthesis of catalysts while efficiently catalyzing ammonia borane to produce hydrogen, solving the problem of relying on inert gas protection during the synthesis of metal catalysts.
此外，发明人在对Pt/Co-MOF纳米催化剂的制备工艺进行优化的过程中，不同于现有技术中常用的水热合成工艺，创造性的采用室温下超声合成的方法，降低了合成的难度，简化了合成方法。并且，现有技术中，通常利用NaBH4、高温H2还原等方式在Co-MOF上负载Pt，很容易破坏Co-MOF的结构，这种非原位还原方式获得的PtCo双金属催化剂在转移过程中很容易被氧化。而本方案中，利用MOF作为载体，不需要提前进行预处理(现有技术中大多是高温锻造或强还原剂将MOF转化为碳)，而是利用贵金属解离氨硼烷产生的氢溢流效应原位将MOF结构后转变为碳载体，不仅能够保证Pt/Co-MOF纳米催化剂高的催化活性，而且在稳定性测试中，Pt/Co-MOF纳米催化剂同样兼具较好的催化稳定性，这在行业内具有重要意义。In addition, in the process of optimizing the preparation process of Pt/Co-MOF nanocatalyst, the inventor creatively adopts the method of ultrasonic synthesis at room temperature, which is different from the hydrothermal synthesis process commonly used in the prior art, reduces the difficulty of synthesis and simplifies the synthesis method. In addition, in the prior art, Pt is usually loaded on Co-MOF by usingNaBH4 , high temperatureH2 reduction and other methods, which easily destroys the structure of Co-MOF. The PtCo bimetallic catalyst obtained by this non-in-situ reduction method is easily oxidized during the transfer process. In this scheme, MOF is used as a carrier, and there is no need to pre-treat in advance (mostly high temperature forging or strong reducing agent converts MOF into carbon in the prior art), but the hydrogen overflow effect generated by the dissociation of noble metal ammonia borane is used to convert the MOF structure into a carbon carrier in situ, which can not only ensure the high catalytic activity of Pt/Co-MOF nanocatalyst, but also in the stability test, Pt/Co-MOF nanocatalyst also has good catalytic stability, which is of great significance in the industry.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例中Co/MOF、Pt/Co-MOF、Pt/Co-MOF-1和Pt/Ni-MOF催化活性对比图。FIG1 is a comparison chart of the catalytic activities of Co/MOF, Pt/Co-MOF, Pt/Co-MOF-1 and Pt/Ni-MOF in the embodiments of the present invention.
图2为本发明实施例中Pt/ZIF-67、Pt/ZIF-8、Pt1％/ZIF-67和Pt1％/ZIF-8催化活性对比图。FIG2 is a comparative diagram of the catalytic activities of Pt/ZIF-67, Pt/ZIF-8, Pt1% /ZIF-67 and Pt1% /ZIF-8 in the examples of the present invention.
图3为本发明实施例中Pt/Co-MOF第一次与第二次反应性能对比图。FIG3 is a comparison chart of the first and second reaction performances of Pt/Co-MOF in an embodiment of the present invention.
图4为本发明实施例中NaBH4和H2预处理与Pt/Co-MOF第二次的反应性能对比图。FIG4 is a comparison chart of the reaction performance of NaBH4 and H2 pretreatment and the second reaction of Pt/Co-MOF in an embodiment of the present invention.
图5为Pt/Co-MOF催化反应前透射电镜图及EDX光谱图。Figure 5 is a transmission electron microscope image and EDX spectrum of Pt/Co-MOF before catalytic reaction.
图6为Pt/Co-MOF催化反应后透射电镜图及EDX光谱图。Figure 6 shows the transmission electron microscope image and EDX spectrum of Pt/Co-MOF after catalytic reaction.
具体实施方式DETAILED DESCRIPTION
下面通过具体实施方式进一步详细说明，但本发明的实施方式不限于此。若未特别指明，下述实施方式所用的技术手段为本领域技术人员所熟知的常规手段；所用的实验方法均为常规方法；所用的材料、试剂等，均可从商业途径得到。The following is further described in detail through specific implementations, but the implementations of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following implementations are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents, etc. used can all be obtained from commercial channels.
方案总述：Program Overview:
一种利用氢溢流原位合成PtCo双金属磁性纳米催化剂高效催化氨硼烷水解产氢的方法，包括如下步骤：A method for in-situ synthesis of PtCo bimetallic magnetic nanocatalysts by hydrogen overflow to efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen comprises the following steps:
步骤一、制备Co-MOF：称取125mg对苯二甲酸溶解在30mL DMF、2mL去离子水和2mL乙醇中。然后在上述溶液加入220mg Co(NO3)2·6H2O，在剧烈搅拌下快速注入1mL TEA，使其形成均匀的胶体悬浮液，密封后超声处理6h。随后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h，获得Co-MOF。Step 1, preparation of Co-MOF: Weigh 125 mg of terephthalic acid and dissolve it in 30 mL of DMF, 2 mL of deionized water and 2 mL of ethanol. Then add 220 mg of Co(NO3 )2 ·6H2 O to the above solution, quickly inject 1 mL of TEA under vigorous stirring to form a uniform colloidal suspension, seal it and treat it by ultrasound for 6 hours. Then wash it with ethanol and centrifuge it at 10000 r/min for three times, then dry it at 65°C for 12 hours to obtain Co-MOF.
步骤二、制备Pt/Co-MOF：称取120mg Co-MOF均匀分散在120mL乙醇中，加入12.2μLH2PtCl6(0.1M)溶液，搅拌15min后在65℃下继续加热搅拌5h。最后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h后制得Pt/Co-MOF。Step 2, preparation of Pt/Co-MOF: 120 mg Co-MOF was weighed and uniformly dispersed in 120 mL ethanol, 12.2 μL H2 PtCl6 (0.1 M) solution was added, and the mixture was stirred for 15 min and heated and stirred at 65°C for 5 h. Finally, the mixture was washed with ethanol and centrifuged at 10,000 r/min for three times, and dried at 65°C for 12 h to obtain Pt/Co-MOF.
步骤三、催化氨硼烷水解：称取20mg制备好的Pt/Co-MOF加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水进行反应。Step 3: Catalytic hydrolysis of ammonia borane: Weigh 20 mg of the prepared Pt/Co-MOF into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir evenly, then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane to react.
实验检测方法：Experimental detection method:
对氨硼烷水解产氢反应采用排水法进行测试：在常压下，将一定量的催化剂(20mg)放入25mL的密闭的圆底烧瓶中浸入水浴中以控制反应温度，加入4mL去离子水充分搅拌分散均匀。再把30.8mg(1mmol)氨硼烷溶解在1mL去离子水后加入圆底烧瓶，反应开始并计时。用一个带刻度充满水的U型管用来检测产生氢气的体积。随着反应的进行，记录U型管的刻度(产氢体积)随反应时间的变化。The water displacement method was used to test the hydrogen production reaction of ammonia borane hydrolysis: Under normal pressure, a certain amount of catalyst (20 mg) was placed in a 25 mL sealed round-bottom flask and immersed in a water bath to control the reaction temperature. 4 mL of deionized water was added and stirred to disperse evenly. Then 30.8 mg (1 mmol) of ammonia borane was dissolved in 1 mL of deionized water and added to the round-bottom flask. The reaction started and the timing was started. A U-shaped tube filled with water with a scale was used to detect the volume of hydrogen produced. As the reaction proceeded, the scale of the U-shaped tube (hydrogen production volume) was recorded as the reaction time changed.
实施例1Example 1
一种利用氢溢流原位合成PtCo双金属磁性纳米催化剂高效催化氨硼烷水解产氢的方法，包括如下步骤：A method for in-situ synthesis of PtCo bimetallic magnetic nanocatalysts by hydrogen overflow to efficiently catalyze the hydrolysis of ammonia borane to produce hydrogen comprises the following steps:
步骤一、称取125mg对苯二甲酸溶解在30mL DMF、2mL去离子水和2mL乙醇中。然后在上述溶液加入220mg Co(NO3)2·6H2O，在剧烈搅拌下快速注入1mL TEA，使其形成均匀的胶体悬浮液，密封后超声处理6h。随后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h。称取120mg Co-MOF均匀分散在120mL乙醇中，加入12.2μL H2PtCl6(0.1M)溶液，搅拌15min后在65℃下继续加热搅拌5h。最后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h后制得Pt/Co-MOF。Step 1: Weigh 125 mg of terephthalic acid and dissolve it in 30 mL of DMF, 2 mL of deionized water and 2 mL of ethanol. Then add 220 mg of Co(NO3 )2 ·6H2 O to the above solution, quickly inject 1 mL of TEA under vigorous stirring to form a uniform colloidal suspension, seal and ultrasonicate for 6 hours. Then wash and centrifuge three times with ethanol at 10000 r/min and dry at 65°C for 12 hours. Weigh 120 mg of Co-MOF and evenly disperse it in 120 mL of ethanol, add 12.2 μL of H2 PtCl6 (0.1M) solution, stir for 15 minutes and continue heating and stirring at 65°C for 5 hours. Finally, wash and centrifuge three times with ethanol at 10000 r/min and dry at 65°C for 12 hours to obtain Pt/Co-MOF.
步骤二、称取20mg制备好的Pt/Co-MOF加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。基于Pt原子总量(负载量为0.2％)计算出反应的转化效率TOF值为3400molH2·molPt·min-1。Step 2: Weigh 20 mg of the prepared Pt/Co-MOF into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir evenly. Then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane and start the reaction and time it. The TOF value of the reaction is calculated to be 3400 molH2 ·molPt ·min-1 based on the total amount of Pt atoms (loading amount is 0.2%).
步骤三、反应一次后催化剂被彻底还原成PtCo/C，再次加入相同含量的氨硼烷后计算出反应的转化效率TOF为4219molH2·molPt·min-1。Step 3: After one reaction, the catalyst was completely reduced to PtCo/C. After adding the same amount of ammonia borane again, the conversion efficiency TOF of the reaction was calculated to be 4219 molH2 ·molPt ·min-1 .
实施例2Example 2
本实施例与实施例1的不同之处在于：本实施例中DMF、去离子水和乙醇的质量比为30:1:1；密封后超声处理时间为4h；Co-MOF与乙醇的质量比为0.2:1。The difference between this embodiment and embodiment 1 is that: in this embodiment, the mass ratio of DMF, deionized water and ethanol is 30:1:1; the ultrasonic treatment time after sealing is 4 hours; and the mass ratio of Co-MOF to ethanol is 0.2:1.
实施例3Example 3
本实施例与实施例1的不同之处在于：本实施例中DMF、去离子水和乙醇的质量比为10:1:1；密封后超声处理时间为48h；Co-MOF与乙醇的质量比为2:1。The difference between this embodiment and embodiment 1 is that: in this embodiment, the mass ratio of DMF, deionized water and ethanol is 10:1:1; the ultrasonic treatment time after sealing is 48h; and the mass ratio of Co-MOF to ethanol is 2:1.
对比例1Comparative Example 1
本对比例中，以Co-MOF催化剂替换实施例1中的Pt/Co-MOF催化剂催化氨硼烷水解产氢，具体包括如下步骤：In this comparative example, the Pt/Co-MOF catalyst in Example 1 is replaced by a Co-MOF catalyst to catalyze the hydrolysis of ammonia borane to produce hydrogen, which specifically includes the following steps:
步骤一、1.称取125mg对苯二甲酸溶解在30mL DMF、2mL去离子水和2mL乙醇中。然后在上述溶液加入220mg Co(NO3)2·6H2O，在剧烈搅拌下快速注入1mL TEA，使其形成均匀的胶体悬浮液，密封后超声处理6h。随后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h，获得Co-MOF。Step 1: 1. Weigh 125 mg of terephthalic acid and dissolve it in 30 mL of DMF, 2 mL of deionized water and 2 mL of ethanol. Then add 220 mg of Co(NO3 )2 ·6H2 O to the above solution, and quickly inject 1 mL of TEA under vigorous stirring to form a uniform colloidal suspension, seal it and treat it by ultrasound for 6 hours. Then wash it with ethanol and centrifuge it at 10000 r/min for three times, and then dry it at 65°C for 12 hours to obtain Co-MOF.
步骤二、称取20mg制备好的Co-MOF加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。经过一段时间反应没有催化活性。Step 2: Weigh 20 mg of the prepared Co-MOF into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir evenly, then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane, and then start the reaction and count. After a period of time, the reaction has no catalytic activity.
对比例2Comparative Example 2
本对比例与实施例1的不同之处在于：本对比例采用现有技术中常用的水热合成法制备Pt/Co-MOF，具体包括如下步骤：The difference between this comparative example and Example 1 is that this comparative example adopts the hydrothermal synthesis method commonly used in the prior art to prepare Pt/Co-MOF, which specifically includes the following steps:
步骤一、1.取0.238g CoCl2·6H2O和0.166g对苯二甲酸加入到35mL DMF中，然后向上述溶液分别缓慢加入2.5mL乙醇和水。轻轻搅拌后，将清澈溶液转移到50mL特氟龙内衬的不锈钢水热釜中，加热至125℃保存12h。自然冷却后，在10000r/min下用乙醇离心、洗涤沉淀数次，在60℃下干燥6h，制得Co-MOF-1。Step 1: 1. Take 0.238g CoCl2 ·6H2 O and 0.166g terephthalic acid and add them to 35mL DMF, then slowly add 2.5mL ethanol and water to the above solution respectively. After gentle stirring, transfer the clear solution to a 50mL Teflon-lined stainless steel hydrothermal autoclave, heat to 125℃ and store for 12h. After natural cooling, centrifuge with ethanol at 10000r/min, wash the precipitate several times, and dry at 60℃ for 6h to obtain Co-MOF-1.
步骤二、称取120mg Co-MOF-1均匀分散在120mL乙醇中，加入12.2μL H2PtCl6(0.1M)溶液，搅拌15min后在65℃下继续加热搅拌5h。最后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h后制得Pt/Co-MOF-1。Step 2: Weigh 120 mg of Co-MOF-1 and disperse it evenly in 120 mL of ethanol, add 12.2 μL of H2 PtCl6 (0.1 M) solution, stir for 15 min, and continue heating and stirring at 65°C for 5 h. Finally, wash with ethanol, centrifuge at 10,000 r/min for three times, and dry at 65°C for 12 h to obtain Pt/Co-MOF-1.
步骤三、称取20mg制备好的Pt/Co-MOF-1加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。基于Pt原子总量(负载量为0.2％)计算出反应的转化效率TOF值为1400molH2·molPt·min-1。Step 3: Weigh 20 mg of the prepared Pt/Co-MOF-1 and add it to a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir it evenly. Then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane and start the reaction and timing. Based on the total amount of Pt atoms (loading amount is 0.2%), the conversion efficiency TOF value of the reaction is calculated to be 1400 molH2 ·molPt ·min-1 .
对比例3Comparative Example 3
本对比例中，催化剂为Pt/Ni-MOF，具体催化氨硼烷水解产氢的过程包括如下步骤：In this comparative example, the catalyst is Pt/Ni-MOF, and the specific process of catalyzing the hydrolysis of ammonia borane to produce hydrogen includes the following steps:
步骤一、称取125mg对苯二甲酸溶解在30mL DMF、2mL去离子水和2mL乙醇中。然后在上述溶液加入180mg NiCl2·6H2O，在剧烈搅拌下快速注入1mL TEA，使其形成均匀的胶体悬浮液，密封后超声处理6h。随后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h，获得Ni-MOF。Step 1: Weigh 125 mg of terephthalic acid and dissolve it in 30 mL of DMF, 2 mL of deionized water and 2 mL of ethanol. Then add 180 mg of NiCl2 ·6H2 O to the above solution, and quickly inject 1 mL of TEA under vigorous stirring to form a uniform colloidal suspension, seal it and perform ultrasonic treatment for 6 hours. Then wash it with ethanol and centrifuge it at 10000 r/min for three times, and then dry it at 65°C for 12 hours to obtain Ni-MOF.
步骤二、称取120mg Ni-MOF均匀分散在120mL乙醇中，加入12.2μL H2PtCl6(0.1M)溶液，搅拌15min后在65℃下继续加热搅拌5h。最后用乙醇洗涤，10000r/min离心，收集沉淀，重复三次，最终制得Pt/Ni-MOF。Step 2: Weigh 120 mg Ni-MOF and disperse it evenly in 120 mL ethanol, add 12.2 μL H2 PtCl6 (0.1 M) solution, stir for 15 min, and continue heating and stirring at 65° C. for 5 h. Finally, wash with ethanol, centrifuge at 10,000 r/min, collect the precipitate, repeat three times, and finally obtain Pt/Ni-MOF.
步骤三、称取20mg制备好的Pt/Ni-MOF加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。基于Pt原子总量(负载量为0.2％)计算出反应的转化效率TOF值为620molH2·molPt·min-1。Step 3: Weigh 20 mg of the prepared Pt/Ni-MOF into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir evenly, then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane, and start the reaction and time it. Based on the total amount of Pt atoms (loading amount is 0.2%), the conversion efficiency TOF value of the reaction is calculated to be 620 molH2 ·molPt ·min-1 .
对比例4Comparative Example 4
本对比例中，催化剂为Pt/ZIF-67，具体催化氨硼烷水解产氢的过程包括如下步骤：In this comparative example, the catalyst is Pt/ZIF-67, and the specific process of catalyzing the hydrolysis of ammonia borane to produce hydrogen includes the following steps:
步骤一、取1.455g Co(NO3)2·6H2O和1.642g 2-甲基咪唑分别溶解在40mL甲醇和40mL乙醇的混合物中。将上述两种溶液快速混合搅拌5min，室温静沉降24h后，过滤收集紫色沉淀，多次用乙醇纯化。最后，将得到的样品在60℃下真空干燥24h，得到ZIF-67。Step 1: Dissolve 1.455 g Co(NO3 )2 ·6H2 O and 1.642 g 2-methylimidazole in a mixture of 40 mL methanol and 40 mL ethanol, respectively. Mix and stir the two solutions rapidly for 5 min, let them settle at room temperature for 24 h, collect the purple precipitate by filtration, and purify it with ethanol several times. Finally, dry the obtained sample under vacuum at 60° C. for 24 h to obtain ZIF-67.
步骤二、负载Pt的方式同上，最终制得Pt/ZIF-67。Step 2: The method of loading Pt is the same as above, and finally Pt/ZIF-67 is obtained.
步骤三、称取20mg制备好的Pt/ZIF-67加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。催化剂几乎没有活性。Step 3: Weigh 20 mg of the prepared Pt/ZIF-67 into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir evenly, then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane, and then start the reaction and time the reaction. The catalyst is almost inactive.
对比例5Comparative Example 5
本对比例中，催化剂为Pt/ZIF-8，具体催化氨硼烷水解产氢的过程包括如下步骤：In this comparative example, the catalyst is Pt/ZIF-8, and the specific process of catalyzing the hydrolysis of ammonia borane to produce hydrogen includes the following steps:
步骤一、取2-甲基咪唑(0.28mol，22.95g)溶解在80ml水中，在35℃下搅拌形成均匀溶液。再称取Zn(NO3)2·6H2O(1.19g，4.0x 10-3mol)溶解在9mL水溶液，然后快速混合两种水溶液。将混合物搅拌1h后用水和乙醇在10000r/min下洗涤离心数次。然后在60℃下真空干燥过夜，制得ZIF-8。Step 1: Dissolve 2-methylimidazole (0.28 mol, 22.95 g) in 80 ml of water and stir at 35°C to form a uniform solution. Then weigh Zn(NO3 )2 ·6H2 O (1.19 g, 4.0 x 10-3 mol) and dissolve it in 9 mL of aqueous solution, and then quickly mix the two aqueous solutions. Stir the mixture for 1 hour, then wash and centrifuge it with water and ethanol at 10000 r/min for several times. Then vacuum dry it at 60°C overnight to obtain ZIF-8.
步骤二、负载Pt的方式同上，最终制得Pt/ZIF-8。Step 2: The method of loading Pt is the same as above, and finally Pt/ZIF-8 is obtained.
步骤三、称取20mg制备好的Pt/ZIF-8加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。催化剂几乎没有活性。Step 3: Weigh 20 mg of the prepared Pt/ZIF-8 into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir it evenly, then add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane, and then start the reaction and time the reaction. The catalyst is almost inactive.
对比例6Comparative Example 6
本对比例中，Pt/Co-MOF催化氨硼烷水解产氢之前增加NaHB4预处理，具体包括如下步骤：In this comparative example, NaHB4 pretreatment is added before Pt/Co-MOF catalyzes the hydrolysis of ammonia borane to produce hydrogen, which specifically includes the following steps:
步骤一、称取125mg对苯二甲酸溶解在30mL DMF、2mL去离子水和2mL乙醇中。然后在上述溶液加入220mg Co(NO3)2·6H2O，在剧烈搅拌下快速注入1mL TEA，使其形成均匀的胶体悬浮液，密封后超声处理6h。随后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h，制得Co-MOF。Step 1: Weigh 125 mg of terephthalic acid and dissolve it in 30 mL of DMF, 2 mL of deionized water and 2 mL of ethanol. Then add 220 mg of Co(NO3 )2 ·6H2 O to the above solution, and quickly inject 1 mL of TEA under vigorous stirring to form a uniform colloidal suspension, seal it and treat it by ultrasound for 6 hours. Then wash it with ethanol and centrifuge it at 10000 r/min for three times, and then dry it at 65°C for 12 hours to obtain Co-MOF.
步骤二、称取120mg Co-MOF均匀分散在120mL乙醇中，加入12.2μL H2PtCl6(0.1M)溶液，搅拌15min后在65℃下继续加热搅拌5h。最后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h后制得Pt/Co-MOF。Step 2: Weigh 120 mg Co-MOF and disperse it evenly in 120 mL ethanol, add 12.2 μL H2 PtCl6 (0.1 M) solution, stir for 15 min, and continue heating and stirring at 65° C. for 5 h. Finally, wash with ethanol, centrifuge at 10,000 r/min for three times, and dry at 65° C. for 12 h to obtain Pt/Co-MOF.
步骤三、称取20mg制备好的Pt/Co-MOF加入25mL密闭的圆底烧瓶分散在3mL去离子水中搅拌均匀，加入1mL硼氢化钠溶液(1M)进行预处理，待搅拌反应均匀后再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。Step 3: Weigh 20 mg of the prepared Pt/Co-MOF and add it to a 25 mL sealed round-bottom flask, disperse it in 3 mL of deionized water and stir evenly. Add 1 mL of sodium borohydride solution (1 M) for pretreatment. After the stirring reaction is uniform, add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane, and then the reaction starts and the timing is started.
对比例7Comparative Example 7
本对比例中，Pt/Co-MOF催化氨硼烷水解产氢之前增加H2预处理，具体包括如下步骤：In this comparative example,H2 pretreatment is added before Pt/Co-MOF catalyzes the hydrolysis of ammonia borane to produce hydrogen, which specifically includes the following steps:
步骤一、称取125mg对苯二甲酸溶解在30mL DMF、2mL去离子水和2mL乙醇中。然后在上述溶液加入220mg Co(NO3)2·6H2O，在剧烈搅拌下快速注入1mL TEA，使其形成均匀的胶体悬浮液，密封后超声处理6h。随后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h，制得Co-MOF。Step 1: Weigh 125 mg of terephthalic acid and dissolve it in 30 mL of DMF, 2 mL of deionized water and 2 mL of ethanol. Then add 220 mg of Co(NO3)2·6H2O to the above solution, and quickly inject 1 mL of TEA under vigorous stirring to form a uniform colloidal suspension, seal it and treat it with ultrasound for 6 hours. Then wash it with ethanol and centrifuge it three times at 10000 r/min, then dry it at 65°C for 12 hours to obtain Co-MOF.
步骤二、称取120mg Co-MOF均匀分散在120mL乙醇中，加入12.2μL H2PtCl6(0.1M)溶液，搅拌15min后在65℃下继续加热搅拌5h。最后用乙醇在10000r/min中洗涤离心三次后在65℃下烘干12h后制得Pt/Co-MOF。Step 2: Weigh 120 mg of Co-MOF and disperse it evenly in 120 mL of ethanol, add 12.2 μL of H2PtCl6 (0.1 M) solution, stir for 15 min, and continue heating and stirring at 65 ° C for 5 h. Finally, wash with ethanol, centrifuge three times at 10000 r/min, and dry at 65 ° C for 12 h to obtain Pt/Co-MOF.
步骤三、将20mg制备好的Pt/Co-MOF在H2条件下500℃加热进行预处理4h，处理后将催化剂加入25mL密闭的圆底烧瓶分散在4mL去离子水中搅拌均匀，再加入1mL溶解了30.8mg氨硼烷的离子水后反应开始并计时。Step 3: Pre-treat 20 mg of the prepared Pt/Co-MOF at 500 °C underH2 conditions for 4 h. After treatment, add the catalyst into a 25 mL sealed round-bottom flask, disperse it in 4 mL of deionized water and stir evenly. Then, add 1 mL of deionized water dissolved with 30.8 mg of ammonia borane and the reaction starts and the timing is started.
实验例1Experimental Example 1
对Co-MOF和不同金属有机骨架(Pt负载量保持0.2％)的Pt基催化剂对氨硼烷水解反应的催化活性，(即：实施例1、对比例1、对比例2、对比例3的催化剂在25℃催化氨硼烷溶液(0.2mol L-1)生成H2的体积)进行对比分析，结果如图1所示。图1结果表明：本实施例1、对比例2、对比例3的催化剂均具有催化氨硼烷产氢的作用，且实施例1的催化剂Pt/Co-MOF催化氨硼烷产氢速率最快，对比例1Co-MOF催化剂基本没有表现出催化活性；这表明Pt物种是负责氨硼烷水解的主要活性位点。The catalytic activity of Co-MOF and Pt-based catalysts of different metal organic frameworks (Pt loading maintained at 0.2%) for the hydrolysis reaction of ammonia borane (i.e., the volume of H2 generated by the catalysts of Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 at 25°C from ammonia borane solution (0.2 mol L-1 )) was compared and analyzed, and the results are shown in Figure 1. The results in Figure 1 show that the catalysts of Example 1, Comparative Example 2, and Comparative Example 3 all have the function of catalyzing the production of hydrogen from ammonia borane, and the catalyst Pt/Co-MOF of Example 1 has the fastest rate of catalyzing the production of hydrogen from ammonia borane, and the Co-MOF catalyst of Comparative Example 1 basically shows no catalytic activity; this indicates that the Pt species is the main active site responsible for the hydrolysis of ammonia borane.
实验例2Experimental Example 2
为了更好地比较不同金属有机骨架负载的Pt基催化剂的催化性能，对ZIF-67和ZIF-8这两种具有代表性的MOF材料作为负载Pt的载体，并探究不同负载量对催化活性的影响，结果如图2所示。Pt/ZIF-67催化剂的产H2曲线呈现较长的诱导期，诱导期约为20min，诱导期后产H2曲线开始逐渐上升。Pt/ZIF-8催化剂反应30min后，产氢体积保持在0。当Pt负载增加到1％时，氨硼烷在Pt1％/ZIF-67上的水解在15min内达到～100％的转化率，并且Pt1％/ZIF-8的产氢曲线在大约10min的诱导期后开始逐渐上升。这些结果表明Pt和MOF都可能对氨硼烷的脱氢有重要作用。值得注意的是，所有Pt基催化剂在开始时都有一个诱导期，一般认为在诱导期会产生新的活性物种。In order to better compare the catalytic performance of Pt-based catalysts supported by different metal organic frameworks, ZIF-67 and ZIF-8, two representative MOF materials, were used as carriers for loading Pt, and the effect of different loading amounts on the catalytic activity was explored. The results are shown in Figure 2. TheH2 production curve of the Pt/ZIF-67 catalyst showed a long induction period of about 20 minutes, and theH2 production curve began to gradually rise after the induction period. After 30 minutes of reaction, the hydrogen production volume of the Pt/ZIF-8 catalyst remained at 0. When the Pt loading increased to 1%, the hydrolysis of ammonia borane on Pt1% /ZIF-67 reached a conversion rate of ~100% within 15 minutes, and the hydrogen production curve of Pt1% /ZIF-8 began to gradually rise after an induction period of about 10 minutes. These results indicate that both Pt and MOF may play an important role in the dehydrogenation of ammonia borane. It is worth noting that all Pt-based catalysts have an induction period at the beginning, and it is generally believed that new active species will be generated during the induction period.
实验例3Experimental Example 3
为探究本发明实施例1Pt/Co-MOF催化剂的稳定性，对Pt/Co-MOF在25℃条件下前5次催化氨硼烷溶液(0.2mol L-1)生成H2的体积进行对比分析，结果如图3所示，结果表明循环反应5次后仍具有较高的催化活性，催化性能稳定，且第二次反应开始诱导期消失。In order to explore the stability of the Pt/Co-MOF catalyst in Example 1 of the present invention, the volumes of H2 generated by Pt/Co-MOF in the first five catalytic reactions of ammonia borane solution (0.2 mol L-1 ) at 25°C were compared and analyzed. The results are shown in FIG3 . The results show that after five cycles of reaction, the catalyst still has high catalytic activity, stable catalytic performance, and the induction period disappears at the beginning of the second reaction.
实验例4Experimental Example 4
对实施例1、对比例6、对比例7催化氨硼烷水解产氢的效果进行对比分析，结果如图4所示，结果表明：经H2预处理催化活性较弱，原位还原及采用硼氢化钠溶液处理表现出较好的氨硼烷水解催化活性，且原位处理能够在相对短的时间内达到催化峰值。The effects of Example 1, Comparative Example 6 and Comparative Example 7 on catalyzing the hydrolysis of ammonia borane to produce hydrogen were compared and analyzed. The results are shown in Figure 4. The results show that the catalytic activity is weak afterH2 pretreatment, while in situ reduction and treatment with sodium borohydride solution show better catalytic activity for the hydrolysis of ammonia borane, and the in situ treatment can reach the catalytic peak in a relatively short time.
实验例5Experimental Example 5
对Pt/Co-MOF催化反应前、后分别进行透射电镜扫描及X射线衍射测试，结果如图5、图6所示，其中，图5-a为Pt/Co-MOF催化反应前的透射电镜图；图5-b为Pt/Co-MOF催化反应前的EDX光谱；图5-c为Pt/Co-MOF催化反应前的EDX元素分布图；图6-a为Pt/Co-MOF一次催化反应前、后的磁性和颜色对比；图6-b为Pt/Co-MOF一次催化反应前、后的X射线衍射图谱；图6-c为Pt/Co-MOF一次催化反应后的透射电镜图；图6-d为Pt/Co-MOF一次催化反应后的高分辨透射电镜图。Transmission electron microscopy scanning and X-ray diffraction tests were performed on the Pt/Co-MOF before and after the catalytic reaction, and the results are shown in Figures 5 and 6, wherein Figure 5-a is a transmission electron microscopy image of the Pt/Co-MOF before the catalytic reaction; Figure 5-b is an EDX spectrum of the Pt/Co-MOF before the catalytic reaction; Figure 5-c is an EDX element distribution map before the catalytic reaction of Pt/Co-MOF; Figure 6-a is a comparison of the magnetism and color of Pt/Co-MOF before and after the first catalytic reaction; Figure 6-b is an X-ray diffraction spectrum before and after the first catalytic reaction of Pt/Co-MOF; Figure 6-c is a transmission electron microscopy image of Pt/Co-MOF after the first catalytic reaction; Figure 6-d is a high-resolution transmission electron microscopy image of Pt/Co-MOF after the first catalytic reaction.
结果表明：Pt/Co-MOF为片状结构，无法观测到明显纳米颗粒。经过一次反应后催化剂里的Co被还原，从而暴露出金属颗粒，是Pt解离氨硼烷产生氢溢流破坏Co-MOF的结果。The results show that Pt/Co-MOF is a sheet-like structure, and no obvious nanoparticles can be observed. After one reaction, the Co in the catalyst is reduced, exposing the metal particles, which is the result of Pt dissociating ammonia borane to produce hydrogen overflow and destroying Co-MOF.
以上所述的仅是本发明的实施例，方案中公知的具体技术方案和/或特性等常识在此未作过多描述。应当指出，对于本领域的技术人员来说，在不脱离本发明技术方案的前提下，还可以作出若干变形和改进，这些也应该视为本发明的保护范围，这些都不会影响本发明实施的效果和专利的实用性。本申请要求的保护范围应当以其权利要求的内容为准，说明书中的具体实施方式等记载可以用于解释权利要求的内容。The above is only an embodiment of the present invention, and the common knowledge such as the known specific technical solutions and/or characteristics in the solution is not described in detail here. It should be pointed out that for those skilled in the art, several modifications and improvements can be made without departing from the technical solution of the present invention, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicality of the patent. The scope of protection required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the specification can be used to interpret the content of the claims.
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| CN117228628A (en)* | 2023-09-19 | 2023-12-15 | 北京理工大学 | Solid hydrogen storage material based on metal organic framework, and preparation method and application thereof |
| WO2024234835A1 (en)* | 2023-05-16 | 2024-11-21 | 安徽理工大学 | Mof-derived nitrogen cobalt heterogeneous nanobox electrocatalyst, preparation method therefor, and use thereof |
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| CN107999132A (en)* | 2017-11-13 | 2018-05-08 | 华东师范大学 | A kind of preparation method of methanol electro-catalysis reforming catalyst |
| CN107930697A (en)* | 2017-11-18 | 2018-04-20 | 桂林电子科技大学 | A kind of 67 composite materials of Pt/ZIF for being used to be catalyzed ammonia borane hydrolysis hydrogen manufacturing |
| CN109485015A (en)* | 2018-12-21 | 2019-03-19 | 安徽工业大学 | With the method for CuNiPt/ porous C exCoyOz nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation |
| WO2024234835A1 (en)* | 2023-05-16 | 2024-11-21 | 安徽理工大学 | Mof-derived nitrogen cobalt heterogeneous nanobox electrocatalyst, preparation method therefor, and use thereof |
| CN117228628A (en)* | 2023-09-19 | 2023-12-15 | 北京理工大学 | Solid hydrogen storage material based on metal organic framework, and preparation method and application thereof |
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