CN117535714A - Preparation method and application of NiFe LDH-loaded single-atom Ru catalyst - Google Patents
Preparation method and application of NiFe LDH-loaded single-atom Ru catalyst Download PDFInfo
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 20
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002028 Biomass Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims 1
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910018661 Ni(OH) Inorganic materials 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical compound [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
Description
技术领域Technical field
本发明属于电催化电极材料制备技术领域，具体涉及一种NiFe LDH负载单原子Ru催化剂及其制备方法和应用。The invention belongs to the technical field of electrocatalytic electrode material preparation, and specifically relates to a NiFe LDH supported single atom Ru catalyst and its preparation method and application.
背景技术Background technique
化石燃料过度使用会导致能源枯竭和环境污染，因此发展清洁能源、推动可持续发展战略至关重要，电解水制氢因条件温和、原料充足，被认为是未来清洁能源行业最具有发展潜力的技术，然而，大规模的电化学分解水受到动力学缓慢的阳极析氧反应(OER)的限制，于是，研究人员尝试用热力学、动力学更为有利的有机小分子氧化反应替代阳极OER，以实现高效耦合制氢。Excessive use of fossil fuels will lead to energy depletion and environmental pollution. Therefore, it is crucial to develop clean energy and promote sustainable development strategies. Hydrogen production from water by electrolysis is considered to be the most promising technology in the future clean energy industry due to its mild conditions and sufficient raw materials. , however, large-scale electrochemical water splitting is limited by the kinetically slow anode oxygen evolution reaction (OER). Therefore, researchers try to replace the anode OER with an organic small molecule oxidation reaction with more favorable thermodynamics and kinetics. Highly efficient coupled hydrogen production.
生物质衍生物5-羟甲基糠醛(HMF)理论氧化电压小，并且阳极能够得到高附加值化学品2，5-呋喃二羧酸(FDCA)，被认为是替代OER反应的良好选择，因此，开发高效催化氧化5-羟甲基糠醛(HMFOR)电催化剂对促进阴极产氢和阳极获得高附加值的产物具有重要意义。The biomass derivative 5-hydroxymethylfurfural (HMF) has a small theoretical oxidation voltage, and the anode can obtain the high value-added chemical 2,5-furandicarboxylic acid (FDCA), which is considered a good choice to replace the OER reaction. Therefore, , the development of high-efficiency catalytic oxidation of 5-hydroxymethylfurfural (HMFOR) electrocatalysts is of great significance to promote hydrogen production at the cathode and obtain high value-added products at the anode.
目前，LDH、Ni(OH)2被认为是HMFOR反应的有效催化剂，其中高价的羟基氧化物，如NiOOH被证实是反应活性位点，然而，Ni(OH)2转变为NiOOH需要施加较高电位，此时阳极反应不可避免存在HMFOR和OER反应的竞争，导致阳极法拉第效率不高，产物FDCA生成率较低。Currently, LDH and Ni(OH) 2 are considered to be effective catalysts for the HMFOR reaction, in which high-valent oxyhydroxides such as NiOOH are confirmed to be reaction active sites. However, the transformation of Ni(OH) 2 into NiOOH requires the application of a higher potential. , at this time, there is inevitably competition between the HMFOR and OER reactions in the anode reaction, resulting in low anode Faradaic efficiency and low production rate of the product FDCA.
发明内容Contents of the invention
本发明的目的在于提供一种NiFe LDH负载单原子Ru催化剂的制备方法及应用，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 preparation method and application of a NiFe LDH supported single atom Ru catalyst to solve the problems raised in the above background technology.
本发明的目的可以通过以下技术方案实现：The object of the present invention can be achieved through the following technical solutions:
一种NiFe LDH负载单原子Ru催化剂的制备方法，其特征在于：包括以下步骤：A method for preparing a NiFe LDH supported single atom Ru catalyst, which is characterized in that it includes the following steps:
S1、将厚度为0.5mm的泡沫镍裁剪成1cm*2cm的标准长方形，依次用去离子水、乙醇超声洗涤，然后烘箱烘干；S1. Cut the 0.5mm thick nickel foam into a standard rectangle of 1cm*2cm, ultrasonically wash it with deionized water and ethanol, and then dry it in an oven;
S2、将Ni(NO3)2·6H2O和Fe(NO3)3·9H2O一同溶于去离子水中，持续搅拌得到混合溶液，再将RuCl3加入上述混合溶液中搅拌，得到均匀溶液；S2. Dissolve Ni(NO 3 ) 2 ·6H 2 O and Fe(NO 3 ) 3 ·9H 2 O in deionized water and stir continuously to obtain a mixed solution. Then add RuCl 3 to the above mixed solution and stir until a uniform solution is obtained. solution;
S3、将步骤S1得到的干净泡沫镍置于步骤S2中得到的均匀溶液中，采用三电极体系进行电沉积，沉积模式选择恒电压模式，沉积后取出，洗涤烘干，得到NiFe LDH负载单原子Ru催化剂。S3. Place the clean nickel foam obtained in step S1 into the uniform solution obtained in step S2. Use a three-electrode system for electrodeposition. Select the constant voltage mode as the deposition mode. After deposition, take it out, wash and dry to obtain NiFe LDH loaded single atoms. Ru catalyst.
优选的，在所述步骤S1中，用去离子水、乙醇超声洗涤步骤为采用水和乙醇交替洗涤3-5次，每次洗涤时间为3-5min。Preferably, in step S1, the ultrasonic washing step with deionized water and ethanol is to alternately wash with water and ethanol 3-5 times, and each washing time is 3-5 minutes.
在所述步骤S1中，烘箱温度为40～80℃，烘干时间为30～70min。In the step S1, the oven temperature is 40-80°C, and the drying time is 30-70 minutes.
在所述步骤S2中，Ni(NO3)2·6H2O的摩尔浓度为0.1～0.3mol/L，Fe(NO3)3·9H2O的摩尔浓度为0.1～0.3mol/L，Ni(NO3)2·6H2O和Fe(NO3)3·9H2O的摩尔比例为1:3，对Ni(NO3)2·6H2O和Fe(NO3)3·9H2O的搅拌速率为30～80r/min，搅拌时间为15-45min。In the step S2, the molar concentration of Ni(NO 3 ) 2 ·6H 2 O is 0.1 to 0.3 mol/L, the molar concentration of Fe(NO 3 ) 3 ·9H 2 O is 0.1 to 0.3 mol/L, and Ni The molar ratio of (NO 3 ) 2 ·6H 2 O and Fe(NO 3 ) 3 ·9H 2 O is 1:3. For Ni(NO 3 ) 2 ·6H 2 O and Fe(NO 3 ) 3 ·9H 2 O The stirring rate is 30~80r/min, and the stirring time is 15-45min.
在所述步骤S2中，RuCl3浓度为0.01～0.07mol/L，所述Ni(NO3)2·6H2O和Fe(NO3)3·9H2O总摩尔浓度是RuCl3的1～20倍，RuCl3加入上述混合溶液后搅拌速率为50-120min，搅拌时间为30-50min。In the step S2, the RuCl 3 concentration is 0.01 to 0.07 mol/L, and the total molar concentration of Ni(NO 3 ) 2 ·6H 2 O and Fe(NO 3 ) 3 ·9H 2 O is 1 to 0.07 mol/L of RuCl 3 20 times, after RuCl 3 is added to the above mixed solution, the stirring rate is 50-120min, and the stirring time is 30-50min.
在所述步骤S3中，电化学工作站的电压工作范围为-1～1V。In the step S3, the voltage working range of the electrochemical workstation is -1~1V.
在所述步骤S3中，电沉积时间为100～700s。In the step S3, the electrodeposition time is 100 to 700 s.
在所述步骤S3中，烘箱温度为40～85℃，烘干时间为1～5h.In the step S3, the oven temperature is 40~85°C, and the drying time is 1~5h.
一种NiFe LDH负载单原子Ru催化剂的制备方法，所制备的NiFe LDH负载单原子Ru催化剂在电催化氧化生物质5-羟甲基糠醛中应用。A method for preparing a NiFe LDH-loaded single-atom Ru catalyst. The prepared NiFe LDH-loaded single-atom Ru catalyst is used in the electrocatalytic oxidation of biomass 5-hydroxymethylfurfural.
本发明的有益效果：Beneficial effects of the present invention:
一、本发明采用电沉积方法，制备NiFe LDH负载单原子Ru催化剂，与常用的水热法、煅烧法相比，电沉积法常温常压下进行，操作条件温和，制备时间短，并且，使用泡沫镍作为基底，形成自支撑电极材料，具有多孔结构、良好的导电性和电化学活性，能够促进电荷转移和加速电极反应的进行。1. The present invention uses an electrodeposition method to prepare a NiFe LDH-supported single-atom Ru catalyst. Compared with the commonly used hydrothermal method and calcination method, the electrodeposition method is carried out at room temperature and pressure, has mild operating conditions, short preparation time, and uses foam. Nickel is used as a base to form a self-supporting electrode material with a porous structure, good conductivity and electrochemical activity, which can promote charge transfer and accelerate electrode reactions.
二、本发明提出了一种利用金属-非金属成键在NiFe LDH表面稳定单原子的方法，在泡沫镍上形成NiFe LDH，并通过钌-氧配位键将Ru固定在NiFe LDH上，提高贵金属原子利用率，降低单原子催化剂不稳定性，与单独的NiFe LDH相比，本发明制备的NiFe LDH负载单原子Ru催化剂电化学阻抗较小、双电层电容较大，同时Ru单原子能够促进底物的吸附，进而提升催化活性。2. The present invention proposes a method of using metal-non-metal bonding to stabilize single atoms on the surface of NiFe LDH, forming NiFe LDH on nickel foam, and fixing Ru on the NiFe LDH through ruthenium-oxygen coordination bonds to improve The utilization rate of precious metal atoms reduces the instability of single-atom catalysts. Compared with NiFe LDH alone, the NiFe LDH-loaded single-atom Ru catalyst prepared by the present invention has smaller electrochemical impedance and larger double-layer capacitance. At the same time, the Ru single atom can Promote the adsorption of substrates, thereby improving catalytic activity.
三、本发明提出了NiFe LDH负载单原子Ru催化剂在HMFOR电催化剂中的应用，通过引入Ru单原子作为Lewis酸位点调节NiFe LDH中Ni的电子结构，在较低电压下促进高价镍活性物种的生成，从而使NiFe LDH电催化氧化生物质5-羟甲基糠醛(HMF)的性能提高，有利于促进阴极产氢以及阳极得到高附加值的氧化产物2,5-呋喃二羧酸(FDCA)，阳极HMF转化率接近100％，FDCA生产率96.2％，法拉第效率96％3. The present invention proposes the application of NiFe LDH supported single atom Ru catalyst in HMFOR electrocatalyst. By introducing Ru single atom as Lewis acid site, the electronic structure of Ni in NiFe LDH is adjusted to promote high-valent nickel active species at lower voltage. The generation of NiFe LDH improves the performance of electrocatalytic oxidation of biomass 5-hydroxymethylfurfural (HMF), which is beneficial to promoting hydrogen production at the cathode and obtaining the high value-added oxidation product 2,5-furandicarboxylic acid (FDCA) at the anode. ), the anode HMF conversion rate is close to 100%, the FDCA productivity is 96.2%, and the Faraday efficiency is 96%
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图；In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings needed to describe the embodiments or the prior art. Obviously, for those of ordinary skill in the art, Speaking of which, other drawings can be obtained based on these drawings without any creative effort;
图1是实施例2和对比例1制备的产品的XRD图谱；Figure 1 is the XRD pattern of the products prepared in Example 2 and Comparative Example 1;
图2是实施例2制备的NiFe LDH负载单原子Ru催化剂的TEM图；Figure 2 is a TEM image of the NiFe LDH supported single atom Ru catalyst prepared in Example 2;
图3是实施例2制备的NiFe LDH负载单原子Ru催化剂的HRTEM图；Figure 3 is an HRTEM image of the NiFe LDH supported single atom Ru catalyst prepared in Example 2;
图4是实施例2制备的NiFe LDH负载单原子Ru催化剂的XAFS谱图；Figure 4 is the XAFS spectrum of the NiFe LDH supported single atom Ru catalyst prepared in Example 2;
图5是实施例2和对比例1制备的样品的线性扫描伏安曲线的对比图；Figure 5 is a comparison diagram of the linear sweep voltammetry curves of the samples prepared in Example 2 and Comparative Example 1;
图6是实施例2和对比例1制备的样品催化性能对比图；Figure 6 is a comparison chart of the catalytic performance of samples prepared in Example 2 and Comparative Example 1;
图7是实施例2和对比例1制备的样品在5次循环测试中的催化性能图。Figure 7 is a diagram of the catalytic performance of the samples prepared in Example 2 and Comparative Example 1 in 5 cycles of testing.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，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作出创造性劳动前提下所获得的所有其它实施例，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 with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
实施例1Example 1
将厚度为0.5mm的泡沫镍裁剪成1cm*2cm的标准长方形，用去离子水、乙醇交替超声洗涤3次，每次洗涤5min，然后在60℃烘箱烘干30min，将6mmol Ni(NO3)2·6H2O(六合水硝酸镍)和6mmol Fe(NO3)3·9H2O(九合水硝酸铁)一起溶于50mL去离子水中，持续搅拌30分钟后，得到混合溶液，将1mmol RuCl3加入上述混合溶液中搅拌，得到均匀溶液，以泡沫镍为工作电极置于上述均匀溶液中，Ag/AgCl电极为参比电极，石墨棒作为对电极构成三电极体系，沉积模式选择恒电压模式，并将电压设置为-0.8V，进行电沉积，沉积时间300s，然后将产品洗涤，置于60℃烘箱中烘干5h，得到红褐色NiFe LDH(层状NiFe双氢氧化物)负载单原子Ru催化剂，经过XRD表征证实了实施例1制得了NiFe LDH负载单原子Ru催化剂。Cut the nickel foam with a thickness of 0.5mm into a standard rectangle of 1cm*2cm, wash it with deionized water and ethanol alternately for 3 times, 5 minutes each time, and then dry it in an oven at 60°C for 30 minutes. 2 ·6H 2 O (nickel nitrate in hexahydrate water) and 6mmol Fe(NO 3 ) 3 ·9H 2 O (ferric nitrate in nine hexahydrate water) were dissolved in 50 mL of deionized water. After continuous stirring for 30 minutes, a mixed solution was obtained. 1 mmol Add RuCl 3 to the above mixed solution and stir to obtain a uniform solution. Use foamed nickel as the working electrode and place it in the above uniform solution, the Ag/AgCl electrode as the reference electrode, and the graphite rod as the counter electrode to form a three-electrode system. Select constant voltage as the deposition mode. mode, and set the voltage to -0.8V, conduct electrodeposition, the deposition time is 300s, then wash the product and dry it in a 60°C oven for 5h to obtain a reddish-brown NiFe LDH (layered NiFe double hydroxide) loaded single Atomic Ru catalyst, XRD characterization confirmed that Example 1 prepared a NiFe LDH supported single atom Ru catalyst.
实施例2Example 2
将厚度为0.5mm的泡沫镍裁剪成1cm*2cm的标准长方形，用去离子水、乙醇交替超声洗涤3次，每次洗涤5min，然后在60℃烘箱烘干30min。将6mmol Ni(NO3)2·6H2O和6mmolFe(NO3)3·9H2O一起溶于50mL去离子水中，持续充分搅拌30分钟后，得到混合溶液，将2.5mmol RuCl3·加入上述混合溶液中搅拌，得到均匀溶液，以泡沫镍为工作电极置于上述均匀溶液中，Ag/AgCl电极为参比电极，石墨棒作为对电极构成三电极体系，沉积模式选择恒电压模式，并将电压设置为-0.8V，进行电沉积，沉积时间300s，然后将产品洗涤，置于60℃烘箱中烘干5h，得到红褐色NiFe LDH负载单原子Ru催化剂，经过XRD表征证实了实施例2制得了NiFe LDH负载单原子Ru催化剂。Cut the nickel foam with a thickness of 0.5mm into a standard rectangle of 1cm*2cm, ultrasonically wash it three times with deionized water and ethanol for 5 minutes each time, and then dry it in an oven at 60°C for 30 minutes. Dissolve 6mmol Ni(NO 3 ) 2 ·6H 2 O and 6mmol Fe(NO 3 ) 3 ·9H 2 O in 50mL deionized water. Continue to stir thoroughly for 30 minutes to obtain a mixed solution. Add 2.5mmol RuCl 3 ·to the above solution. Stir in the mixed solution to obtain a uniform solution. Place the nickel foam as the working electrode in the above uniform solution, the Ag/AgCl electrode as the reference electrode, and the graphite rod as the counter electrode to form a three-electrode system. Select the constant voltage mode as the deposition mode, and set The voltage was set to -0.8V, electrodeposition was performed, and the deposition time was 300s. The product was then washed and dried in a 60°C oven for 5 hours to obtain a reddish-brown NiFe LDH supported single-atom Ru catalyst. XRD characterization confirmed that the product was prepared in Example 2. NiFe LDH supported single atom Ru catalyst was obtained.
实施例3Example 3
将厚度为0.5mm的泡沫镍裁剪成1cm*2cm的标准长方形，用去离子水、乙醇交替超声洗涤3次，每次洗涤5min，然后在60℃烘箱烘干30min。将6mmol Ni(NO3)2·6H2O和6mmolFe(NO3)3·9H2O一起溶于50mL去离子水中，持续充分搅拌30分钟后，得到混合溶液，将3.5mmol RuCl3·加入上述混合溶液中搅拌，得到均匀溶液，以泡沫镍为工作电极置于上述均匀溶液中，Ag/AgCl电极为参比电极，石墨棒作为对电极构成三电极体系，沉积模式选择恒电压模式，并将电压设置为-0.8V，进行电沉积，沉积时间300s，然后将产品洗涤，置于60℃烘箱中烘干5h，得到红褐色NiFe LDH负载单原子Ru催化剂，经过XRD表征证实了实施例3制得了NiFe LDH负载单原子Ru催化剂。Cut the nickel foam with a thickness of 0.5mm into a standard rectangle of 1cm*2cm, ultrasonically wash it three times with deionized water and ethanol for 5 minutes each time, and then dry it in an oven at 60°C for 30 minutes. Dissolve 6mmol Ni(NO 3 ) 2 ·6H 2 O and 6mmol Fe(NO 3 ) 3 ·9H 2 O in 50mL deionized water. Continue to stir thoroughly for 30 minutes to obtain a mixed solution. Add 3.5mmol RuCl 3 ·to the above solution. Stir in the mixed solution to obtain a uniform solution. Place the nickel foam as the working electrode in the above uniform solution, the Ag/AgCl electrode as the reference electrode, and the graphite rod as the counter electrode to form a three-electrode system. Select the constant voltage mode as the deposition mode, and set The voltage was set to -0.8V, electrodeposition was performed, and the deposition time was 300s. The product was then washed and dried in a 60°C oven for 5 hours to obtain a reddish-brown NiFe LDH supported single-atom Ru catalyst. XRD characterization confirmed that the product was prepared in Example 3. NiFe LDH supported single atom Ru catalyst was obtained.
实施例4Example 4
将厚度为0.5mm的泡沫镍裁剪成1cm*2cm的标准长方形，用去离子水、乙醇交替超声洗涤3次，每次洗涤5min，然后在60℃烘箱烘干30min，将6mmol Ni(NO3)2·6H2O和6mmolFe(NO3)3·9H2O一起溶于50mL去离子水中，持续充分搅拌30分钟后，得到混合溶液，将2.5mmol RuCl3·加入上述混合溶液中搅拌，得到均匀溶液，以泡沫镍为工作电极置于上述均匀溶液中，Ag/AgCl电极为参比电极，石墨棒作为对电极构成三电极体系，沉积模式选择恒电压模式，并将电压设置为-0.8V，进行电沉积，沉积时间500s，然后将产品洗涤，置于60℃烘箱中烘干5h，得到红褐色NiFe LDH负载单原子Ru催化剂，经过XRD表征证实了实施例4制得了NiFe LDH负载单原子Ru催化剂。Cut the nickel foam with a thickness of 0.5mm into a standard rectangle of 1cm*2cm, wash it with deionized water and ethanol alternately for 3 times, 5 minutes each time, and then dry it in an oven at 60°C for 30 minutes. 2 ·6H 2 O and 6mmol Fe(NO 3 ) 3 ·9H 2 O were dissolved in 50 mL of deionized water. After stirring for 30 minutes, a mixed solution was obtained. Add 2.5 mmol RuCl 3 · to the above mixed solution and stir until a uniform solution was obtained. Solution, use nickel foam as the working electrode in the above uniform solution, the Ag/AgCl electrode as the reference electrode, and the graphite rod as the counter electrode to form a three-electrode system. Select the constant voltage mode as the deposition mode, and set the voltage to -0.8V. Electrodeposition was carried out for 500 seconds, and then the product was washed and dried in a 60°C oven for 5 hours to obtain a reddish-brown NiFe LDH-supported single-atom Ru catalyst. XRD characterization confirmed that the NiFe LDH-supported single-atom Ru catalyst was obtained in Example 4. catalyst.
对比例1Comparative example 1
将厚度为0.5mm的泡沫镍裁剪成1cm*2cm的标准长方形，用去离子水、乙醇交替超声洗涤3次，每次洗涤5min，然后在60℃烘箱烘干30min，将6mmol Ni(NO3)2·6H2O和6mmolFe(NO3)3·9H2O一起溶于50mL去离子水中，持续充分搅拌30分钟后，得到混合溶液，以泡沫镍为工作电极置于上述混合溶液中，Ag/AgCl电极为参比电极，石墨棒作为对电极构成三电极体系，沉积模式选择恒电压模式，并将电压设置为-0.8V，进行电沉积，沉积时间300s，然后将产品洗涤，置于60℃烘箱中烘干5h，得到深黄色NiFe LDH催化剂，经过XRD表征证实了对比例1制得了NiFe LDH催化剂。Cut the nickel foam with a thickness of 0.5mm into a standard rectangle of 1cm*2cm, wash it with deionized water and ethanol alternately for 3 times, 5 minutes each time, and then dry it in an oven at 60°C for 30 minutes. 2 ·6H 2 O and 6 mmol Fe(NO 3 ) 3 ·9H 2 O were dissolved in 50 mL of deionized water. After continuous stirring for 30 minutes, a mixed solution was obtained. Foamed nickel was used as the working electrode and placed in the above mixed solution. Ag/ The AgCl electrode is used as the reference electrode, and the graphite rod is used as the counter electrode to form a three-electrode system. Select the constant voltage mode as the deposition mode, and set the voltage to -0.8V for electrodeposition. The deposition time is 300s, and then the product is washed and placed at 60°C. After drying in an oven for 5 hours, a dark yellow NiFe LDH catalyst was obtained. XRD characterization confirmed that the NiFe LDH catalyst was prepared in Comparative Example 1.
图1是实施例2和对比例1制备的产品的X射线衍射图谱(XRD)，通过图1的XRD结果可知，实施例2制备的NiFe LDH负载单原子Ru催化剂的衍射峰对应于对比例1的NiFe LDH(JCPDS:40-0215)，说明NiFe LDH的成功制备，与纯NiFe LDH相比没有出现新的衍射峰，说明实施例2中掺入Ru后没有改变NiFe LDH的原始物相结构，说明Ru原子并未掺杂到Ni或者Fe的晶格中，没有形成新的物相，为Ru原子在NiFe LDH表面成键形成单原子提供了证据。Figure 1 is the X-ray diffraction pattern (XRD) of the products prepared in Example 2 and Comparative Example 1. From the XRD results in Figure 1, it can be seen that the diffraction peak of the NiFe LDH-loaded single-atom Ru catalyst prepared in Example 2 corresponds to Comparative Example 1 NiFe LDH (JCPDS:40-0215), indicating the successful preparation of NiFe LDH. Compared with pure NiFe LDH, no new diffraction peak appeared, indicating that the original phase structure of NiFe LDH was not changed after incorporating Ru in Example 2. This shows that Ru atoms are not doped into the Ni or Fe crystal lattice, and no new phase is formed, which provides evidence that Ru atoms bond to form single atoms on the NiFe LDH surface.
图2为NiFe LDH负载单原子Ru催化剂的透射电镜图(TEM图)，图3为NiFe LDH负载单原子Ru催化剂的高分辨透射电镜图(HRTEM图)，从图2中可以看出，样品呈二维层状结构，大小为200nm～300nm，从图3的样品高分辨图像中可以观察到清晰的晶格条纹，根据晶格间距可以判断出该晶面对应于NiFe LDH的(012)和(015)面，与XRD结果相对应。Figure 2 is the transmission electron microscope image (TEM image) of the NiFe LDH-supported single-atom Ru catalyst. Figure 3 is the high-resolution transmission electron microscope image (HRTEM image) of the NiFe LDH-supported single-atom Ru catalyst. As can be seen from Figure 2, the sample exhibits The two-dimensional layered structure has a size of 200nm to 300nm. Clear lattice stripes can be observed from the high-resolution image of the sample in Figure 3. According to the lattice spacing, it can be judged that the crystal plane corresponds to the (012) and (012) of NiFe LDH. (015) surface, corresponding to the XRD results.
图4是实施例2制备的的NiFe LDH负载单原子Ru催化剂中Ru K边的X射线吸收精细结构谱图(XAFS)，为Ru-O键，/>为Ru-Cl键，/>为Ru-Ru键，从图3中可以看到NiFe LDH负载单原子Ru催化剂中没有出现Ru-Ru配位以及Ru-Cl配位，只在第一壳层出现Ru-O峰，说明Ru原子负载在NiFe LDH表面，并与LDH表面氧成键，进一步说明的单原子Ru的成功负载。Figure 4 is the X-ray absorption fine structure spectrum (XAFS) of the Ru K edge in the NiFe LDH supported single atom Ru catalyst prepared in Example 2, is the Ru-O bond,/> is the Ru-Cl bond,/> It is the Ru-Ru bond. It can be seen from Figure 3 that there is no Ru-Ru coordination and Ru-Cl coordination in the NiFe LDH supported single-atom Ru catalyst, and only the Ru-O peak appears in the first shell layer, indicating that Ru atoms It is loaded on the surface of NiFe LDH and bonds with the oxygen on the surface of LDH, which further illustrates the successful loading of single-atom Ru.
为了评估实施例2中的NiFe LDH负载单原子Ru催化剂和对比例1中的NiFe LDH催化剂在碱性条件下的OER(析氧反应)和HMFOR(用5-羟甲基糠醛氧化反应)活性，分别对其进行了电催化性能测试，具体测试步骤和结果如下：In order to evaluate the OER (oxygen evolution reaction) and HMFOR (oxidation reaction with 5-hydroxymethylfurfural) activities of the NiFe LDH supported single atom Ru catalyst in Example 2 and the NiFe LDH catalyst in Comparative Example 1 under alkaline conditions, The electrocatalytic performance tests were conducted on them respectively. The specific test steps and results are as follows:
一、在1M KOH溶液中以石墨棒作为对电极、银/氯化银电极作为参比电极、实施例2和对比例1分别作为工作电极，采用三电极模式进行测试，阳极线性伏安扫描速度控制为5mV s-1，IR补偿为90％。1. In 1M KOH solution, a graphite rod was used as the counter electrode, the silver/silver chloride electrode was used as the reference electrode, Example 2 and Comparative Example 1 were used as the working electrode respectively, and the three-electrode mode was used for testing. The anode linear voltammetry scan speed Control is 5mV s -1 and IR compensation is 90%.
二、在1M KOH+10mM HMF溶液中以石墨棒作为对电极、银/氯化银电极作为参比电极、实施例2和对比例1分别作为工作电极，采用三电极模式进行测试，阳极线性伏安扫描速度控制为5mV s-1，IR补偿为90％。2. In the 1M KOH+10mM HMF solution, use the graphite rod as the counter electrode, the silver/silver chloride electrode as the reference electrode, Example 2 and Comparative Example 1 as the working electrode respectively, and use the three-electrode mode to conduct the test. The anode linear voltage The scanning speed is controlled to 5mV s -1 and the IR compensation is 90%.
测试结果如图5所示，图5为实施例2和对比例1产品分别在1M KOH和1M KOH+10mMHMF溶液中，扫速为5mV/s和90％IR补偿条件下的线性扫描伏安曲线，从该图中可以看出，在KOH溶液中，与对比例1相比，实施例2制备得到的NiFe LDH负载单原子Ru催化剂具有较好的碱性OER活性，电流密度高于NiFe LDH，在含有10mM HMF的KOH溶液中，NiFe LDH负载单原子Ru催化剂和NiFe LDH的电流密度均得到提升，说明HMFOR反应动力学优于OER过程，并且NiFe LDH负载单原子Ru催化剂对HMF有良好的催化效果。The test results are shown in Figure 5. Figure 5 is the linear sweep voltammetry curve of the products of Example 2 and Comparative Example 1 in 1M KOH and 1M KOH+10mMHMF solutions respectively, with a scanning speed of 5mV/s and 90% IR compensation. , it can be seen from this figure that in KOH solution, compared with Comparative Example 1, the NiFe LDH-supported single-atom Ru catalyst prepared in Example 2 has better alkaline OER activity, and the current density is higher than NiFe LDH. In the KOH solution containing 10mM HMF, the current density of NiFe LDH-supported single-atom Ru catalyst and NiFe LDH was improved, indicating that the HMFOR reaction kinetics is better than the OER process, and the NiFe LDH-supported single-atom Ru catalyst has good catalysis for HMF. Effect.
图6是实施例2和对比例1制备的产品催化氧化HMF的性能图，在1MKOH+100mM HMF溶液中以石墨棒作为对电极、银/氯化银电极作为参比电极、实施例2和对比例1分别作为工作电极，采用恒电压模式电解，并通过液体核磁定量分析阳极产物，从图中可以看到，NiFeLDH负载单原子Ru催化剂的HMF转化率接近100％，FDCA生成率96.2％，法拉第效率96％，明显优于对比例1制备的NiFe LDH。Figure 6 is a performance diagram of the catalytic oxidation of HMF of the products prepared in Example 2 and Comparative Example 1. In a 1MKOH+100mM HMF solution, a graphite rod is used as the counter electrode and a silver/silver chloride electrode is used as the reference electrode. Example 2 and Comparative Example Ratio 1 is used as the working electrode respectively, using constant voltage mode electrolysis, and quantitatively analyzing the anode product through liquid nuclear magnetic field. As can be seen from the figure, the HMF conversion rate of the NiFeLDH supported single atom Ru catalyst is close to 100%, the FDCA generation rate is 96.2%, and the Faraday The efficiency is 96%, which is significantly better than the NiFe LDH prepared in Comparative Example 1.
图7是实施例2制备的产品催化氧化HMF的循环稳定性图，在1M KOH+100mM HMF溶液中以石墨棒作为对电极、银/氯化银电极作为参比电极、实施例2作为工作电极，采用恒电压模式循环电解5次，并通过液体核磁定量分析阳极产物，从图中可以看到，NiFe LDH负载单原子Ru催化剂的HMF转化率和FDCA生成率均维持在90％以上，说明催化剂稳定性良好。Figure 7 is a cycle stability diagram of the catalytic oxidation of HMF of the product prepared in Example 2. In a 1M KOH+100mM HMF solution, a graphite rod is used as the counter electrode, a silver/silver chloride electrode is used as the reference electrode, and Example 2 is used as the working electrode. , electrolysis was cycled 5 times in constant voltage mode, and the anode product was quantitatively analyzed by liquid nuclear magnetic resonance. As can be seen from the figure, the HMF conversion rate and FDCA generation rate of the NiFe LDH supported single atom Ru catalyst are maintained above 90%, indicating that the catalyst Good stability.
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have other aspects. Various changes and modifications are possible, which fall within the scope of the claimed invention.
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