CN115896822A - Method for producing hydrogen by coupling preparation of polyol and alkyd through electrocatalysis of polyol - Google Patents
Method for producing hydrogen by coupling preparation of polyol and alkyd through electrocatalysis of polyol Download PDFInfo
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Abstract
本发明公开了一种电催化多元醇制备多元醇酸耦合产氢的方法，以负载阳极催化剂贵金属/氢氧化物的导电基底作为阳极、以阴极催化剂作为阴极、与电解液组装成电解池，在电解液中加入多元醇，在电压条件下，多元醇在阳极被氧化生成多元醇酸，水在阴极还原生成氢气。本发明构筑贵金属/氢氧化物作为阳极催化剂，以水中氢原子/氧原子作为氧化还原反应中[H]/[O]来源，利用氢氧化物表面羟基和多元醇羟基之间的氢键作用，在催化剂表面吸附富集多元醇，提高反应物局部浓度从而提高电流密度，使其达到工业生产需求，同时水在阴极被还原为氢气，进一步提高其工业应用潜力。
The invention discloses a method for electrocatalyzing polyols to prepare polyol-acid coupled hydrogen production. The electrolytic cell is assembled by using a conductive substrate loaded with an anode catalyst noble metal/hydroxide as an anode, using a cathode catalyst as a cathode, and an electrolytic solution to form an electrolytic cell. Polyhydric alcohol is added to the electrolyte, and under voltage conditions, polyhydric alcohol is oxidized at the anode to generate polyol acid, and water is reduced at the cathode to generate hydrogen. The present invention constructs noble metal/hydroxide as the anode catalyst, uses hydrogen atom/oxygen atom in water as the source of [H]/[O] in the oxidation-reduction reaction, and utilizes the hydrogen bond between the hydroxide surface hydroxyl group and the polyol hydroxyl group, Adsorption and enrichment of polyols on the surface of the catalyst increases the local concentration of reactants to increase the current density, making it meet the needs of industrial production. At the same time, water is reduced to hydrogen at the cathode, further improving its industrial application potential.
Description
技术领域technical field
本发明属于多元醇酸生产技术领域，具体涉及一种电催化多元醇制备多元醇酸耦合产氢的方法。The invention belongs to the technical field of polyol acid production, and in particular relates to a method for electrocatalyzing polyalcohol to prepare polyalcohol-acid coupled hydrogen production.
背景技术Background technique
随着对可持续发展社会的呼吁，变废为宝的思路越来越受到科研人员的青睐。例如：甘油是生物柴油生产过程中的主要副产物，每生产九吨生物柴油就伴随着一吨甘油的产出。2020年生物柴油的产量已超468亿升(Renewables 2021-global status report)，这使得甘油产出过剩。另一方面，乙二醇是聚对苯二甲酸乙二醇酯(PET)塑料的关键单体。目前PET的年产量约7000万吨，然而只有不到20％的PET通过传统机械方法回收，剩下的被填埋或丢弃，这不仅严重污染环境且浪费大量乙二醇(Nat.Commun.,2021,12,4679)。如何升值甘油和乙二醇“废料”成为目前的科研难题。With the call for a sustainable society, the idea of turning waste into treasure is increasingly favored by researchers. For example: Glycerol is the main by-product in the biodiesel production process, and every nine tons of biodiesel produced is accompanied by the output of one ton of glycerin. The production of biodiesel in 2020 has exceeded 46.8 billion liters (Renewables 2021-global status report), which makes glycerin production surplus. Ethylene glycol, on the other hand, is a key monomer in polyethylene terephthalate (PET) plastic. At present, the annual output of PET is about 70 million tons, yet only less than 20% of PET is recycled by traditional mechanical methods, and the rest is landfilled or discarded, which not only seriously pollutes the environment but also wastes a lot of ethylene glycol (Nat.Commun., 2021, December, 4679). How to appreciate glycerin and ethylene glycol "waste" has become a current scientific research problem.
乳酸、乙醇酸分别是甘油、乙二醇的氧化产物，同时也分别是生物可降解塑料聚乳酸(PLA)、聚乙醇酸(PGA)的单体，且两者被广泛应用于化妆品和医疗等领域。目前乳酸和乙醇酸的生产均以微生物发酵法为主，但发酵法生产时间过于冗长且涉及复杂的分离步骤，限制了乳酸和乙醇酸的进一步发展。热催化甘油/乙二醇制乳酸/乙醇酸已被广泛研究(Appl.Catal.B,2021,284:119803；Nat.Commun.,2014,5(1):1-9)，但其需要高温高压的环境，不利于工业化生产。电催化法以可再生能源电能驱动，以水作为氧化还原反应中[O]和[H]来源，绿色无污染，近年来备受研究人员的关注。然而由于甘油和乙二醇的多羟基结构，使得C-C键易断裂，所以目前电催化多元醇的产物以附加值较低的甲酸为主。Lactic acid and glycolic acid are the oxidation products of glycerin and ethylene glycol respectively, and they are also the monomers of biodegradable plastics polylactic acid (PLA) and polyglycolic acid (PGA), respectively, and both are widely used in cosmetics and medical treatment, etc. field. At present, the production of lactic acid and glycolic acid is mainly based on microbial fermentation, but the production time of fermentation method is too long and involves complicated separation steps, which limits the further development of lactic acid and glycolic acid. Thermal catalysis of glycerol/ethylene glycol to lactic acid/glycolic acid has been extensively studied (Appl.Catal.B,2021,284:119803; Nat.Commun.,2014,5(1):1-9), but it requires high temperature The high-pressure environment is not conducive to industrial production. The electrocatalytic method is driven by renewable energy and uses water as the source of [O] and [H] in the redox reaction. It is green and pollution-free, and has attracted the attention of researchers in recent years. However, due to the polyhydric structure of glycerol and ethylene glycol, the C-C bond is easy to break, so the current electrocatalytic polyol products are mainly formic acid with low added value.
虽然近年已有文献利用贵金属基催化剂通过电催化甘油/乙二醇成功制备了乳酸/乙醇酸(J.Catal.,2017,356,14-21；Chem Catal.,2021,1,941-955)，但其电流密度难以达到工业生产的需求(>300mA cm-2)且乳酸/乙醇酸选择性和法拉第效率仍有待于提高。Although in recent years, lactic acid/glycolic acid has been successfully prepared by electrocatalyzing glycerol/ethylene glycol using noble metal-based catalysts (J. Catal., 2017, 356, 14-21; Chem Catal., 2021, 1, 941-955), but Its current density is difficult to meet the needs of industrial production (>300mA cm -2 ), and the selectivity of lactic acid/glycolic acid and faradaic efficiency still need to be improved.
发明内容Contents of the invention
本发明是为了克服现有贵金属基催化剂电催化多元醇制备多元醇酸技术中存在的缺点而提出的，其目的是提供一种电催化多元醇制备多元醇酸耦合产氢的方法，例如实现对过剩甘油和乙二醇的充分利用，将甘油和乙二醇在大电流密度下转化为更具有价值的乳酸和乙醇酸，变废为宝。The present invention is proposed in order to overcome the shortcomings existing in the existing technology of preparing polyol acid by electrocatalyzing polyol with noble metal catalyst, and its purpose is to provide a method for coupling hydrogen production by electrocatalyzing polyol to prepare polyol acid, such as realizing The full use of excess glycerin and ethylene glycol converts glycerin and ethylene glycol into more valuable lactic acid and glycolic acid under high current density, turning waste into treasure.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种电催化多元醇制备多元醇酸耦合产氢的方法，包括以下步骤：A method for electrocatalyzing polyhydric alcohols to prepare polyol-acid coupled hydrogen production, comprising the following steps:
(Ⅰ)组装电解池(I) Assembling the electrolytic cell
将负载阳极催化剂的导电基底作为阳极，将阴极催化剂作为阴极，与电解液组装成电解池；The conductive substrate supporting the anode catalyst is used as the anode, the cathode catalyst is used as the cathode, and the electrolytic cell is assembled with the electrolyte;
所述阳极催化剂为氢氧化物负载贵金属；The anode catalyst is a hydroxide supported noble metal;
(Ⅱ)电催化反应(Ⅱ) Electrocatalytic reaction
在电解液中加入多元醇，在电压条件下多元醇在阳极被氧化生成多元醇酸，水在阴极还原产生氢气。Polyhydric alcohol is added to the electrolyte, and polyhydric alcohol is oxidized at the anode to generate polyol acid under voltage conditions, and water is reduced at the cathode to generate hydrogen.
在上述技术方案中，所述多元醇为甘油、乙二醇、葡萄糖、山梨醇、***糖、木糖醇等。In the above technical solution, the polyhydric alcohol is glycerin, ethylene glycol, glucose, sorbitol, arabinose, xylitol and the like.
在上述技术方案中，当所述多元醇为甘油时，所述多元醇酸为乳酸；当所述多元醇为乙二醇时，所述多元醇酸为乙醇酸；当所述多元醇为葡萄糖时，所述多元醇酸为葡萄糖酸、葡萄糖二酸或乙醇酸；当所述多元醇为山梨醇、***糖、木糖醇时，所述多元醇酸为乳酸或乙醇酸。In the above technical solution, when the polyol is glycerol, the polyol acid is lactic acid; when the polyol is ethylene glycol, the polyol acid is glycolic acid; when the polyol is glucose When, the polyol acid is gluconic acid, glucaric acid or glycolic acid; when the polyalcohol is sorbitol, arabinose, xylitol, the polyol acid is lactic acid or glycolic acid.
在上述技术方案中，所述贵金属为铂、金、银、钌、铱、钯、铜或铑中的任意一种或几种。In the above technical solution, the noble metal is any one or more of platinum, gold, silver, ruthenium, iridium, palladium, copper or rhodium.
在上述技术方案中，所述氢氧化物为镍基、钴基、铜基等氢氧化物或水滑石材料。In the above technical solution, the hydroxide is nickel-based, cobalt-based, copper-based and other hydroxides or hydrotalcite materials.
在上述技术方案中，所述氢氧化物的制备方法为电沉积法、水热法、刻蚀法。In the above technical solution, the method for preparing the hydroxide is an electrodeposition method, a hydrothermal method, and an etching method.
在上述技术方案中，所述阳极的制备方法为电沉积法、液相还原法。In the above technical solution, the preparation method of the anode is an electrodeposition method and a liquid phase reduction method.
在上述技术方案中，所述电解液为氢氧化钠、氢氧化钾、氢氧化锂、碳酸氢钾、碳酸钾、碳酸氢钠、碳酸钠中的一种或几种水溶液，所述电解液中电解质的浓度为20g/L～300g/L。In the above technical scheme, the electrolyte is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, and sodium carbonate. The concentration of the electrolyte is 20g/L-300g/L.
在上述技术方案中，所述阴极催化剂为过渡金属氧化物、过渡金属磷化物、过渡金属硫化物、过渡金属氮化物、过渡金属硼化物、铂基催化剂、钯基催化剂、钌基催化剂、铑基催化剂、镍基催化剂或铜基催化剂中的任意一种或几种的混合物；当阴极催化剂为粉体时，所述阴极由导电基底负载阴极催化剂组成。In the above technical scheme, the cathode catalyst is transition metal oxide, transition metal phosphide, transition metal sulfide, transition metal nitride, transition metal boride, platinum-based catalyst, palladium-based catalyst, ruthenium-based catalyst, rhodium-based Any one or a mixture of catalysts, nickel-based catalysts or copper-based catalysts; when the cathode catalyst is powder, the cathode is composed of a conductive substrate supporting the cathode catalyst.
在上述技术方案中，所述导电基底为碳布、碳纸、泡沫镍、镍片、镍网、泡沫铜、铜片、铜网、钛片、钛网、不锈钢片、不锈钢网、ITO导电玻璃或FTO导电玻璃中的任意一种。In the above technical solution, the conductive substrate is carbon cloth, carbon paper, nickel foam, nickel sheet, nickel mesh, copper foam, copper sheet, copper mesh, titanium sheet, titanium mesh, stainless steel sheet, stainless steel mesh, ITO conductive glass Or any one of FTO conductive glass.
在上述技术方案中，所述电解液中多元醇的浓度为1g/L～50g/L。In the above technical solution, the concentration of the polyhydric alcohol in the electrolyte is 1 g/L-50 g/L.
在上述技术方案中，所述步骤(Ⅱ)电催化反应的电压为0V～2V vs Ag/AgCl。In the above technical scheme, the voltage of the electrocatalytic reaction in the step (II) is 0V-2V vs Ag/AgCl.
一种用于电催化多元醇制备多元醇酸的催化剂，所述催化剂为氢氧化物负载贵金属，所述氢氧化物为镍基、钴基、铜基等氢氧化物或水滑石材料；所述贵金属为铂、金、银、钌、铱、钯、铜或铑中的任意一种或几种；所述催化剂通过电沉积法、水热法、刻蚀法和液相还原法制备；所述催化剂在电催化反应中用作阳极催化剂。A catalyst for electrocatalyzing polyhydric alcohols to prepare polyol acids, the catalyst is a hydroxide-loaded noble metal, and the hydroxide is a nickel-based, cobalt-based, copper-based or other hydroxide or hydrotalcite material; the The noble metal is any one or more of platinum, gold, silver, ruthenium, iridium, palladium, copper or rhodium; the catalyst is prepared by electrodeposition, hydrothermal method, etching method and liquid phase reduction method; the The catalyst is used as an anode catalyst in the electrocatalytic reaction.
一种氢氧化物负载贵金属催化剂的应用，用于电催化多元醇制备多元醇酸。The application of a hydroxide-loaded noble metal catalyst is used to electrocatalyze polyols to prepare polyol acids.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明提供了一种电催化多元醇制备多元醇酸耦合产氢的方法，构筑贵金属/氢氧化物作为阳极电催化剂，以水中氢原子/氧原子作为氧化还原反应中[H]/[O]来源，利用氢氧化物表面羟基和多元醇羟基之间的氢键作用，在催化剂表面吸附富集多元醇，提高反应物局部浓度从而提高电流密度，使其达到工业生产需求，同时水在阴极被还原为氢气，进一步提高其工业应用潜力；在室温常压下就可实现高效电催化多元醇(如甘油、乙二醇)制备多元醇酸(如乳酸、乙醇酸)，同时阴极联产氢气，为多元醇酸(如乳酸、乙醇酸)的绿色高效制备提供了新的思路和方法。The invention provides a method for electrocatalyzing polyols to prepare polyol-acid coupled hydrogen production, constructing noble metal/hydroxide as an anode electrocatalyst, using hydrogen atoms/oxygen atoms in water as [H]/[O] in the oxidation-reduction reaction Source, using the hydrogen bond between the hydroxide surface hydroxyl group and the polyol hydroxyl group, adsorbs and enriches the polyol on the surface of the catalyst, increases the local concentration of the reactant to increase the current density, and makes it meet the needs of industrial production. At the same time, water is absorbed by the cathode It can be reduced to hydrogen to further improve its industrial application potential; high-efficiency electrocatalysis of polyols (such as glycerol, ethylene glycol) to prepare polyol acids (such as lactic acid, glycolic acid) can be achieved at room temperature and normal pressure, and the cathode co-produces hydrogen at the same time. It provides new ideas and methods for the green and efficient preparation of polyol acids (such as lactic acid and glycolic acid).
附图说明Description of drawings
图1是本发明的反应原理示意图(以乳酸为例)；Fig. 1 is a schematic diagram of the reaction principle of the present invention (taking lactic acid as an example);
图2是本发明实施例1中阳极催化剂的扫描电镜图；Fig. 2 is the scanning electron micrograph of anode catalyst in the
图3是本发明实施例1中阳极催化剂的X-射线衍射图；Fig. 3 is the X-ray diffraction figure of anode catalyst in the embodiment of the
图4是本发明实施例1中阳极催化剂电催化甘油的线性极化曲线图；Fig. 4 is the linear polarization curve diagram of electrocatalyzed glycerol by the anode catalyst in Example 1 of the present invention;
图5是本发明实施例1中阳极催化剂的电流密度同文献对比图；Fig. 5 is the current density of anode catalyst in the embodiment of the
图6是本发明实施例1甘油氧化产物的高效液相色谱图；Figure 6 is a high performance liquid chromatogram of the glycerin oxidation product of Example 1 of the present invention;
图7是本发明实施例2中阳极催化剂的扫描电镜图；Fig. 7 is the scanning electron micrograph of anode catalyst in the
图8是本发明实施例2乙二醇氧化产物的高效液相色谱图；Fig. 8 is the high performance liquid phase chromatogram of the ethylene glycol oxidation product of
图9是本发明实施例3中阳极催化剂的扫描电镜图；Fig. 9 is a scanning electron micrograph of the anode catalyst in Example 3 of the present invention;
图10是本发明实施例3乙二醇氧化产物的高效液相色谱图。Fig. 10 is a high performance liquid chromatogram of the oxidation product of ethylene glycol in Example 3 of the present invention.
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，可以根据以上附图获得其他的相关附图。For those skilled in the art, other related drawings can be obtained according to the above drawings without any creative effort.
具体实施方式Detailed ways
为了使本技术领域的人员更好地理解本发明技术方案，下面结合说明书附图并通过具体实施方式来进一步说明本发明的技术方案。In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be further described below in conjunction with the accompanying drawings and specific implementation methods.
实施例1Example 1
电催化甘油制备乳酸耦合产氢：Electrocatalytic Glycerin Preparation of Lactic Acid Coupled Hydrogen Production:
(1)制备阳极和阴极(1) Preparation of anode and cathode
A.阳极(泡沫镍负载的Au/Ni(OH)2)的制备A. Preparation of anode (Au/Ni(OH) 2 supported on nickel foam)
首先，制备泡沫镍负载的Ni(OH)2，具体方法为：首先将泡沫镍在乙醇中超声5分钟，后在稀盐酸中浸泡1h，随后在去离子水中超声5分钟，最后将其放入装有去离子水的反应釜中，在60℃下反应5天，以得到泡沫镍负载的Ni(OH)2。First, Ni(OH) 2 supported on nickel foam was prepared by ultrasonicating nickel foam for 5 minutes in ethanol, soaking in dilute hydrochloric acid for 1 hour, ultrasonicating in deionized water for 5 minutes, and finally putting it into React at 60° C. for 5 days in a reactor filled with deionized water to obtain Ni(OH) 2 supported on nickel foam.
然后，制备泡沫镍负载的Au/Ni(OH)2，具体方法为：配置10mM的氯金酸溶液并加入0.5M硼酸，将泡沫镍负载的Ni(OH)2用作工作电极、铂片用作对电极、饱和甘汞电极为参比电极组成三电极体系；在-1V vs Ag/AgCl下电沉积600s，获得阳极，即泡沫镍负载的Au/Ni(OH)2。Then, prepare Au/Ni(OH) 2 supported by foamed nickel, the specific method is: configure 10mM chloroauric acid solution and add 0.5M boric acid, use the Ni(OH) 2 supported by foamed nickel as the working electrode and platinum sheet A three-electrode system was formed as a counter electrode and a saturated calomel electrode as a reference electrode; electrodeposited at -1V vs Ag/AgCl for 600s to obtain the anode, that is, Au/Ni(OH) 2 supported on nickel foam.
所得阳极催化剂Au/Ni(OH)2的扫描电镜图和X-射线衍射图如图2、3所示，由图2/3可以看出，Ni(OH)2为纳米片阵列结构，金颗粒分布在纳米片阵列上，粒径为100nm～200nm。Gained anode catalyst Au/Ni(OH) The scanning electron microscope picture and the X-ray diffraction figure are as shown in Figure 2, 3, as can be seen from Figure 2/3, Ni (OH) 2 is nanosheet array structure, gold particles Distributed on the nano sheet array, the particle size is 100nm-200nm.
B.阴极(铂片)的制备B. Preparation of cathode (platinum sheet)
剪裁尺寸为15mm*15mm*2mm的铂片，剪裁后铂片用去离子水冲洗干净，即可使用。Cut the platinum sheet with a size of 15mm*15mm*2mm, rinse the platinum sheet with deionized water after cutting, and then use it.
(2)配置电解液(2) Configure the electrolyte
将5g甘油加入100mL质量浓度为50g/L的NaOH水溶液中，得到电解液。Add 5 g of glycerin into 100 mL of NaOH aqueous solution with a mass concentration of 50 g/L to obtain an electrolyte solution.
(3)电催化反应(3) Electrocatalytic reaction
将步骤(1)得到的阳极(泡沫镍负载的Au/Ni(OH)2)和阴极(铂片)放入步骤(2)得到的电解液中组成电解池，然后在常温常压，1.0V vs RHE偏压下电解1h，完成乳酸的制备。Put the anode (Au/Ni(OH) 2 supported by nickel foam) and the cathode (platinum sheet) obtained in step (1) into the electrolyte obtained in step (2) to form an electrolytic cell, and then at normal temperature and pressure, 1.0V vs RHE bias electrolysis for 1h to complete the preparation of lactic acid.
(4)检测(4) Detection
反应结束后，取1mL反应液并用酸中和，过滤掉杂质后，用高效液相色谱检测产物，结果如图6所示，乳酸的选择性为80％。同时，从图4本实施例的阳极催化剂电催化甘油的线性极化曲线图以及图5的本实施例的阳极催化剂的电流密度同文献对比图，可以看出，Au/Ni(OH)2在0.95V和1.05V vs RHE的电流密度高达384mA cm-2、605mA cm-2远超现有文献报导值。由于本发明反应电压未达到OER起始电压(>1.45V vs RHE)，且由液相结果计算法拉第效率可知，总法拉第效率为100％。After the reaction, 1mL of the reaction solution was taken and neutralized with acid. After filtering out impurities, the product was detected by high performance liquid chromatography. As shown in Figure 6, the selectivity of lactic acid was 80%. Simultaneously, from the linear polarization curve diagram of the electrocatalyzed glycerol of the anode catalyst of the present embodiment of Fig. 4 and the current density of the anode catalyst of the present embodiment of Fig. 5 and the literature comparison figure, it can be seen that Au/Ni(OH) The current densities of 0.95V and 1.05V vs RHE are as high as 384mA cm -2 and 605mA cm -2 , far exceeding the values reported in the existing literature. Since the reaction voltage of the present invention does not reach the OER initiation voltage (>1.45V vs RHE), and the Faraday efficiency is calculated from the liquid phase results, the total Faraday efficiency is 100%.
实施例2Example 2
电催化乙二醇制备乙醇酸耦合产氢：Coupling Hydrogen Production from Ethylene Glycol to Glycolic Acid:
(1)制备阳极和阴极(1) Preparation of anode and cathode
A.阳极(泡沫铜负载的Pd/Co(OH)2)的制备A. Preparation of anode (Pd/Co(OH) 2 supported on copper foam)
首先，制备泡沫铜负载的Co(OH)2，具体方法为：配置0.2M的硝酸钴溶液作为电解液，将泡沫铜用作工作电极、铂片用作对电极、饱和甘汞电极为参比电极组成三电极体系，在-1.2V下电沉积300s，获得泡沫铜负载的Co(OH)2。First, prepare Co(OH) 2 supported by foamed copper, the specific method is: configure 0.2M cobalt nitrate solution as electrolyte, use foamed copper as working electrode, platinum sheet as counter electrode, and saturated calomel electrode as reference electrode A three-electrode system was formed and electrodeposited at -1.2V for 300s to obtain Co(OH) 2 supported on foamed copper.
然后，制备泡沫铜负载的Pd/Co(OH)2，具体方法为：配置2mM的氯亚钯酸钾溶液，将泡沫铜负载的Pd/Co(OH)2放置于溶液中，在搅拌的情况下加入0.5g硼氢化钠，以制备泡沫铜负载的Pd/Co(OH)2。Then, prepare Pd/Co(OH) 2 supported by foamed copper, the specific method is: configure 2mM potassium chloropalladate solution, place Pd/Co(OH) 2 supported by foamed copper in the solution, and stir 0.5 g of sodium borohydride was added to prepare Pd/Co(OH) 2 supported on copper foam.
所得阳极催化剂Pd/Co(OH)2的扫描电镜图如图7所示。The scanning electron microscope image of the obtained anode catalyst Pd/Co(OH) 2 is shown in Figure 7.
B.阴极(碳布负载的磷化钴)的制备B. Preparation of cathode (cobalt phosphide supported on carbon cloth)
配置0.2M的硝酸钴溶液，将碳布用作工作电极、铂片用作对电极、饱和甘汞电极为参比电极组成三电极体系。在-1.2V下电沉积300s，获得碳布负载Co(OH)2；将1g次亚磷酸钠和碳布负载的Co(OH)2同时放入管式炉中，用Ar气进行吹扫，在300℃下煅烧2h，以获得碳布负载的磷化钴。Prepare 0.2M cobalt nitrate solution, use carbon cloth as working electrode, platinum sheet as counter electrode, and saturated calomel electrode as reference electrode to form a three-electrode system. Electrodeposit at -1.2V for 300s to obtain Co(OH) 2 supported on carbon cloth; put 1 g of sodium hypophosphite and Co(OH) 2 supported on carbon cloth into the tube furnace at the same time, and purge with Ar gas, Calcined at 300°C for 2h to obtain cobalt phosphide supported on carbon cloth.
(2)配置电解液(2) Configure the electrolyte
将3.5g乙二醇加入100mL质量浓度为60g/L的KOH水溶液中，得到电解液。Add 3.5 g of ethylene glycol into 100 mL of KOH aqueous solution with a mass concentration of 60 g/L to obtain an electrolyte solution.
(3)电催化反应(3) Electrocatalytic reaction
将步骤(1)得到的阳极(泡沫铜负载的Pd/Co(OH)2)和阴极(碳布负载的磷化钴)放入步骤(2)得到电解液中组成电解池，然后在常温常压下、1.1V vs RHE偏压下电解1h，完成乙醇酸的制备。由液相结果计算法拉第效率可知，总法拉第效率为100％。Put the anode (Pd/Co(OH) 2 supported by foam copper) and the cathode (cobalt phosphide supported by carbon cloth) obtained in step (1) into the electrolyte obtained in step (2) to form an electrolytic cell, and then The preparation of glycolic acid was completed by electrolysis for 1 h under pressure and 1.1V vs RHE bias. The Faradaic efficiency calculated from the liquid phase results shows that the total Faradaic efficiency is 100%.
(4)检测(4) Detection
反应结束后，取1mL反应液并用酸中和，过滤掉杂质后，用高效液相色谱检测产物，结果如图8所示，乙醇酸的选择性为95％。After the reaction, 1mL of the reaction solution was taken and neutralized with acid, and the impurities were filtered out, and the product was detected by high performance liquid chromatography. As shown in Figure 8, the selectivity of glycolic acid was 95%.
实施例3：电催化甘油制备乳酸耦合产氢Example 3: Electrocatalytic Glycerin Preparation of Lactic Acid Coupled Hydrogen Production
(1)制备阳极和阴极(1) Preparation of anode and cathode
A.阳极(钛网负载的Pt/NiFe(OH)x)的制备A. Preparation of anode (Pt/NiFe(OH) x supported on titanium mesh)
首先，制备钛网负载的NiFe(OH)x，具体方法为：配置0.25mmol的硝酸镍和0.15mmol的硫酸亚铁混合溶液80mL，并加入1.25mmol氟化铵和9mmol尿酸，搅拌均匀后倒入高压反应釜中，随后将清洗好的钛网放入溶液中。在120℃下反应6h，以制备NiFe(OH)x。然后制备钛网负载的Au/NiFe(OH)x，具体方法为：配置10mM的氯铂酸溶液并加入0.15M氯化钠作为电解液，将钛网负载的NiFe(OH)x用作工作电极、铂片用作对电极、饱和甘汞电极为参比电极组成三电极体系，在-1V下电沉积600s，获得阳极，即钛网负载的Pt/NiFe(OH)x。First, prepare NiFe(OH) x supported by titanium mesh. The specific method is: prepare 80 mL of a mixed solution of 0.25 mmol of nickel nitrate and 0.15 mmol of ferrous sulfate, add 1.25 mmol of ammonium fluoride and 9 mmol of uric acid, stir well and pour In the autoclave, the cleaned titanium mesh is then put into the solution. React at 120°C for 6h to prepare NiFe(OH) x . Then prepare Au/NiFe(OH) x supported by titanium mesh, the specific method is: configure 10mM chloroplatinic acid solution and add 0.15M sodium chloride as electrolyte, and use NiFe(OH) x supported by titanium mesh as working electrode A three-electrode system consisting of a platinum sheet as the counter electrode and a saturated calomel electrode as the reference electrode was electrodeposited at -1V for 600s to obtain the anode, that is, Pt/NiFe(OH) x supported on titanium mesh.
所得阳极催化剂Pt/NiFe(OH)x的扫描电镜图如图9所示。The scanning electron microscope image of the obtained anode catalyst Pt/NiFe(OH) x is shown in FIG. 9 .
B.阴极(镍网负载的硫化镍)的制备B. Preparation of cathode (nickel sulfide supported on nickel mesh)
配置0.2M的硝酸镍溶液作为电解液，将镍网用作工作电极、铂片用作对电极、饱和甘汞电极为参比电极组成三电极体系。在-1.2V下电沉积300s，获得镍网负载的Ni(OH)2；将镍网负载的Ni(OH)2和0.1g硫代乙酰胺放入高压反应釜中，在120℃下反应6h，以获得镍网负载的硫化镍即得到阴极。A 0.2M nickel nitrate solution was used as the electrolyte, a nickel mesh was used as the working electrode, a platinum sheet was used as the counter electrode, and a saturated calomel electrode was used as the reference electrode to form a three-electrode system. Electrodeposit at -1.2V for 300s to obtain Ni(OH) 2 supported on nickel mesh; put Ni(OH) 2 supported on nickel mesh and 0.1g thioacetamide in an autoclave, and react at 120°C for 6h To obtain the nickel sulfide supported by the nickel mesh to obtain the cathode.
(2)配置电解液(2) Configure the electrolyte
将10g乙二醇加入100mL质量浓度为100g/L的KOH水溶液中，得到电解液。Add 10 g of ethylene glycol into 100 mL of KOH aqueous solution with a mass concentration of 100 g/L to obtain an electrolyte solution.
(3)电催化反应(3) Electrocatalytic reaction
将步骤(1)得到的阳极(钛网负载的Pt/NiFe(OH)x)和阴极(镍网负载的硫化镍)放入步骤(2)得到电解液中组成电解池，然后在常温常压下、1.2V vs RHE偏压下电解1h，完成乙醇酸的制备。Put the anode (Pt/NiFe(OH) x supported by titanium mesh) and the cathode (nickel sulfide supported by nickel mesh) obtained in step (1) into the electrolyte obtained in step (2) to form an electrolytic cell, and then at normal temperature and pressure Glycolic acid was prepared by electrolysis for 1 h at 1.2 V vs RHE bias.
(4)检测(4) Detection
反应结束后，取1mL反应液并用酸中和，过滤掉杂质后，用高效液相色谱检测产物，结果如图10所示，乙醇酸的选择性为86％。且由液相结果计算法拉第效率可知，总法拉第效率为100％。After the reaction, 1 mL of the reaction solution was taken and neutralized with acid, and after impurities were filtered out, the product was detected by high performance liquid chromatography. As shown in Figure 10, the selectivity of glycolic acid was 86%. And it can be seen from the calculation of Faradaic efficiency from the liquid phase results that the total Faradaic efficiency is 100%.
本发明的设计原理：Design principle of the present invention:
如图1所示，本发明构筑贵金属/氢氧化物作为阳极电催化剂，以水中氢原子/氧原子作为氧化还原反应中[H]/[O]来源，利用氢氧化物表面羟基和多元醇羟基之间的氢键作用，在催化剂表面吸附富集多元醇，提高反应物局部浓度从而提高电流密度，使其达到工业生产需求，同时水在阴极被还原为氢气。As shown in Figure 1, the present invention constructs noble metal/hydroxide as an anode electrocatalyst, uses hydrogen atom/oxygen atom in water as the source of [H]/[O] in the redox reaction, and utilizes hydroxide surface hydroxyl and polyol hydroxyl The hydrogen bond between the catalysts adsorbs and enriches polyols on the surface of the catalyst, increasing the local concentration of reactants to increase the current density, so that it can meet the needs of industrial production, and at the same time, water is reduced to hydrogen at the cathode.
化学反应方程式为：The chemical reaction equation is:
(1)以甘油为例(1) Taking glycerin as an example
阳极反应为：C3H8O3+2OH--2e-→C3H6O3+2H2O；The anode reaction is: C 3 H 8 O 3 +2OH - -2e - →C 3 H 6 O 3 +2H 2 O;
阴极反应为：2H2O+2e-→H2+2OH-。The cathode reaction is: 2H 2 O+2e - →H 2 +2OH - .
(2)以乙二醇为例(2) Taking ethylene glycol as an example
阳极反应为：C2H6O2+4OH--4e-→C2H4O3+2H2O；The anode reaction is: C 2 H 6 O 2 +4OH - -4e - →C 2 H 4 O 3 +2H 2 O;
阴极反应为：2H2O+2e-→H2+2OH-。The cathode reaction is: 2H 2 O+2e - →H 2 +2OH - .
本发明响应可持续发展社会的呼吁，开发了可用于多元醇绿色高效制备多元醇酸的生产方法，通过氢氧化物表面羟基和多元醇羟基的氢键作用吸附富集多元醇，从而大幅提高反应速率，为高效绿色制备多元醇酸提供了新的思路和方法。The present invention responds to the appeal of a sustainable development society, and develops a production method that can be used for the green and efficient preparation of polyol acids from polyols. It absorbs and enriches polyols through the hydrogen bond between the hydroxyl groups on the surface of hydroxide and the hydroxyl groups of polyols, thereby greatly improving the reaction rate. The speed provides new ideas and methods for the efficient and green preparation of polyol acids.
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, and those skilled in the art should understand that any person skilled in the art should be aware of any disclosure in the present invention Within the technical scope, easily conceivable changes or substitutions all fall within the scope of protection and disclosure of the present invention.
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