TWI415792B - Method for making carbon composite material - Google Patents
Method for making carbon composite material Download PDFInfo
- Publication number
- TWI415792B TWI415792B TW98110289A TW98110289A TWI415792B TW I415792 B TWI415792 B TW I415792B TW 98110289 A TW98110289 A TW 98110289A TW 98110289 A TW98110289 A TW 98110289A TW I415792 B TWI415792 B TW I415792B
- Authority
- TW
- Taiwan
- Prior art keywords
- metal
- composite material
- solution
- carbon composite
- terephthalic acid
- Prior art date
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
本發明涉及一種碳複合材料之製備方法。The invention relates to a method for preparing a carbon composite material.
碳複合材料具有多種用途，可以用作氣敏材料、電極材料等。先前之碳複合材料主要係通過溶膠-凝膠法製備，該製備過程一般包括：製備一含有金屬之有機溶膠；該有機溶膠形成凝膠；該凝膠中之水與有機溶劑等物質進行交換，以形成有機凝膠；超臨界乾燥該有機凝膠為雜化氣凝膠；以及碳化該雜化氣凝膠等步驟。其中，所述有機溶膠之形成過程一般包括原料之水解、縮合化學反應等過程。所述凝膠之形成過程為該有機溶膠經陳化膠粒間緩慢聚合，形成三維空間網路結構之凝膠。所述有機凝膠之形成過程為所述三維空間網絡結構之凝膠中之水與有機溶劑等物質進行交換，使得該凝膠之網絡間充滿了失去流動性之有機溶劑，以形成有機凝膠。目前該製備方法所使用之原料之價格比較昂貴，有些有機物原料對健康有害；該製備過程製備週期長，主要係由於溶膠-凝膠過程之週期長，通常需要幾天或幾週之時間，凝膠中之水與有機溶劑之交換緩慢，時間長；另外，採用超臨界乾燥技術需要高壓設備，因而成本較高。Carbon composites have a variety of uses and can be used as gas sensing materials, electrode materials, and the like. The previous carbon composite material is mainly prepared by a sol-gel method, and the preparation process generally comprises: preparing a metal-containing organosol; the organosol forms a gel; and the water in the gel is exchanged with an organic solvent or the like. To form an organogel; supercritical drying of the organogel as a hybrid aerogel; and carbonization of the hybrid aerogel. Wherein, the formation process of the organosol generally includes a process of hydrolysis of a raw material, a condensation chemical reaction, and the like. The gel is formed by slowly polymerizing the organosol through the aged colloidal particles to form a gel of a three-dimensional network structure. The formation process of the organogel is such that the water in the gel of the three-dimensional network structure exchanges with a substance such as an organic solvent, so that the network of the gel is filled with an organic solvent that loses fluidity to form an organogel. . At present, the raw materials used in the preparation method are relatively expensive, and some organic materials are harmful to health; the preparation process has a long preparation period, mainly due to the long period of the sol-gel process, which usually takes several days or several weeks, and is usually condensed. The exchange of water in the glue with the organic solvent is slow and takes a long time; in addition, the use of supercritical drying technology requires high-pressure equipment, and thus the cost is high.
為解決上述問題，朱珍平等人提供了一種碳複合材料之製備方法。具體請參閱朱珍平等人於2004年9月22日公告的、公告號為CN1167614C、標題為“一種製備金屬-碳複合奈米材料之方法”之中國大陸專利。該專利中揭示了一種製備金屬-碳複合奈米材料之方法，該方法係將瀝青與濃硫酸和濃硝酸進行硝化氧化反應，然後過濾硝化氧化反應後之溶液得到一濾餅；用強鹼溶解該濾餅，然後過濾，得到一濾液；向該濾液中加入鹽酸或硝酸，使之絮凝得到一碳基凝膠；加熱該碳基凝膠使之轉化為碳基溶膠，將金屬鹽溶液加入該碳基溶膠中進行混合、乾燥，制得含金屬之***前驅物；將該***前驅物在熱引發下***，製備出金屬-碳複合奈米材料。In order to solve the above problems, Zhu Zhenping provided a method for preparing a carbon composite material. For details, please refer to the mainland China patent entitled "A Method for Preparing Metal-Carbon Composite Nanomaterials" announced by Zhu Zhenping on September 22, 2004, with the announcement number CN1167614C. The patent discloses a method for preparing a metal-carbon composite nano material by performing nitrification oxidation reaction of the asphalt with concentrated sulfuric acid and concentrated nitric acid, and then filtering the solution after the nitrification oxidation reaction to obtain a filter cake; dissolving with a strong alkali; The filter cake is then filtered to obtain a filtrate; hydrochloric acid or nitric acid is added to the filtrate to flocculate to obtain a carbon-based gel; the carbon-based gel is heated to be converted into a carbon-based sol, and a metal salt solution is added thereto. The carbon-based sol is mixed and dried to obtain a metal-containing explosive precursor; the explosive precursor is exploded under heat initiation to prepare a metal-carbon composite nanomaterial.
該製備方法雖然較前述製備方法簡單、週期短，需要一兩天之時間，但其製備過程仍繁瑣；而且該製備過程中需要用濃硫酸、濃硝酸以及***過程，故該方法具有較高之危險性。另外，該製備方法成本較高。Although the preparation method is simpler than the foregoing preparation method and has a short cycle, it takes one or two days, but the preparation process is still cumbersome; and the preparation process requires concentrated sulfuric acid, concentrated nitric acid and an explosion process, so the method has a higher method. Dangerous. In addition, the preparation method is costly.
有鑒於此，實為必要提供一種簡單、安全且成本較低之碳複合材料之製備方法。In view of this, it is necessary to provide a simple, safe and low cost method for preparing carbon composite materials.
一種碳複合材料之製備方法，包括：提供一金屬對苯二甲酸配位聚合物；以及在一惰性氣體或氮氣之環境下，在500攝氏度至1300攝氏度加熱所述金屬對苯二甲酸配位聚合物，得到一碳複合材料。A method for preparing a carbon composite material, comprising: providing a metal terephthalic acid coordination polymer; and heating the metal terephthalic acid coordination polymerization at 500 degrees Celsius to 1300 degrees Celsius in an inert gas or nitrogen atmosphere To obtain a carbon composite.
相較於先前技術，所述碳複合材料之製備方法，充分利用金屬對苯二甲酸配位聚合物中之配位體對苯二甲酸之高含碳量，通過熱解金屬對苯二甲酸配位聚合物獲得碳複合材料。因此，該製備方法簡單、安全、成本較低、有利於工業上實現。Compared with the prior art, the carbon composite material preparation method fully utilizes the high carbon content of the ligand terephthalic acid in the metal terephthalic acid coordination polymer, and pyrolyzes the metal terephthalic acid. The polymer is obtained as a carbon composite. Therefore, the preparation method is simple, safe, and low in cost, and is industrially advantageous.
下面將結合附圖及實施例對本發明提供之碳複合材料之製備方法作進一步之詳細說明。The preparation method of the carbon composite material provided by the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.
請參閱圖1，本發明提供之碳複合材料之製備方法包括以下步驟：Referring to FIG. 1 , a method for preparing a carbon composite material provided by the present invention includes the following steps:
第一，提供一金屬對苯二甲酸配位聚合物。First, a metal terephthalic acid coordination polymer is provided.
下面介紹一種所述金屬對苯二甲酸配位聚合物之製備方法。首先，將可溶性金屬鹽溶解在適量蒸餾水中得到第一溶液。其中，所述金屬對苯二甲酸配位聚合物不容易溶入水中；該金屬對苯二甲酸配位聚合物中之金屬元素優選為過渡金屬元素，如，鋅元素、鎘元素、錳元素、鈷元素、鎳元素或銅元素等。所述可溶性金屬鹽包括氯化鹽、硫酸鹽、硝酸鹽、醋酸鹽或其任意組合。A method for preparing the metal terephthalic acid coordination polymer is described below. First, a soluble metal salt is dissolved in an appropriate amount of distilled water to obtain a first solution. Wherein, the metal terephthalic acid coordination polymer is not easily dissolved in water; the metal element in the metal terephthalic acid coordination polymer is preferably a transition metal element, such as zinc element, cadmium element, manganese element, Cobalt, nickel or copper. The soluble metal salt includes a chloride salt, a sulfate salt, a nitrate salt, an acetate salt, or any combination thereof.
其次，將對苯二甲酸混合在適量蒸餾水中，加入鹼性溶液使其溶解得到第二溶液。其中，所述對苯二甲酸之物質的量不超過可溶性金屬鹽之物質的量，優選地，該對苯二甲酸之物質的量與該可溶性金屬鹽之物質的量相等。所述鹼性溶液包括NaOH溶液、氨水溶液、Na2 CO3 溶液、NaHCO3 溶液、K2 CO3 溶液、KHCO3 溶液或其任意組合。所述鹼性溶液之作用係促進對苯二甲酸之溶解。Next, terephthalic acid is mixed in an appropriate amount of distilled water, and an alkaline solution is added to dissolve it to obtain a second solution. Wherein the amount of the terephthalic acid substance does not exceed the amount of the substance of the soluble metal salt, preferably, the amount of the substance of the terephthalic acid is equal to the amount of the substance of the soluble metal salt. The alkaline solution includes a NaOH solution, an aqueous ammonia solution, a Na 2 CO 3 solution, a NaHCO 3 solution, a K 2 CO 3 solution, a KHCO 3 solution, or any combination thereof. The action of the alkaline solution promotes the dissolution of terephthalic acid.
然後，將第一溶液和第二溶液混合，並在室溫下攪拌2小時至12小時後過濾，得到一濾餅；用去離子水淋洗該濾餅，並乾燥該淋洗後之濾餅，即得到所述金屬對苯二甲酸配位聚合物。其中，所述用去離子水淋洗該濾餅之目之係為了去除該濾餅中之鹼性溶液、多餘之可溶性金屬鹽、多餘之對苯二甲酸等雜質，使得該濾餅之組成更單一。所述乾燥之方法包括真空乾燥、冷凍乾燥、氣流乾燥、熱固乾燥或自然乾燥。根據所述金屬對苯二甲酸配位聚合物在水中之溶解度之不同，所述攪拌時間也不同。具體地，金屬對苯二甲酸配位聚合物在水中之溶解度越高，所需要之攪拌時間越短；反之，金屬對苯二甲酸配位聚合物在水中之溶解度越低，所需要之攪拌時間就越長。Then, the first solution and the second solution are mixed, and stirred at room temperature for 2 hours to 12 hours, followed by filtration to obtain a filter cake; the filter cake is rinsed with deionized water, and the rinsed filter cake is dried. That is, the metal terephthalic acid coordination polymer is obtained. Wherein, the purpose of rinsing the filter cake with deionized water is to remove impurities such as an alkaline solution, excess soluble metal salt, and excess terephthalic acid in the filter cake, so that the composition of the filter cake is further single. The drying method includes vacuum drying, freeze drying, air flow drying, thermosetting drying or natural drying. The stirring time varies depending on the solubility of the metal terephthalate coordination polymer in water. Specifically, the higher the solubility of the metal terephthalic acid coordination polymer in water, the shorter the stirring time required; on the contrary, the lower the solubility of the metal terephthalic acid coordination polymer in water, the required stirring time The longer it is.
應當指出，採用其他方法得到金屬對苯二甲酸配位聚合物，並使用本發明構思來製備碳複合材料，也應在本專利申請之保護範圍之內。It should be noted that the use of other methods to obtain a metal terephthalic acid coordination polymer and the use of the inventive concept to prepare a carbon composite material is also within the scope of the present patent application.
第二，在一惰性氣體或氮氣之環境下，在500攝氏度至1300攝氏度加熱所述金屬對苯二甲酸配位聚合物，得到一碳複合材料。Second, the metal terephthalic acid coordination polymer is heated at 500 degrees Celsius to 1300 degrees Celsius in an inert gas or nitrogen atmosphere to obtain a carbon composite material.
具體地，將所述金屬對苯二甲酸配位聚合物可以置於一瓷舟(陶瓷或石英容器)中，在惰性氣體或氮氣保護下，在500攝氏度到1300攝氏度加熱該金屬對苯二甲酸配位聚合物一段時間，然後自然降至室溫便可得到所述碳複合材料。其中，所述惰性氣體包括氦氣、氖氣、氬氣、氪氣、氙氣。所述金屬對苯二甲酸配位聚合物加熱一段時間之目的係為了確保該金屬對苯二甲酸配位聚合物充分加熱，完全轉化為碳複合材料。所述一段時間優選為1小時至3小時。Specifically, the metal terephthalic acid coordination polymer may be placed in a porcelain boat (ceramic or quartz container), and the metal terephthalic acid is heated at 500 degrees Celsius to 1300 degrees Celsius under the protection of an inert gas or nitrogen gas. The carbon composite is obtained by complexing the polymer for a period of time and then naturally dropping it to room temperature. Wherein, the inert gas includes helium, neon, argon, helium, neon. The purpose of heating the metal terephthalic acid coordination polymer for a period of time is to ensure that the metal terephthalic acid coordination polymer is sufficiently heated to be completely converted into a carbon composite. The period of time is preferably from 1 hour to 3 hours.
另外，根據金屬元素之化學性質之不同，具體地，根據金屬之化學性質之活潑性不同，所述碳複合材料為金屬氧化物與碳之複合材料或金屬與碳之複合材料。一般地，當金屬之化學性質比較活潑時，金屬較容易與氧結合形成金屬氧化物，故所述碳複合材料為金屬氧化物與碳之複合材料；當金屬元素之化學性質不活潑時，金屬就不容易與氧結合形成金屬氧化物，故所述碳複合材料為金屬與碳之複合材料。如，當所述金屬元素為鋅元素、鎘元素、錳元素或其任意組合時，所述碳複合材料為金屬氧化物與碳之複合材料；當所述金屬元素為鈷元素、鎳元素、銅元素或其任意組合時，所述碳複合材料為金屬與碳之複合材料。Further, depending on the chemical nature of the metal element, specifically, the carbon composite material is a composite material of metal oxide and carbon or a composite material of metal and carbon depending on the reactivity of the chemical properties of the metal. Generally, when the chemical nature of the metal is relatively active, the metal is more easily combined with oxygen to form a metal oxide, so the carbon composite material is a composite material of metal oxide and carbon; when the chemical property of the metal element is not active, the metal It is not easy to combine with oxygen to form a metal oxide, so the carbon composite material is a composite material of metal and carbon. For example, when the metal element is a zinc element, a cadmium element, a manganese element or any combination thereof, the carbon composite material is a composite material of a metal oxide and carbon; when the metal element is a cobalt element, a nickel element, or a copper When the element or any combination thereof, the carbon composite material is a composite of metal and carbon.
第一實施例：First embodiment:
本發明第一實施例提供氧化鋅與碳之複合材料ZnO-C之製備方法，該方法具體包括以下步驟：The first embodiment of the present invention provides a method for preparing a composite material of zinc oxide and carbon, ZnO-C, which comprises the following steps:
第一，提供一鋅對苯二甲酸配位聚合物Zn(BDC)。First, a zinc terephthalic acid coordination polymer Zn (BDC) is provided.
所述Zn(BDC)之製備方法為：首先，將10毫摩爾(mmol)可溶性鋅鹽溶解在50毫升(ml)蒸餾水中得到第一溶液；在100ml蒸餾水中溶解20mmol NaOH溶液後加入10mmol對苯二甲酸攪拌至溶解，得到第二溶液。其中，所述可溶性鋅鹽包括氯化鋅、硫酸鋅、硝酸鋅、醋酸鋅或其任意組合。本實施例中，所述鋅鹽為硫酸鋅。The Zn (BDC) is prepared by first dissolving 10 millimoles (mmol) of soluble zinc salt in 50 milliliters (ml) of distilled water to obtain a first solution; after dissolving 20 mmol of NaOH solution in 100 ml of distilled water, adding 10 mmol of benzene to the benzene The dicarboxylic acid was stirred until dissolved to give a second solution. Wherein, the soluble zinc salt comprises zinc chloride, zinc sulfate, zinc nitrate, zinc acetate or any combination thereof. In this embodiment, the zinc salt is zinc sulfate.
然後，將第一溶液和第二溶液混合，在室溫下攪拌5小時後過濾，得到一濾餅；用50ml去離子水淋洗該濾餅，並乾燥該淋洗後之濾餅，即可得到Zn(BDC)。其中，乾燥之方法為將所述清洗後之濾餅加熱至50攝氏度進行乾燥。Then, the first solution and the second solution are mixed, stirred at room temperature for 5 hours, and then filtered to obtain a filter cake; the filter cake is rinsed with 50 ml of deionized water, and the rinsed filter cake is dried. Zn (BDC) was obtained. The method of drying is to heat the filter cake after washing to 50 degrees Celsius for drying.
第二，加熱該Zn(BDC)，以得到ZnO-C材料。Second, the Zn (BDC) is heated to obtain a ZnO-C material.
具體地，取1克Zn(BDC)置於瓷舟(陶瓷或石英容器)中，在氬氣保護下，在800攝氏度加熱該Zn(BDC)2小時，然後自然降至室溫便可得到ZnO-C材料。Specifically, 1 g of Zn (BDC) was placed in a porcelain boat (ceramic or quartz container), and the Zn (BDC) was heated at 800 ° C for 2 hours under argon gas protection, and then naturally cooled to room temperature to obtain ZnO. -C material.
圖2為所述ZnO-C材料之掃描電鏡照片。該ZnO-C材料中之粒子之直徑不超過10微米。由於ZnO可以用作氣敏材料，而且該ZnO-C材料中之C具有多孔結構可以增強ZnO之吸附能力，吸附能力增強有利於ZnO氣敏作用之發揮，所以，該ZnO-C材料可以用作氣敏材料，以用於氣體感測器和石油脫硫材料。Figure 2 is a scanning electron micrograph of the ZnO-C material. The particles in the ZnO-C material have a diameter of no more than 10 microns. Since ZnO can be used as a gas sensing material, and the porous structure of C in the ZnO-C material can enhance the adsorption capacity of ZnO, and the adsorption capacity is enhanced to facilitate the gas sensing of ZnO, the ZnO-C material can be used as a material. Gas-sensitive materials for gas sensors and petroleum desulfurization materials.
其中，該第一實施例中之可溶性鋅鹽可以用可溶性鎘鹽代替，以製備氧化鎘與碳之複合材料CdO-C。該CdO-C材料可用作氣敏材料，以用於氣體感測器和石油脫硫材料。Wherein, the soluble zinc salt in the first embodiment can be replaced by a soluble cadmium salt to prepare a composite material CdO-C of cadmium oxide and carbon. The CdO-C material can be used as a gas sensing material for gas sensors and petroleum desulfurization materials.
第二實施例：Second embodiment:
本發明第二實施例提供一氧化錳與碳之複合材料MnO-C之製造方法，該方法具體包括以下步驟：A second embodiment of the present invention provides a method for manufacturing a composite material of manganese monoxide and carbon, MnO-C, which comprises the following steps:
第一，提供一錳對苯二甲酸配位聚合物Mn(BDC)。First, a manganese terephthalate coordination polymer Mn (BDC) is provided.
首先，將10mmol可溶性錳鹽溶解在50ml蒸餾水中得到第一溶液；在100ml蒸餾水中溶解20mmol KHCO3 溶液後加入10mmol對苯二甲酸攪拌至溶解，得到第二溶液。所述可溶性錳鹽包括氯化錳、硫酸錳、硝酸錳、醋酸錳或其任意組合。本實施例中，所述可溶性錳鹽為水合Mn(NO3 )2 。First, 10 mmol of the soluble manganese salt was dissolved in 50 ml of distilled water to obtain a first solution; after dissolving 20 mmol of KHCO 3 solution in 100 ml of distilled water, 10 mmol of terephthalic acid was added and stirred until dissolved, to obtain a second solution. The soluble manganese salt includes manganese chloride, manganese sulfate, manganese nitrate, manganese acetate or any combination thereof. In this embodiment, the soluble manganese salt is hydrated Mn(NO 3 ) 2 .
然後，將第一溶液和第二溶液混合，在室溫下攪拌3小時後過濾，得到一濾餅；用50ml去離子水淋洗該濾餅，並於50攝氏度下乾燥該淋洗後之濾餅，即製備出錳對苯二甲酸配位聚合物Mn(BDC)。Then, the first solution and the second solution are mixed, stirred at room temperature for 3 hours, and then filtered to obtain a filter cake; the filter cake is rinsed with 50 ml of deionized water, and the filtered filter is dried at 50 degrees Celsius. The cake, that is, the manganese terephthalic acid coordination polymer Mn (BDC) was prepared.
第二，加熱該Mn(BDC)，以得到MnO-C材料。Second, the Mn (BDC) is heated to obtain a MnO-C material.
取1克Mn(BDC)置於瓷舟(陶瓷或石英容器)中，在氮氣保護下，從室溫經升至600攝氏度，維持600攝氏度並加熱3小時後自然降至室溫便可得到MnO-C材料。Take 1 gram of Mn (BDC) in a porcelain boat (ceramic or quartz container), raise it to 600 ° C from room temperature under nitrogen protection, maintain 600 ° C and heat for 3 hours, then naturally drop to room temperature to obtain MnO-C material.
圖3為所述MnO-C材料之掃描電鏡照片。該MnO-C材料中之粒子之直徑不超過5微米。該MnO-C材料可用作鋰離子電池負極材料。Figure 3 is a scanning electron micrograph of the MnO-C material. The diameter of the particles in the MnO-C material does not exceed 5 microns. The MnO-C material can be used as a negative electrode material for a lithium ion battery.
本發明第二實施例提供之MnO-C材料之製備方法與第一實施例提供之ZnO-C材料之製備方法基本相同。第二實施例之MnO-C材料之用途與第一實施例之ZnO-C材料之用途不同。由於MnO可以作為鋰離子電池之負極材料，而且該MnO-C材料中之C具有導電性，可以增強MnO之導電性能；所以MnO-C材料可用作鋰離子電池之負極材料。The preparation method of the MnO-C material provided by the second embodiment of the present invention is basically the same as the preparation method of the ZnO-C material provided by the first embodiment. The use of the MnO-C material of the second embodiment is different from that of the ZnO-C material of the first embodiment. Since MnO can be used as a negative electrode material for a lithium ion battery, and C in the MnO-C material has electrical conductivity, the electrical conductivity of MnO can be enhanced; therefore, the MnO-C material can be used as a negative electrode material for a lithium ion battery.
第三實施例：Third embodiment:
本發明第三實施例提供鈷與碳之複合材料Co-C之製備方法，該方法具體步驟如下：A third embodiment of the present invention provides a method for preparing Co-C composite material of cobalt and carbon, and the specific steps of the method are as follows:
第一，提供一鈷對苯二甲酸配位聚合物Co(BDC)。First, a cobalt terephthalic acid coordination polymer Co (BDC) is provided.
首先將10mmol可溶性鈷鹽溶解在50ml蒸餾水中得到第一溶液；在100ml蒸餾水中溶解25mmol氨水溶液後加入10mmol對苯二甲酸攪拌至溶解，得到第二溶液。所述可溶性鈷鹽包括氯化鈷、硫酸鈷、硝酸鈷、醋酸鈷或其任意組合。本實施例中，所述可溶性鈷鹽為水合Co(NO3 )2 。First, 10 mmol of the soluble cobalt salt was dissolved in 50 ml of distilled water to obtain a first solution; after dissolving 25 mmol of an aqueous ammonia solution in 100 ml of distilled water, 10 mmol of terephthalic acid was added and stirred until dissolved to obtain a second solution. The soluble cobalt salt includes cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt acetate or any combination thereof. In this embodiment, the soluble cobalt salt is hydrated Co(NO 3 ) 2 .
然後，將第一溶液和第二溶液混合，並在室溫下攪拌12小時後過濾，得到一濾餅；用50ml去離子水淋洗該濾餅，並在50攝氏度下乾燥該淋洗後之濾餅，以得到Co(BDC)。Then, the first solution and the second solution were mixed, and stirred at room temperature for 12 hours, and then filtered to obtain a filter cake; the filter cake was rinsed with 50 ml of deionized water, and dried at 50 ° C. Filter cake to obtain Co(BDC).
第二，加熱該Co(BDC)，以得到Co-C材料。Second, the Co(BDC) is heated to obtain a Co-C material.
取1克Co(BDC)置於瓷舟(陶瓷或石英容器)中，在氮氣保護下，從室溫升至900攝氏度，維持900攝氏度並加熱1小時後自然降至室溫便可得到Co-C材料。Take 1 gram of Co (BDC) in a porcelain boat (ceramic or quartz container), raise it to 900 ° C from room temperature under nitrogen protection, maintain 900 ° C and heat for 1 hour, then naturally drop to room temperature to obtain Co- C material.
圖4為所述Co-C材料之掃描電鏡照片。該Co-C材料中之粒子之直徑不超過1微米。該Co-C材料可用作複合催化劑材料。Figure 4 is a scanning electron micrograph of the Co-C material. The particles in the Co-C material have a diameter of no more than 1 micron. The Co-C material can be used as a composite catalyst material.
本發明第三實施例提供之Co-C材料之製備方法與第一實施例提供之ZnO-C材料之製備方法基本相同。第三實施例之Co-C材料之用途與第一實施例之ZnO-C材料之用途不同。因為鈷Co可以作為催化劑，而且Co-C材料中之碳C具有多孔結構，可以增強Co之吸附能力，有利於Co充分發揮催化特性；所以該Co-C材料可以用作複合催化劑材料。The preparation method of the Co-C material provided by the third embodiment of the present invention is basically the same as the preparation method of the ZnO-C material provided by the first embodiment. The use of the Co-C material of the third embodiment is different from the use of the ZnO-C material of the first embodiment. Since cobalt Co can be used as a catalyst, and the carbon C in the Co-C material has a porous structure, the adsorption capacity of Co can be enhanced, and Co can be sufficiently utilized to exert catalytic characteristics; therefore, the Co-C material can be used as a composite catalyst material.
第四實施例：Fourth embodiment:
本發明第四實施例提供鎳與碳之複合材料Ni-C之製備方法，該方法具體步驟如下：A fourth embodiment of the present invention provides a method for preparing a nickel-carbon composite material Ni-C, and the specific steps of the method are as follows:
第一，提供一鎳對苯二甲酸配位聚合物Ni(BDC)。First, a nickel terephthalic acid coordination polymer Ni (BDC) is provided.
首先，將10mmol可溶性鎳鹽溶解在50ml蒸餾水中得到第一溶液；在100ml蒸餾水中溶解20.2mmol NaOH溶液後加入10mmol對苯二甲酸攪拌至溶解，得到第二溶液。所述可溶性鎳鹽包括氯化鎳、硫酸鎳、硝酸鎳、醋酸鎳或其任意組合。本實施例中，所述可溶性鎳鹽為水合NiCl2 。First, 10 mmol of the soluble nickel salt was dissolved in 50 ml of distilled water to obtain a first solution; after dissolving 20.2 mmol of NaOH solution in 100 ml of distilled water, 10 mmol of terephthalic acid was added and stirred until dissolved to obtain a second solution. The soluble nickel salt includes nickel chloride, nickel sulfate, nickel nitrate, nickel acetate or any combination thereof. In this embodiment, the soluble nickel salt is hydrated NiCl 2 .
然後，將第一溶液和第二溶液混合，並在室溫下攪拌12小時後過濾，得到一濾餅；用50ml去離子水淋洗該濾餅，並在50攝氏度下乾燥該淋洗後之濾餅，得到Ni(BDC)。Then, the first solution and the second solution were mixed, and stirred at room temperature for 12 hours, and then filtered to obtain a filter cake; the filter cake was rinsed with 50 ml of deionized water, and dried at 50 ° C. The filter cake was obtained to obtain Ni (BDC).
第二，加熱該Ni(BDC)，以得到Ni-C材料。Second, the Ni (BDC) is heated to obtain a Ni-C material.
取1克Ni(BDC)置於瓷舟(陶瓷或石英容器)中，在氬氣保護下，從室溫升至1000攝氏度，維持1000攝氏度並加熱2小時後自然降至室溫便可得到Ni-C材料。Take 1 gram of Ni (BDC) in a porcelain boat (ceramic or quartz container), raise it from room temperature to 1000 ° C under argon atmosphere, maintain 1000 ° C and heat for 2 hours, then naturally drop to room temperature to obtain Ni -C material.
圖5為所述Ni-C材料之掃描電鏡照片。該Ni-C材料中之粒子之直徑不超過2微米。該Ni-C材料可用作複合催化劑材料。Figure 5 is a scanning electron micrograph of the Ni-C material. The particles in the Ni-C material have a diameter of no more than 2 microns. The Ni-C material can be used as a composite catalyst material.
本發明第四實施例提供之Ni-C材料之製備方法與第一實施例提供之ZnO-C材料之製備方法基本相同。第四實施例之Ni-C材料之用途與第一實施例之ZnO-C材料之用途不同。因為鎳Ni可以作為催化劑，而且Ni-C材料中之碳C具有多孔結構，可以增強Ni之吸附能力，有利於Ni充分發揮催化特性；所以該Ni-C材料可以用作複合催化劑材料。The preparation method of the Ni-C material provided by the fourth embodiment of the present invention is basically the same as the preparation method of the ZnO-C material provided by the first embodiment. The use of the Ni-C material of the fourth embodiment is different from that of the ZnO-C material of the first embodiment. Since nickel Ni can be used as a catalyst, and the carbon C in the Ni-C material has a porous structure, the adsorption capacity of Ni can be enhanced, and Ni is sufficiently utilized to exert catalytic characteristics; therefore, the Ni-C material can be used as a composite catalyst material.
其中，所述第三實施例中之可溶性鈷鹽或第四實施例中之可溶性鎳鹽可以用可溶性銅鹽代替，以製備銅與碳之複合材料Cu-C。該Cu-C材料亦可用作複合催化劑材料。Wherein, the soluble cobalt salt in the third embodiment or the soluble nickel salt in the fourth embodiment may be replaced with a soluble copper salt to prepare a composite material Cu-C of copper and carbon. The Cu-C material can also be used as a composite catalyst material.
本發明實施例提供之碳複合材料之製備方法具有以下優點：第一，充分利用金屬對苯二甲酸配位聚合物中對苯二甲酸之高含碳量，通過熱解金屬對苯二甲酸配位聚合物獲得含碳複合材料，該製備方法簡單、週期短、易於操作，比較安全，有利於工業上大規模生產。第二，本發明實施例所採用之原料比較廉價，成本較低。第三，由該製備方法製備之碳複合材料中之碳可以增強金屬氧化物或金屬之吸附能力和增加金屬氧化物電極材料之導電性，因此，可以用作氣敏材料、鋰離子電極材料或催化劑材料等。The preparation method of the carbon composite material provided by the embodiment of the invention has the following advantages: First, fully utilize the high carbon content of terephthalic acid in the metal terephthalic acid coordination polymer, and pyrolyze the metal terephthalic acid The bit polymer obtains the carbon-containing composite material, and the preparation method is simple, the cycle is short, the operation is easy, the safety is safe, and the industrial mass production is favorable. Second, the materials used in the embodiments of the present invention are relatively inexpensive and low in cost. Third, the carbon in the carbon composite prepared by the preparation method can enhance the adsorption ability of the metal oxide or the metal and increase the conductivity of the metal oxide electrode material, and thus can be used as a gas sensitive material, a lithium ion electrode material or Catalyst materials, etc.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍內。In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims.
圖1係本發明提供之碳複合材料之製備方法流程圖。1 is a flow chart of a method for preparing a carbon composite material provided by the present invention.
圖2係本發明第一實施例提供之ZnO-C掃描電鏡照片。2 is a SEM-C scanning electron micrograph of the first embodiment of the present invention.
圖3係本發明第二實施例提供之MnO-C掃描電鏡照片。Figure 3 is a SEM image of a MnO-C provided by a second embodiment of the present invention.
圖4係本發明第三實施例提供之Co-C掃描電鏡照片。4 is a photograph of a Co-C scanning electron microscope provided by a third embodiment of the present invention.
圖5係本發明第四實施例提供之Ni-C掃描電鏡照片。Fig. 5 is a photograph of a Ni-C scanning electron microscope provided by a fourth embodiment of the present invention.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98110289A TWI415792B (en) | 2009-03-27 | 2009-03-27 | Method for making carbon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98110289A TWI415792B (en) | 2009-03-27 | 2009-03-27 | Method for making carbon composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201034944A TW201034944A (en) | 2010-10-01 |
| TWI415792B true TWI415792B (en) | 2013-11-21 |
Family
ID=44855732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW98110289A TWI415792B (en) | 2009-03-27 | 2009-03-27 | Method for making carbon composite material |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI415792B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138604A (en) * | 1996-05-06 | 1996-12-25 | 中国科学院化学研究所 | Composite containing carbon fibre and liquid crystal polymer |
| CN101006007A (en) * | 2004-08-16 | 2007-07-25 | 王静 | Processes for producing monolithic porous carbon disks from aromatic organic precursors |
| CN101100563A (en) * | 2007-05-24 | 2008-01-09 | 同济大学 | Nano composite material of asymmetric phthalocyanine and carbon nano-tube and preparation method thereof |
-
2009
- 2009-03-27 TW TW98110289A patent/TWI415792B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138604A (en) * | 1996-05-06 | 1996-12-25 | 中国科学院化学研究所 | Composite containing carbon fibre and liquid crystal polymer |
| CN101006007A (en) * | 2004-08-16 | 2007-07-25 | 王静 | Processes for producing monolithic porous carbon disks from aromatic organic precursors |
| CN101100563A (en) * | 2007-05-24 | 2008-01-09 | 同济大学 | Nano composite material of asymmetric phthalocyanine and carbon nano-tube and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201034944A (en) | 2010-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meng et al. | Advances and challenges in 2D MXenes: From structures to energy storage and conversions | |
| Ahmad et al. | Self-sacrifice MOFs for heterogeneous catalysis: Synthesis mechanisms and future perspectives | |
| Zhang et al. | Rice husks as a sustainable silica source for hierarchical flower-like metal silicate architectures assembled into ultrathin nanosheets for adsorption and catalysis | |
| Zhu et al. | Recent progress in the syntheses and applications of multishelled hollow nanostructures | |
| Balach et al. | Metal-based nanostructured materials for advanced lithium–sulfur batteries | |
| Lee et al. | Transformation of metal–organic frameworks/coordination polymers into functional nanostructured materials: experimental approaches based on mechanistic insights | |
| Mai et al. | Nano metal‐organic framework‐derived inorganic hybrid nanomaterials: synthetic strategies and applications | |
| CN103072968B (en) | Carbon nano composite and preparation method thereof | |
| Wu et al. | Porous cobalt phosphide/graphitic carbon polyhedral hybrid composites for efficient oxygen evolution reactions | |
| Yu et al. | Nitrogen-doped mesoporous carbon nanosheets derived from metal-organic frameworks in a molten salt medium for efficient desulfurization | |
| CN101837967B (en) | Method for preparing carbon composite material | |
| EP2660198A1 (en) | Porous graphene material and preparation method and uses as electrode material thereof | |
| Li et al. | Synthetic control of Prussian blue derived nano-materials for energy storage and conversion application | |
| Li et al. | Rational microstructure design on metal–organic framework composites for better electrochemical performances: design principle, synthetic strategy, and promotion mechanism | |
| US20200147591A1 (en) | Preparation method for hollow molybdate composite microspheres and their application | |
| Ren et al. | Advanced hybrid supercapacitors assembled with beta-Co (OH) 2 microflowers and microclews as high-performance cathode materials | |
| Yang et al. | Construction of core-shell mesoporous carbon nanofiber@ nickel cobaltite nanostructures as highly efficient catalysts towards 4-nitrophenol reduction | |
| Wang et al. | Synthesis of a magnetic 2D Co@ NC-600 material by designing a MOF precursor for efficient catalytic reduction of water pollutants | |
| TW201119939A (en) | Porous carbon and method for producing the same | |
| KR101267317B1 (en) | Transition metal oxide/graphene composites by using microwave-polyol process and synthesizing method thereof | |
| Bornamehr et al. | Prussian blue and its analogues as functional template materials: control of derived structure compositions and morphologies | |
| Azadeh et al. | Three-dimensional rice husk-originated mesoporous silicon and its electrical properties | |
| Xu et al. | Zinc cobalt bimetallic nanoparticles embedded in porous nitrogen-doped carbon frameworks for the reduction of nitro compounds | |
| Cendrowski et al. | Graphene nanoflakes functionalized with cobalt/cobalt oxides formation during cobalt organic framework carbonization | |
| Poon et al. | Synergistic effect of Co catalysts with atomically dispersed CoN x active sites on ammonia borane hydrolysis for hydrogen generation |