TW200800388A - Photocatalyst for reduction of carbon dioxide to produce methanol and its process thereof - Google Patents

Photocatalyst for reduction of carbon dioxide to produce methanol and its process thereof Download PDF

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TW200800388A
TW200800388A TW095120508A TW95120508A TW200800388A TW 200800388 A TW200800388 A TW 200800388A TW 095120508 A TW095120508 A TW 095120508A TW 95120508 A TW95120508 A TW 95120508A TW 200800388 A TW200800388 A TW 200800388A
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indium
carbon dioxide
oxide
nickel
hours
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TW095120508A
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TWI317301B (en
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Pei-Wen Pen
Tsong-Yang Wei
Yu-Wen Chen
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Univ Nat Central
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

This invention declares the preparation of indium-tantalum photocatalysts for carbon dioxide reduction to produce methanol using indium-tantalum- supported micro nickel catalysts. Indium-tantalum was synthesized by a solid-state reaction method. The pre-dried In2O3, Ta2O5 with purity of 99.99% were used as starting materials. The stoichiometric amounts of precursors were mixed and reacted in an aluminum crucible in air at 900-1400 DEG C for 2-24 h. In order to obtain high photocatalytic activity, it is essential to load a metal or metal oxide on the surface of photocatalyst as electron acceptors. We tested loading NiOx on surface of the catalyst. The nickel was loaded on surface of the catalysts powders from aqueous Ni(NO3)2 solution. The Ni-loaded photocatalysts were calcined at 300-500 DEG C for 1-10h in air, then prepared by H2 (200 Torr) reduction at 300-600 DEG C for 1-10 h and subsequent O2 (100 Torr) oxidation at 150-300 DEG C for 1-5 h. The double-layered structure of metallic Ni and NiO was formed on the surface of photocatalyst by this reduction-oxidation procedure. The content of Ni-loaded is controlled at weight percent between 0.3 and 1. The particle size of indium-tantalum photocatalysts is less than 3 μm. Nickel species is in metallic state. Photocatalytic reactions were carried out in a closed gas circulation system. A 0.14 g powder sample was suspended in 50 ml 0.2 M potassium hydrogen carbonate aqueous solution bubbling with carbon dioxide using a Pyrex glass cell (75 ml). A 500W halogen lamp was placed onto the down face of the Pyrex glass cell. The temperature of reduction of carbon dioxide is controlled between 10 DEG C and 80 DEG C. NiO-loaded InTaO4 showed a high photocatalytic activity for carbon dioxide reduction into methanol in a stoichiometric amount under visible irradiation.

Description

200800388 九、發明說明： 【發明所屬之技術領域】 本發縣-種承餅岭化她之_叙製備綠，及—種承載於 銦钽氧化物讀觸触光激魏轉财巾的二氧化雜低㈣。C下反應 生成甲醇之製程，其中氧化鎳/四氧化她觸之製法為分綱錮和组的氧 化物為起始物f，均勻混合上述兩種物f，經研磨後，在_至14默之200800388 IX. Description of the invention: [Technical field of invention] This county----------------------------------------------------------------------------------------------------------------------------------------------------------------------- Miscellaneous low (four). The process of reacting to form methanol under C, wherein the method of preparing nickel oxide/tetraoxide is the starting material f and the oxide of the group is the starting material f, uniformly mixing the above two substances f, after grinding, in the _ to 14 It

間煆燒2至24小時’ _岭化她，將四氧化她放置於容器中，再加 入硝酸_水絲，独糖加麟杉餘的水分後，在至蕭c間 瑕燒1至1G小時，氧化鎳/四氧化銦奴重量比介於⑽％至〖％之間， 然後用氫氣於300至_ %間還原！至1〇小時，再用氧氣於15〇至獅。C 間氧化1至5小時’以使光觸媒表關時具有金屬鎳與氧化錄，其中四氧 化銦组為微米級顆粒直徑，其顆粒直徑在彳微米至3微米之間，且其為結 晶型態。本發《包齡室溫至8代_战觸進行二氧化碳_反應 的製程’二氧化碳_反雜程係在—反應財進行，以水及二氧化碳為 原料，反應温度在10至80之間，所使用的觸媒為銦组系列的觸媒，所 使用的光源為-般太陽光或可見光或紫外光。本發明所揭示之方法製傷含 有銦鈕的微米光觸媒，其顆粒直徑在微米範圍，能帶間_2.7^，而且 氧化銦㈣'·晶鶴存在，此絲騎柯見細二概韻原為甲醇 之反應’具有南的活性。 【先前技術】 在太陽光射就的紐下，二氧化销辆原錢轉之半導體光 觸媒’已有許多研究，其中包含了氧化鎢，二氧化欽， 氧化鋅，硫化鎘， 200800388 磷化鎵，碳化矽，含鈦γ型觸媒，含鈦万型觸媒以及含銅二氧化鈦觸媒等； Inoue等人之論文第277卷，第637頁，1979年]首次揭示以氧化鎢，二氧 化鈦，氧化鋅，硫化鎘，磷化鎵以及碳化矽等半導體光觸媒，各別在氙燈 及汞燈照射下，將二氧化碳與水還原成為曱醇，甲酸，甲醛以及微量之甲 烷；H· Yamasita等人之論文[CataLT〇day，第必卷，第221_227頁，揭示 以離子父換法製備含氧化鈦之γ型觸媒，其二氧化鈦之承載量為U脱。/❹， 在高壓汞燈(波長大於28〇nm)的照射下，甲醇之產生量約為4却·ihV g'TiO^K· &eue等人[j· Phys. chem B，第 1〇5卷第835〇 随 以水熱法製備含鈦/3型(OH)觸媒，在紫外光強度為265_^-2的照射下，甲 醇之產生s約有0.7l，〇lh-ig-LTi ; Tseng等人之論文c祕第瓜卷，第 432-44〇胃，2〇〇4年]揭示以溶膠凝膠法製備含銅二氧化鈦光觸媒，其銅之承 載量為2%，在WC(254㈣的照射下，甲醇之產生量約有; 吴國專利6156211號揭示以一種多孔性半導體光觸媒薄膜經由三相反應系 統可將甲鋪化成甲醇之方法；美國專利6267849號揭示將銅，鑭，翻以及 鋰金屬各雜躲氧似I，氧化鈦以及氧德可縣―觀化轉化生成 甲醇以及氫氣之光觸媒。文獻與專利均是二氧化碳與水還原製成甲醇所使 用的觸媒麵與生成甲醇的方法，而文獻與專利中所使用觸媒，方法皆不 松同。本發明特點即在創新未曾揭示之方法，先以固態反應法製備四氧化 錮组’以初濕含浸法製備鎳觸媒，經由精碟控制製備過程，所得到之觸媒 在至/皿至5〇 C之間’於飽和—氧化碳之碳酸氫卸液體中能成功的產生甲醇。 【發明内容】 本發鴨綠吨似_之_叙製備，及—種承載於 8 200800388 銦!一氧化物之鎳觸媒由光激發將溶解於水中的二氧化礙於低於8〇〇c下反應 生成f醇之製程’其巾氧傾/四氧仙轉叙製法為分卿姉叙的氧 化物為起始物貝，均勻混合上述兩種物質，經研磨後，在彻至工働^之 間煆k 2至24小日守’得到四氧化銦|旦，將四氧化銦鈕放置於容器中，再加 入硝鎳的水溶液，並以水浴加熱趕走多餘的水分後，在3⑻至$⑽。^間 煅燒1至10小時，氧化鎳/四氧化銦!旦之重量比介於〇·3 %至工％之間， 然後用氫氣於300至600 間還原1至1〇小時，再用氧氣於15〇至3〇〇〇c _ 間氧化1至5小時，以使細媒表面同時具有金屬鎳與氧化鎳，其中四氧 化銦鈕為微米級顆粒直徑，其顆粒直徑在丨微米至3微米之間，且其為結 曰a型恶。本發明亦包括在室溫至8〇 〇C間以上述觸媒進行二氧化碳還原反應 r 的製程，一氧化碳還原反應製程係在一反應器中進行，以水及二氧化石炭為 原料，反應溫度在10至80 〇C之間，所使用的觸媒為銦鈕系列的觸媒，所 使用的光源為一般太陽光或可見光或紫外光。本發明亦包括一種生成甲醇 的方法。其係以含有氧化鎳/四氧化銦钽之光觸媒，藉由太陽光或可見光或 馨紫外光的照射下，以產生甲醇。其中銦、钽的氧化物分別係三氧化二銦和 五氧化二鈕；產生甲醇反應之溶液以碳酸氫鉀水溶液為主，並通入純一氧 化碳溶液，使二氧化後飽和於溶液中；產生曱醇反應溫度是在1〇〇c至 之間。 實施方式1 : 稱取氧化銦2·7764克(10毫莫耳)(購自Merck公司），研磨之；稱取氧化知 4.4189克(10毫莫耳X購自Aldrich公司），研磨之；將氧化銦與氧化鈕充份 9 200800388 混合’研磨之；將氧化銦與氧化钽放於容器内，在1100 °C下煆燒12小時， 冷卻至室溫，即生成InTa04粉末。 實施方: ———— 稱取氧化銦2.7764克(10毫莫耳)(購自Merck公司），研磨之；稱取氧化钽 4,4189克(10毫莫耳X購自Merck公司），研磨之；將氧化銦與氧化組充份混 合’研磨之；將氧化銦與氧化組放於容器内，在1100 °C下煆燒12小時， 冷卻至至溫；稱取所製備的銦组氧化物⑽克，置於容器内；稱取硝酸 鎳0.0123克，溶於L0500毫升的純水中，此為硝酸鎳水溶液；將硝酸鎳水 >谷液，逐滴地滴在錮钽氧化物上，並持續攪拌；使用水浴加熱的方式，並 適時地攪拌，以將銦鈕氧化物上多餘的水分趕走；在35〇 〇c下煆燒丨小時， 即生成 0.3 wt·% NiO/InTa04 粉末。 實施方式3 : 稱取氧化銦2,7764克(10毫莫耳)(購自他她公司），研磨之；稱取氧化组 4.柳克(H)毫莫耳X購自Merck公司）’研磨之；將氧化銦與氧化麵充份混 合’研磨之；將氧化銦與氧化组放於容_，在· %下域12小時， 冷卻至室溫；稱輯製她氧化物克，置於容訊；稱取石肖酸 錄0.0204克，溶於1.0500毫升的純水中，此為石肖酸鎳水溶液，·將确酸錦水 溶液’逐滴地滴在銦组氧化物上’並持魏拌；個水浴加熱的方式，並 適時地授拌，以將錮组氧化物上多餘的水分趕走；在35代下瑕燒丨小時， 即生成 〇·5 wt·% Ni0/InTa04 粉末。 200800388 # 實施方 稱取氧化銦2.7764克(10毫莫耳)(購自Merck公§])，研磨之；稱取氧化钽 4·4189克(1〇耄莫耳)(購自Merck公司），研磨之；將氧化銦與氧化钽充份混 否’研磨之，將氧化銦與氧化钽放於容器内，在1100 °C下煆燒12小時， ~卻至至槪，稱取所製備的銦鈕氧化物1〇5〇〇克，置於容器内；稱取硝酸 錄0.0409克’溶於1〇5〇〇毫升的純水中，此為硝酸鎳水溶液；將石肖酸鎳水 洛液，逐滴地滴在銦钽氧化物上，並持續攪拌；使用水浴加熱的方式，並 Φ 適化地授拌’以將銦钽氧化物上多餘的水分趕走；在35〇。。下煆燒1小時， 即生成 l.Owt·% NiO/InTa04粉末。 4 實施方式5 : 稱取氧化銦2.7764克(10毫莫耳)(購自Merck公司），研磨之；稱取氧化组 4.4189克(1〇毫莫耳)(購自Merck公司），研磨之；將氧化銦與氧化钽充份混 合’研磨之；將氧化銦與氧化鈕放於容器内，在u⑽。c下煅燒小時， 籲 冷卻至室溫；稱取所製備的銦I旦氧化物1 0500克，置於容器内；稱取石肖酸 鎳0·0123克，溶於L0500毫升的純水中，此為硝酸鎳水溶液；將硝酸鎳水 溶液，逐滴地滴在錮组氧化物上，並持續攪拌；使用水浴加熱的方式，並 適時地攪拌’以將銦鈒氧化物上多餘的水分趕走；在350 °C下煆燒1小時， 即生成0.3 wt·% NiO/InTa〇4粉末；然後使用氩氣於5〇〇〇c下還原2小時， 再用氧氣於200 C下乳化1小時’以在光觸媒表面產生金屬说與NiOx·， 其組成可以用 NiO(0.3%)/InTa04R500-0200 表示。 11 200800388 貫施方式6 : 稱取氧化銦2·7764克(1〇毫莫耳)(購自論成公司），研磨之；稱取氧化钽 屯獅克(10毫莫耳X購自Merck公司），研磨之；將氧化銦與氧化组充份混 合，研磨之，將氧化錮與氧化鈕放於容器内，在11〇〇 〇c下煆燒小時， 冷部至室溫；稱取所製備的她氧化物i•剛克，置於容黏：稱取頌酸 鎳0.02〇4克，溶於L〇5〇〇毫升的純水中，此為頌酸鎳水溶液丨將确酸錄水 溶液，逐滴地滴在銦鈕氧化物上，並持續攪拌；使用水浴加熱的方式，並 _ 斜地翻1，⑽她氧絲上乡細水分趕走；在35G下煆燒1小時， 即生成〇·5 wt·% NiO/InTa〇4粉末；然後使用氫氣於5〇〇〇c下還原2小時， 再用氧氣於2〇0。€：下氧化1小時，以在光觸媒表面產生金屬说與腦^， 其組成可以用 NiO(0.5%)/InTaO4 R500-0200 表示。 實施方式7 : 稱取氧化銦2·7764克(10毫莫耳)⑽自Merck^)，研磨之；稱取氧化鈕 ❿ 4.4189克(10笔莫耳)(購自Merck公司），研磨之；將氧化錮與氧化叙充份混 合，研磨之；將氧化銦與氧化鈕放於容器内，在n〇〇 〇c下煆燒12小時， 冷卻至室溫；稱取所製備_轉化物！·〇克，置於容㈣；稱取硝酸 鎳0.0409克，溶於1.0500毫升的純水中，此為硝酸鎳水溶液；將确酸錄水 溶液，逐滴地滴在她氧化物上，並持續攪拌；使用水浴加熱的方式，並 適Μ也攪拌’以將銦鈕氧化物上多餘的水分趕走；在35〇下假燒丨小時， 即生成1.0被％ NiO/InTa〇4粉末；然後使用氫氣於5〇〇〇c下還原2小時， 再用氧氣於2〇0。(：下氧化1小時，以在光觸媒表面產生金屬⑽與吨·， 12 200800388 、 其組成可以用 NiO(1.0%)/InTaO4 R500_0200 表示。 實施方式8 將實施方式1所製得的觸媒與50毫升濃度為0.2M之碳酸氫鉀水溶液皆置 於反應器内；先以二氧化碳沖洗反應系統60分鐘，以除去系統内的空氣， 並使二氧化碳飽和於碳酸氫鉀水溶液中，使水溶液之酸驗值達到7 ;打開 500W鹵素燈開關，此時定為反應開始時刻（t=〇);二氧化碳氣體於反應開 ^ 始後仍持續通入反應系統，反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後，停止燈源供給，並冷卻至室溫；將樣品裝 入離心管内，以離心機(奥特蒙HSIANGTAI)離心10分鐘，取出上層液， 以氣相色層分析儀(中國層析8900)分析產物濃度，分析之層析管柱為3公 尺長，直徑1/8英吋之不繡鋼管，填充物為6〇至8〇網目的p〇rapakQ分子 篩0 反應結果如下Between simmering for 2 to 24 hours' _ Linghua her, put the tetraoxide in the container, then add nitric acid _ water silk, the sugar and the water of the cedar, after the smolder 1 to 1G hour The weight ratio of nickel oxide/indium tetraoxide is between (10)% and 〖%, and then hydrogen is reduced between 300 and _%! For 1 hour, use oxygen for 15 lions. The oxidation between C and C is 1 to 5 hours' to make the photocatalyst have metal nickel and oxidation record, wherein the indium tetraoxide group is a micron particle diameter, the particle diameter is between 彳 micrometer and 3 micrometer, and it is a crystalline form. . This issue of "Chen age from room temperature to 8 generations _ combat process of carbon dioxide _ reaction" carbon dioxide _ anti-interference system in the reaction of the financial, water and carbon dioxide as raw materials, the reaction temperature is between 10 and 80, used The catalyst is a series of catalysts for the indium group, and the light source used is general sunlight or visible light or ultraviolet light. The method disclosed in the invention damages a micro photocatalyst containing an indium button, the particle diameter of which is in the micrometer range, the band between the band is _2.7^, and the indium oxide (four)'·crystal crane exists, and the wire rides the ke to see the fine two The reaction of methanol 'has a south activity. [Prior Art] Under the sun's rays, there have been many studies on the semiconductor photocatalysts that have been converted into raw materials, including tungsten oxide, dioxins, zinc oxide, cadmium sulfide, 200800388 gallium phosphide, Tantalum carbide, titanium-containing γ-type catalyst, titanium-containing catalyst and copper-containing titanium dioxide catalyst; Inoue et al., Vol. 277, p. 637, 1979] first disclosed tungsten oxide, titanium dioxide, zinc oxide Semiconductor photocatalysts such as cadmium sulfide, gallium phosphide and tantalum carbide, respectively, reduce carbon dioxide and water to sterol, formic acid, formaldehyde and trace amounts of methane under the irradiation of xenon lamps and mercury lamps; H. Yamasita et al. [CataLT] 〇day, vol. 221_227, discloses the preparation of a γ-type catalyst containing titanium oxide by ion father replacement method, wherein the loading amount of titanium dioxide is U detachment. /❹, under the irradiation of a high-pressure mercury lamp (wavelength greater than 28〇nm), the amount of methanol produced is about 4 but ihV g'TiO^K· &eue et al [j· Phys. chem B, page 1 Volume 5, No. 835, was prepared by hydrothermal method with titanium/type 3 (OH) catalyst. Under the irradiation of ultraviolet light intensity of 265_^-2, the yield of methanol was about 0.71, 〇lh-ig-LTi Tseng et al. paper c secret melon, 432-44 〇 stomach, 2 〇〇 4 years] revealed the preparation of copper-containing titanium dioxide photocatalyst by sol-gel method, the copper loading capacity is 2%, in WC (254 (4) Under the irradiation, the amount of methanol produced is about; Wuguo Patent No. 6156121 discloses a method for forming a porous semiconductor photocatalyst film into a methanol via a three-phase reaction system; and U.S. Patent No. 6,267,849 discloses copper, bismuth, and Lithium metal is mixed with oxygen, I, titanium oxide and oxygen decoxian - the photocatalyst of methanol and hydrogen is formed by the process of chemical conversion. The literature and patents are the catalyst surface used for the reduction of carbon dioxide and water to form methanol and the method for producing methanol. However, the methods used in the literature and the patents are not the same. The characteristics of the present invention are not revealed in the innovation. The method comprises the steps of: preparing a ruthenium tetroxide group by a solid state reaction method to prepare a nickel catalyst by an incipient wetness impregnation method, and controlling the preparation process through a fine disc, wherein the obtained catalyst is in a saturated state between -to and 5 〇C. The carbon dioxide hydrogen carbonate can be successfully produced in the liquid to remove the liquid. [Summary of the Invention] The present invention is prepared by using the duck green ton, and the seed is carried on 8 200800388. The nickel catalyst of the indium oxide is excited by light. The oxidation in water is caused by the reaction of lower than 8 〇〇c to form the alcohol. The method of the oxidative decanting/tetraoxane reversal method is the starting material of the sulphur. After the two materials are ground, between 2 and 24 hours, the indium oxide is obtained. The indium oxide button is placed in a container, and then an aqueous solution of nickel nitrate is added. After the excess water is removed by heating in a water bath, calcination is carried out between 3 (8) and $10 (10) for 1 to 10 hours, and the weight ratio of nickel oxide/indium tetraoxide to denier is between 〇·3 % and %, and then hydrogen is used. Reducing between 1 and 1 hour between 300 and 600, and then oxidizing with oxygen for 15 to 3 〇〇〇c _ for 1 to 5 hours to The surface of the fine medium has both metallic nickel and nickel oxide, wherein the indium tetraoxide button has a micron-sized particle diameter, the particle diameter is between 丨micrometer and 3 micrometers, and it is a crucible a-type evil. The invention also includes at room temperature. The process of carbon dioxide reduction reaction r is carried out by using the above catalyst to 8 〇〇C, and the carbon monoxide reduction reaction process is carried out in a reactor, and water and carbon dioxide carbon are used as raw materials, and the reaction temperature is between 10 and 80 〇C. The catalyst used is a catalyst of the indium button series, and the light source used is general sunlight or visible light or ultraviolet light. The present invention also includes a method of producing methanol. It is produced by a photocatalyst containing nickel oxide/indium tetraoxide strontium by irradiation with sunlight or visible light or fragrant ultraviolet light to produce methanol. The oxides of indium and bismuth are respectively indium trioxide and pentoxide oxide; the solution for generating methanol reaction is mainly aqueous solution of potassium hydrogencarbonate, and is passed through a pure carbon monoxide solution to make it saturated with hydrogen dioxide after solution; The alcohol reaction temperature is between 1 〇〇c and between. Embodiment 1: Weigh in 2,7764 g of indium oxide (10 mmol) (purchased from Merck), grind it; weigh 4.4189 g (10 mmol X purchased from Aldrich), and grind it; Indium oxide and oxidizing button full portion 9 200800388 mixed 'grinding'; indium oxide and cerium oxide were placed in a container, calcined at 1100 ° C for 12 hours, and cooled to room temperature to form InTa04 powder. Implementer: ———— Weigh 2.7764g (10mmol) of indium oxide (purchased from Merck), grind it; weigh 4,4189g of yttrium oxide (10mmol X from Merck), grinding Indium oxide is mixed with the oxidation group to be 'grinded'; the indium oxide and the oxidation group are placed in a container, calcined at 1100 ° C for 12 hours, cooled to a temperature; and the prepared indium group oxide is weighed (10) gram, placed in a container; weighed 0.0123 g of nickel nitrate, dissolved in L0500 ml of pure water, this is a nickel nitrate aqueous solution; nickel nitrate water > gluten solution, drop by drop on the cerium oxide, Stirring was continued; the water bath was heated and stirred in time to remove excess water from the indium button oxide; after burning at 35 ° C for 3 hours, 0.3 wt.% NiO/InTa04 powder was formed. Embodiment 3: Weigh 2,7764 g of indium oxide (10 mmol) (purchased from other companies), grind it; weigh the oxidation group 4. Liuke (H) millimolar X was purchased from Merck) Grinding; indium oxide and the oxidation surface are mixed and mixed 'grinding; the indium oxide and the oxidation group are placed in the volume _, in the lower area for 12 hours, cooled to room temperature; said to make her oxide grams, placed in the volume Weighing 0.0204 g of Shixiao acid, dissolved in 1.0500 ml of pure water, this is an aqueous solution of nickel tartaric acid, and the aqueous solution of the acid broth is dripped onto the indium oxide group and holds the mixture; A water bath is heated and mixed in time to remove excess water from the oxides of the niobium; in the 35th generation, the niobium 5 wt·% NiO/InTa04 powder is formed. 200800388 # The implementer weighed 2.7764 g (10 mmol) of indium oxide (purchased from Merck), and grinded it; weighed 4. 4189 g of yttrium oxide (purchased from Merck). Grinding; indium oxide and cerium oxide are fully mixed or not, grinding indium oxide and cerium oxide in a container, simmering at 1100 ° C for 12 hours, but until 槪, weigh the prepared indium Button oxide 1〇5〇〇g, placed in the container; weighed 0.0409 g of nitric acid dissolved in 1〇5〇〇ml of pure water, this is a nickel nitrate aqueous solution; Drop on the indium lanthanum oxide dropwise and continue to stir; use a water bath to heat the Φ and mix it properly to remove excess water from the indium bismuth oxide; at 35 〇. . After simmering for 1 hour, l.Owt·% NiO/InTa04 powder was formed. 4 Embodiment 5: Weigh 2.7764 g (10 mmol) of indium oxide (purchased from Merck), grind it; weigh 4.4189 g (1 〇 mmol) (purchased from Merck) and grind it; The indium oxide is mixed with the cerium oxide in a mixture of 'grinding'; the indium oxide and the oxidizing button are placed in a container at u(10). After calcination for 5 hours, it was cooled to room temperature; weighed 10 500 g of the prepared indium I oxide, and placed in a container; weighed 0. 0123 g of nickel oxalic acid and dissolved in L0500 ml of pure water. It is an aqueous solution of nickel nitrate; the aqueous solution of nickel nitrate is dripped onto the ruthenium group oxide and stirring is continued; using a water bath heating method and stirring at appropriate time to drive off excess water on the indium bismuth oxide; After calcination at 350 ° C for 1 hour, 0.3 wt·% NiO/InTa〇4 powder was formed; then it was reduced with argon at 5 ° C for 2 hours, and then emulsified with oxygen at 200 C for 1 hour. The surface of the photocatalyst produces metal and NiOx·, and its composition can be expressed by NiO (0.3%)/InTa04R500-0200. 11 200800388 Permeation method 6 : Weigh 2,7764 g of indium oxide (1 〇 millim) (purchased from the company), grind it; weigh 钽屯 钽屯 ( (10 mAh X purchased from Merck Grinding; indium oxide and the oxidation group are fully mixed, ground, the cerium oxide and oxidation button are placed in a container, simmered at 11 ° C for a while, cold to room temperature; weighed prepared Her oxide i•Gangke, placed in the viscosity: weigh 0.02 〇 4 grams of nickel ruthenate, dissolved in L 〇 5 〇〇 ml of pure water, this is a nickel ruthenate solution, the acid will be recorded Drop on the indium button oxide dropwise, and continue to stir; use a water bath to heat the way, and _ obliquely turn 1, (10) her oxygen wire to the town to remove the water; simmer for 1 hour at 35G, the formation of 〇 • 5 wt·% NiO/InTa〇4 powder; then reduced with hydrogen at 5 ° C for 2 hours and then with oxygen at 2 〇 0. €: Oxidation for 1 hour to produce metal and brain on the photocatalyst surface, the composition of which can be expressed by NiO (0.5%) / InTaO4 R500-0200. Embodiment 7: Indium oxide 2·7764 g (10 mmol) was weighed (10) from Merck^), ground; 4.4189 g (10 moules) (purchased from Merck) was weighed; The cerium oxide is mixed with the oxidized sulphate and ground; the indium oxide and the oxidizing button are placed in a container, simmered under n〇〇〇c for 12 hours, cooled to room temperature; and the prepared _transformant is weighed! · 〇克, placed in the volume (4); weighed 0.0409 grams of nickel nitrate, dissolved in 1.0500 ml of pure water, this is a nickel nitrate aqueous solution; the acid is recorded in an aqueous solution, drop by drop on her oxide, and continue to stir Use a water bath to heat and mix and stir to remove excess water from the indium button oxide; when simmering at 35 丨 for a few hours, 1.0% NiO/InTa〇4 powder is formed; then hydrogen is used. Reduce at 2 〇〇〇c for 2 hours, then use oxygen at 2 〇0. (: Oxidation for 1 hour to produce metal (10) and ton·, 12 200800388 on the surface of the photocatalyst, and the composition thereof can be represented by NiO (1.0%) / InTaO4 R500_0200. Embodiment 8 The catalyst prepared in Embodiment 1 and 50 A 0.5 M aqueous solution of potassium bicarbonate was placed in the reactor; the reaction system was flushed with carbon dioxide for 60 minutes to remove air from the system, and the carbon dioxide was saturated in an aqueous solution of potassium hydrogencarbonate to determine the acidity of the aqueous solution. Reach 7; open the 500W halogen lamp switch, which is set as the reaction start time (t=〇); the carbon dioxide gas continues to pass into the reaction system after the reaction starts, and the liquid generated by the reaction is stored in the reaction system until the reaction The time is up to 20 hours; after the reaction is completed, the lamp source is stopped and cooled to room temperature; the sample is placed in a centrifuge tube, centrifuged for 10 minutes in a centrifuge (Utmon HSIANGTAI), and the supernatant liquid is taken out for gas phase chromatography analysis. The instrument (China Chromatography 8900) was used to analyze the product concentration. The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel tube, and the filling material was 6〇 to 8〇 mesh p〇rapakQ molecular sieve. The results should be as follows

時間 (小時) 濃度Time (hours) concentration

甲醇產生量 (微莫耳/克觸媒） 21.112 實施方式9 : 將實施对2所製得__ 5〇糾濃料α2Μ之碰缺水溶液皆置 於反H先以―氧化洗反1%統6〇分鐘，赠n助的空氣， 並使二氧化碳飽和於魏氫鉀水缝卜使水溶液之麵值_ 7 ;打開 蕭鹵細，鱗定献應_日_㈣）；二氧化魏體於反應開 13 200800388 始後仍持續通入反應系統，反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後’停止燈源供給，並冷卻至室溫；將樣品裝 入離心管内，以離心機(奥特蒙HSIANGTAI)離心10分鐘，取出上層液， 以氣相色層分析儀(中國層析8900)分析產物濃度，分析之層析管柱為3公 尺長，直徑1/8英吋之不繡鋼管，填充物為60至80網目的Porapak Q分子 篩。 反應結果如下： 時間 (小時） 濃度 (ppm) 甲醇產生量 (微莫耳/克觸媒） 20 2.259 20.167 實施方^^ 將實施方式3所製得的觸媒與50毫升濃度為〇.2M之碳酸氫鉀水溶液皆置 於反應器内；先以二氧化破沖洗反應系統60分鐘，以除去系統内的空氣， 並使二氧化碳飽和於碳酸氫鉀水溶液中，使水溶液之酸驗值達到7 ;打開 500W _素燈開關，此時定為反應開始時刻（t=〇);二氧化碳氣體於反應開 始後仍持續通入反應系統，反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後，停止燈源供給，並冷卻至室溫；將樣品裝 入離心管内，以離心機(奥特蒙HSIANGTAI)離心10分鐘，取出上層液， 以氣相色層分析儀(中國層析8900)分析產物濃度，分析之層析管柱為3公 尺長’直徑1/8英吋之不繡鋼管，填充物為60至80網目的Porapak Q分子 篩。 14 200800388 反應結果如下： 時間 (小時） 20 濃度 (ppm) 曱醇產生量 (微莫耳/克觸媒)Methanol production amount (micromol/gram catalyst) 21.112 Embodiment 9: The solution of the __ 5 〇 浓 α α α α α α α α α α α α α α 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液 水溶液6 minutes, give n help air, and make carbon dioxide saturated with Wei hydrogen potassium water to make the surface value of the aqueous solution _ 7; open Xiao halogen fine, scale set should be _ day _ (four)); Open 13 200800388 After continuous introduction into the reaction system, the liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; after the reaction is completed, the supply of the light source is stopped and cooled to room temperature; In the tube, centrifuge for 10 minutes with a centrifuge (Otmon HSIANGTAI), remove the supernatant, and analyze the product concentration with a gas chromatograph analyzer (China Chromatography 8900). The chromatographic column is 3 meters long and 1 in diameter. /8 inches of non-embroidered steel pipe, filled with Porapak Q molecular sieve of 60 to 80 mesh. The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst) 20 2.259 20.167 Implementer ^^ The catalyst prepared in Embodiment 3 and the concentration of 50 ml are 〇.2M The aqueous solution of potassium hydrogencarbonate is placed in the reactor; the reaction system is first rinsed with dioxide for 60 minutes to remove the air in the system, and the carbon dioxide is saturated with the aqueous solution of potassium hydrogencarbonate to make the acid value of the aqueous solution reach 7; 500W _ prime lamp switch, this time is set as the reaction start time (t = 〇); carbon dioxide gas continues to pass into the reaction system after the start of the reaction, the liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; After the reaction is completed, the lamp source is stopped and cooled to room temperature; the sample is placed in a centrifuge tube, centrifuged for 10 minutes in a centrifuge (Utmon HSIANGTAI), and the supernatant liquid is taken out to obtain a gas chromatography layer analyzer (Chinese chromatography). 8900) Analyze the product concentration. The chromatographic column was analyzed to be a 3 mm long '1" diameter non-embroidered steel tube, and the filling was a Porapak Q molecular sieve of 60 to 80 mesh. 14 200800388 The reaction results are as follows: Time (hours) 20 Concentration (ppm) Sterol production (micromol/gram catalyst)

實施方式11 ： 將實施方式4所製得賴媒與SG毫升濃度為〇观之碳酸氫鉀水溶液皆置 於反應器内；先以二氧化碳沖洗反應系統6〇分鐘，以除去系統内的空氣， 並使二氧化碳飽和於碳酸氫鉀水溶液中，使水溶液之酸驗值達到7 ;打開 500W鹵素燈開關，此時定為反應開始時刻（t=〇);二氧化碳氣體於反應開 始後仍持續通入反應系統，反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後，停止燈源供給，並冷卻至室溫；將樣品裝 入離心管内，以離心機(奥特蒙HSIANGTAI)離心1〇分鐘，取出上層液， 以氣相色層分析儀(中國層析8900)分析產物濃度，分析之層析管柱為3公 尺長，直徑1/8英吋之不繡鋼管，填充物為6〇至8〇網目的Porapak Q分子 篩。 反應結果如下： 時間 (小時） 濃度 (ppm) 甲醇產生量 (微莫耳/克觸媒） 20 3.040 27.145 — 實施方式12 : 將實施方式5所製得的觸媒與50毫升濃度為〇 2M之破酸氫鉀水溶液皆置 15 200800388 *於反應器内；先以二氧化碳沖洗反應系統6〇分鐘，以除去系統内的空氣， 並使二氧化碳飽和於碳酸氫鉀水溶液中’使水溶液之酸鹼值達到7 ;打開 蕭«燈開關，此時定為反應開始時刻㈣）二氧化碳氣體於反應開 始後仍持續通入反應系統’反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後，停止燈源供給，並冷卻至室溫；將樣品裝 入離心㈣’以細機(奥 hSIanGTAI)_ 1G分鐘，取出上層液， 以氣相色層分析儀(巾國層析_0)分析產物濃度，分析之層析管柱為3公 _ 尺長’直徑1/8英时之不繡鋼管，填充物為60至80網目的P〇rapakQ分子 篩。 反應結果如下： 時間 (小時） 濃度 (ppm) 甲醇產生量 (微莫耳/克觸媒） 20 2.463 21.990 實施方式13 : 將實施方式6所製付的觸媒與50宅升濃度為〇 [之碳酸氫卸水溶液皆置 於反應器内；先以二氧化碳沖洗反應系統60分鐘，以除去系統内的空氣， 並使二氧化碳飽和於碳酸氫鉀水溶液中，使水溶液之酸鹼值達到7 ;打開 500W鹵素燈開關，此時定為反應開始時刻（t=0);二氧化碳氣體於反應開 始後仍持續通入反應系統，反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後’停止燈源供給，並冷卻至室溫；將樣品裝 入離心管内，以離心機(奥特’HSIANGTAI)離心10分鐘，取出上層液， 16 200800388 以氣相色層分析儀(中國層析8900)分析產物濃度，分析之層析管柱為3公 尺長，直徑1/8英吋之不繡鋼管，填充物為60至80網目的Porapak Q分子 篩。 反應結果如下： 時間 (小時） 濃度 (ppm) 甲醇產生量 (微莫耳/克觸媒） 20 2.867 25.601 實施方式14 : 將貫施方式7所製得的觸媒與50毫升濃度為〇·2Μ之碳酸氫鉀水溶液皆置 於反應器内；先以二氧化碳沖洗反應系統6〇分鐘，以除去系統内的空氣， 並使二氧化碳飽和於碳酸氫鉀水溶液中，使水溶液之酸鹼值達到7 ;打開 5〇ow鹵素燈開關，此時定為反應開始時刻Γ二氧化碳氣體於反應開 始後仍持繽通入反應系統，反應所產生的液體儲存於反應系統内，直到反 應時間達20小時；反應完畢後，停止燈源供給，並冷卻至室溫；將樣品裝 入離心管内，以離心機(奥特蒙HSIANGTAI)離心10分鐘，取出上層液， 以氣相色層分析儀(中國層析8900)分析產物濃度，分析之層析管柱為3公 尺長，直徑1/8英对之不義管，填充物為6〇至8〇網目的ρ〇亭k Q分子 篩。 反應結果如下： 時間 濃度 曱醇產生量 (小時) _) (微莫耳/克觸媒） 17 200800388 20 3.123 27.880 上述實施方式之反應結果如下表；由這些結果證實本發明之觸媒在室溫 下，能有效的生成甲醇。 實施方式 反應時間 (小時） 甲醇產生量 (微莫耳/小時•克觸媒） 8 20 1.056 9 20 1.008 10 20 1.Γ95 11 20 1.357 12 20 1.100 13 20 L280 14 20 1.394 18Embodiment 11: The solvent prepared in Embodiment 4 and the aqueous solution of potassium hydrogencarbonate having a concentration of SG milliliters are placed in the reactor; the reaction system is first flushed with carbon dioxide for 6 minutes to remove air in the system, and The carbon dioxide is saturated with the aqueous solution of potassium hydrogencarbonate to make the acid value of the aqueous solution reach 7; the 500W halogen lamp switch is turned on, and the reaction start time (t=〇) is determined; the carbon dioxide gas continues to pass into the reaction system after the reaction starts. The liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; after the reaction is completed, the light source is stopped and cooled to room temperature; the sample is placed in a centrifuge tube to be centrifuged (Utmon HSIANGTAI) After centrifugation for 1 minute, the supernatant was taken out, and the product concentration was analyzed by a gas chromatograph analyzer (China Chromatography 8900). The chromatographic column was analyzed to be 3 m long, and the diameter of 1/8 inch of non-embroidered steel tube was filled. The product is a Porapak Q molecular sieve from 6〇 to 8〇. The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst) 20 3.040 27.145 - Embodiment 12: The catalyst prepared in Embodiment 5 and 50 ml of a concentration of 〇2M The aqueous solution of potassium hydrogen sulphate is placed in the reactor. The reaction system is flushed with carbon dioxide for 6 minutes to remove the air in the system and make the carbon dioxide saturated in the aqueous solution of potassium hydrogencarbonate. 7; Open Xiao «light switch, this time is set as the reaction start time (four)) Carbon dioxide gas continues to pass into the reaction system after the start of the reaction 'The liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; the reaction is completed After that, stop the light source supply and cool to room temperature; load the sample into the centrifuge (4) 'with a fine machine (Ohhtan GTAI) _ 1G minutes, take out the upper layer liquid, and use the gas chromatograph analyzer (Wool National Chromatography_0) The concentration of the product was analyzed, and the chromatographic column was analyzed to be a 3 mm ft. length 1/8 inch diameter non-embroidered steel tube, and the filling was a P〇rapakQ molecular sieve of 60 to 80 mesh. The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst) 20 2.463 21.990 Embodiment 13: The catalyst prepared in Embodiment 6 and the concentration of 50 liters are 〇 [ The aqueous solution of hydrogencarbonate is placed in the reactor; the reaction system is first flushed with carbon dioxide for 60 minutes to remove the air in the system, and the carbon dioxide is saturated with the aqueous solution of potassium hydrogencarbonate to make the pH value of the aqueous solution reach 7; open 500W halogen The light switch is set as the reaction start time (t=0); the carbon dioxide gas continues to pass into the reaction system after the reaction starts, and the liquid generated by the reaction is stored in the reaction system until the reaction time reaches 20 hours; 'Stop the lamp supply and cool to room temperature; place the sample into the centrifuge tube, centrifuge for 10 minutes with a centrifuge (Otto 'HSIANGTAI), remove the supernatant, 16 200800388 with a gas chromatograph (China Chromatography 8900) The concentration of the product was analyzed. The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel tube, and the filling was a Porapak Q molecular sieve of 60 to 80 mesh. The reaction results are as follows: Time (hours) Concentration (ppm) Methanol production (micromol/gram catalyst) 20 2.867 25.601 Embodiment 14: The catalyst prepared by the method 7 and the concentration of 50 ml are 〇·2Μ The potassium bicarbonate aqueous solution is placed in the reactor; the reaction system is first flushed with carbon dioxide for 6 minutes to remove the air in the system, and the carbon dioxide is saturated in the aqueous solution of potassium hydrogencarbonate to make the pH value of the aqueous solution reach 7; 5〇ow halogen light switch, this time is set as the reaction start time Γ carbon dioxide gas is still passed into the reaction system after the start of the reaction, the liquid produced by the reaction is stored in the reaction system until the reaction time reaches 20 hours; after the reaction is completed The lamp source was stopped and cooled to room temperature; the sample was placed in a centrifuge tube, centrifuged for 10 minutes in a centrifuge (Utmon HSIANGTAI), and the supernatant liquid was taken out and analyzed by a gas chromatograph analyzer (China Chromatography 8900). The concentration of the product was analyzed by a column of 3 meters long, 1/8 inch diameter of the unsense tube, and the filling material was 6 〇 to 8 〇 mesh 〇 〇 k k molecular sieve. The reaction results are as follows: Time concentration sterol production amount (hours) _) (micromol/gram catalyst) 17 200800388 20 3.123 27.880 The reaction results of the above embodiments are shown in the following table; from these results, the catalyst of the present invention was confirmed at room temperature. Under the same, can effectively produce methanol. EXAMPLES Reaction time (hours) Methanol production (micromoles/hour•gram catalyst) 8 20 1.056 9 20 1.008 10 20 1.Γ95 11 20 1.357 12 20 1.100 13 20 L280 14 20 1.394 18

Claims (1)

200800388 十、申請專利範園： L 一種承載於四氧化銦鈕之鎳觸媒的製造方法，其包括 以銦的氧化物為起始物質；以钽的氧化物為起始物質；混合上述兩種物 質’並研磨之，在900至1400 °C間煆燒2至24小時，得到四氧化錮 組；將四氧化銦鈕置於容器中，再加入硝酸鎳水溶液，並以水浴加熱法 趕走多餘的水分後，於300至500 °C間加熱1至10小時，使氧化鎳之 重量為全部觸媒重量的〇·3 %至1 %之間；之後在300至600 °C間以 氫氣還原1至10小時，再用氧氣或空氣於室溫至15〇至3〇〇〇C間氧化 1至5小時。 2·如申請專利範圍第1項的方法，其中氧化鎳之重量比最佳是0.5 %至1 %之間。 3· 種生成曱醇的方法，其係以含有氧化鎳/氧化錮钽觸媒在太陽光或可 見光或紫外光的照射下，於10至8〇。(：間反應，以生成曱醇，其特徵是 以四氧化銦组為光觸媒，以碳酸氫鉀或氫氧化納水溶液通入二氧化碳為 反應物，其製法為 a.以銦的氧化物為起始物質； b·以纽的氧化物為起始物質； 匕混合上述兩種物質，並研磨，在9〇〇至14〇〇 %間煆燒2至％小時， 得到四氧化銦组； d·將四氧化銦鈕置於容器中，再加入硝酸鎳水溶液，並以水浴加熱法 趕走多餘的水分後，於350 °C間加熱1小時，使氧化鎳之重量為全 部觸媒重量的〇.3 %到1 %之間； 19 200800388 e·在500間以氫氣還原2小時，再用氧氣於 〇c間氧化1小時。 f•將四氧化銦鈕置於反應器中，加入碳酸氫鉀水溶液，並通入二氧化 碳氣體1小時，使二氧化碳飽和於水溶液中，於10至8〇〇c間置於 太陽光、可見光或紫外光下照射。 4·如申請專利範圍第3項的方法，其中鎳的比例最佳的是〇·5%至2%之 間。 20 200800388 七、指定代表圖： (一) 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件代表符號簡單說明: 無指定代表圖 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 200800388 ' 、 、 _ 登里專利說明書和 (本說明書格式、順序及粗體字，請勿任意更動，※記號部分請勿填寫） ※申請案號 ※申請日期·· 《ipc分類：/沒0 β 一、發明名稱··（〒文/英文） ^ % % ^ ^ (2006·01) 二氧化碳還原生產甲醇之光觸媒及其製程/ PHOTOCATALYST FOR REDUCTION OF CARBON DIOXIDE TO PRODUCE METHANOL AND ITS PROCESS THEREOF _ 二、申請人：（共1人） 姓名或名稱：（中文/英文）（簽章） 國立中央大學/NATIONAL CENTRAL UNIVERSITY • 代表人：（中文/英文）（簽章） _ 李羅權/Lou-Chuang Lee 住居所或營業所地址：（中文/英文） 320桃園縣中壢市中大路3〇〇號/ No.300, Jhongda Rd., Jhongli City, Taoyuan County 320, Taiwan, R.O.C. 國籍：（中文/英文） ^ 中華民國/R.O.C. 三、發明人：（共3人） 姓名：（中文/英文） 潘珮尨/Pei-WenPen 魏聰揚/Tsong-Yang Wei 陳郁文/ Yu-Wen Chen 住居所地址：（中文/英文） 220板橋市四維路1〇3巷26號4樓 114台北市成功路四段324巷2弄5號3樓200800388 X. Patent application: L. A method for producing a nickel catalyst supported on an indium oxide button, comprising: using an oxide of indium as a starting material; using an oxide of cerium as a starting material; mixing the above two The substance is 'grinded and calcined between 900 and 1400 °C for 2 to 24 hours to obtain the osmium tetroxide group; the indium tetraoxide button is placed in a container, then an aqueous solution of nickel nitrate is added, and the excess is removed by heating in a water bath. After the water is heated, it is heated at 300 to 500 ° C for 1 to 10 hours so that the weight of the nickel oxide is between 3 3% and 1% of the total catalyst weight; after that, it is reduced by hydrogen at 300 to 600 ° C. After 10 hours, oxidize with oxygen or air at room temperature to 15 Torr to 3 Torr for 1 to 5 hours. 2. The method of claim 1, wherein the weight ratio of nickel oxide is preferably between 0.5% and 1%. 3. A method for producing sterols, which comprises a nickel oxide/yttria catalyst in the presence of sunlight or visible light or ultraviolet light at 10 to 8 Torr. (: inter-reaction to form sterol, characterized by indium tetraoxide as a photocatalyst, with carbon dioxide or sodium hydroxide aqueous solution as carbon dioxide as a reactant, the preparation method is a. starting from indium oxide Substance; b. Oxide oxide as a starting material; 匕 mixing the above two substances, and grinding, simmering between 9 〇〇 and 14 〇〇% for 2 to % hours to obtain an indium oxide group; d· The indium tetraoxide button is placed in a container, and then an aqueous solution of nickel nitrate is added, and the excess water is removed by heating in a water bath, and then heated at 350 ° C for 1 hour, so that the weight of the nickel oxide is the weight of the total catalyst. Between 1% and 1%; 19 200800388 e·Reducing in 500 hydrogen for 2 hours, and then oxidizing with oxygen for 1 hour between 〇c. f• Place the indium tetraoxide button in the reactor and add potassium bicarbonate solution. And carbon dioxide gas is introduced for 1 hour to make the carbon dioxide saturated in the aqueous solution, and is irradiated under sunlight, visible light or ultraviolet light between 10 and 8 〇〇c. 4. The method of claim 3, wherein nickel The best ratio is between 5% and 2%. 20 200800388 VII. Designated representative map: (1) The representative representative figure of this case is: (). (2) The representative symbol of the representative figure is a simple description: No designation is shown in Figure 8. If there is a chemical formula in this case, please reveal the best Chemical formula showing the characteristics of the invention: 200800388 ' , 、 登 登 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利Classification: / No 0 β I. Inventor Name··(〒文/英文) ^ % % ^ ^ (2006·01) Photocatalyst for the production of methanol by carbon dioxide reduction and its process / PHOTOCATALYST FOR REDUCTION OF CARBON DIOXIDE TO PRODUCE METHANOL AND ITS PROCESS THEREOF _ II. Applicant: (1 in total) Name: (Chinese/English) (Signature) National Central University/NATIONAL CENTRAL UNIVERSITY • Representative: (Chinese/English) (signature) _ Li Luoquan/Lou- Chuang Lee Residence or Business Office Address: (Chinese/English) 320 No.300, Zhongda Road, Zhongli City, Taoyuan County, No.300, Jhongda Rd., Jhongli City, Taoyuan County 320, Taiwan, ROC Nationality: (Chinese / English) ^ Republic of China / ROC III. Inventor: (3 in total) Name: (Chinese / English) Pan Wei / Pei-WenPen Wei Congyang / Tsong-Yang Wei Chen Yuwen / Yu -Wen Chen Residence Address: (Chinese / English) 220, 4th Floor, No. 26, Lane 3, Lane 3, Siwei Road, Banqiao City, 114, 3rd Floor, No. 5, Lane 2, Lane 324, Section 4, Success Road, Taipei
TW095120508A 2006-06-08 2006-06-08 Photocatalyst for reduction of carbon dioxide to produce methanol and its process thereof TWI317301B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102921423A (en) * 2012-04-26 2013-02-13 南开大学 Efficient nickel/nickel oxide/nickel borate composite photocatalyst
CN107043277A (en) * 2016-09-28 2017-08-15 陈楚松 Many sky formula photocatalyst ceramic wafers
CN109529851A (en) * 2018-12-26 2019-03-29 大连海事大学 A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method
CN110586064A (en) * 2019-09-27 2019-12-20 天津大学 Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof

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US10047027B1 (en) 2017-11-08 2018-08-14 King Fahd University Of Petroleum And Minerals Method of forming methanol via photocatalytic reduction of carbon dioxide
TWI655180B (en) * 2018-03-15 2019-04-01 國立清華大學 Catalyst for manufacturing methanol, method for fabricating thereof and method for manufacturing methanol

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102921423A (en) * 2012-04-26 2013-02-13 南开大学 Efficient nickel/nickel oxide/nickel borate composite photocatalyst
CN107043277A (en) * 2016-09-28 2017-08-15 陈楚松 Many sky formula photocatalyst ceramic wafers
CN109529851A (en) * 2018-12-26 2019-03-29 大连海事大学 A kind of Supported Nickel Catalyst and utilize its plasma-catalytic CO2Preparing methanol by hydrogenation method
CN109529851B (en) * 2018-12-26 2021-10-01 大连海事大学 Nickel-based supported catalyst and method for catalyzing CO by using plasma of nickel-based supported catalyst2Method for preparing methanol by hydrogenation
CN110586064A (en) * 2019-09-27 2019-12-20 天津大学 Lithium-doped zirconium oxide loaded indium oxide catalyst and preparation method and application thereof

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