TW202037586A - Method for reducing carbon dioxide to manufacture carbon compound - Google Patents

Method for reducing carbon dioxide to manufacture carbon compound Download PDF

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TW202037586A
TW202037586A TW108112171A TW108112171A TW202037586A TW 202037586 A TW202037586 A TW 202037586A TW 108112171 A TW108112171 A TW 108112171A TW 108112171 A TW108112171 A TW 108112171A TW 202037586 A TW202037586 A TW 202037586A
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photocatalyst
carbon dioxide
compound
present
shows
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TW108112171A
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TWI776041B (en
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陳錦章
江秋亮
戴永銘
劉馥毓
鄒香妃
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鋐錕實業股份有限公司
國立臺中教育大學
陳錦章
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Priority to TW108112171A priority Critical patent/TWI776041B/en
Priority to CN201911100557.1A priority patent/CN111790412B/en
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Abstract

The present disclosure provides a method for reducing carbon dioxide to manufacture carbon compound. The method includes following steps: providing a photocatalyst, providing a reduction reaction device, performing a mixing step, performing a venting step, and performing an irradiating step. The photocatalyst includes a compound represented by formula (i) or formula (ii): BiOX formula (i); MBiO2X formula (ii). The reduction reaction device includes a reactor, a light source and a first gas storage device. The mixing step is for mixing the photocatalyst and the liquid solution in the reactor to form a mixed solution. The venting step is for venting the carbon dioxide gas from the first gas storage device into the mixed solution to form a saturated solution. The irradiating step is for irradiating the saturated solution under the light source to form a carbon compound. Accordingly, the present disclosure can reduce carbon dioxide by the photocatalyst to form the carbon compound.

Description

還原二氧化碳產製碳化合物之方法 Method for reducing carbon dioxide to produce carbon compounds

本發明是關於一種還原二氧化碳產製碳化合物之方法，尤其是關於一種利用光觸媒還原二氧化碳產製碳化合物之方法。 The present invention relates to a method for reducing carbon dioxide to produce carbon compounds, in particular to a method for reducing carbon dioxide to produce carbon compounds using photocatalyst.

石化燃料為目前最普遍的動力來源，且在工業發展、交通運輸以及農業發展上都佔據重要的地位，然而，石化燃料在使用的過程中會排放大量的二氧化碳，造成溫室效應、空氣汙染等環境問題，為了使環境能夠永續發展，如何降低二氧化碳的排放量與能源再生為現今重視的議題。 Petrochemical fuels are currently the most common source of power, and occupy an important position in industrial development, transportation and agricultural development. However, fossil fuels emit a large amount of carbon dioxide during the process of use, causing the greenhouse effect and air pollution. The question is how to reduce carbon dioxide emissions and energy regeneration in order to make the environment sustainable.

目前降低二氧化碳排放方法係使用高效率的發電系統，但其耗能且需高成本運作不符合經濟效益，為了可以節省成本、減少耗能並兼具環境保護，電化學催化與光催化還原二氧化碳為主要的研究技術，其中光催化比起電化學催化最大的優點在於不需要透過電能即能產生催化反應，而是利用太陽光作為能量來源，使用光觸媒進行反應時不會額外製造二氧化碳，因此相關研究學者致力於找尋合適的光觸媒來還原二氧化碳，達到環境保護以及永續能源的發展。 The current method of reducing carbon dioxide emissions uses high-efficiency power generation systems, but its energy-consuming and costly operation is not economical. In order to save costs, reduce energy consumption and have environmental protection, electrochemical catalysis and photocatalytic reduction of carbon dioxide are The main research technology, of which the biggest advantage of photocatalysis over electrochemical catalysis is that it does not need to transmit electricity to produce catalytic reactions, but uses sunlight as an energy source. When photocatalysts are used for reactions, no additional carbon dioxide is produced, so related research Scholars are committed to finding suitable photocatalysts to reduce carbon dioxide to achieve environmental protection and sustainable energy development.

有鑑於此，如何製備出高效能的光觸媒並應用於還原二氧化碳以符合經濟效益，遂成相關業者努力的目標。 In view of this, how to prepare high-efficiency photocatalysts and apply them to reduce carbon dioxide in order to meet economic benefits has become the goal of relevant industry efforts.

本發明之一目的是在於提供一種還原二氧化碳產製碳化合物之方法，透過合成良好光催化性之鉍基材料作為光觸媒以及複合光觸媒，使其可有效地運用於還原二氧化碳並產製甲烷。 One purpose of the present invention is to provide a method for reducing carbon dioxide to produce carbon compounds, by synthesizing a bismuth-based material with good photocatalytic properties as a photocatalyst and a composite photocatalyst, so that it can be effectively used to reduce carbon dioxide and produce methane.

本發明之一實施方式提供一種還原二氧化碳產製碳化合物之方法，其包含提供一光觸媒、提供一還原反應裝置、進行一混合步驟、進行一通氣步驟以及進行一照光步驟。其中，前述光觸媒包含由下列式(i)或式(ii)所示之化合物：BiOX 式(i)、MBiO2X 式(ii)，其中M為鉛、鈣、鍶、鋇、銅或鐵，X為氟、氯、溴或碘。前述還原反應裝置包含一反應器、一光源以及一第一氣體儲存裝置，光源以及第一氣體儲存裝置皆與反應器連接，且第一氣體儲存裝置係用於儲存一二氧化碳氣體。前述混合步驟係將光觸媒與一液體溶液於反應器中混合並震盪均勻以形成一混合溶液。前述通氣步驟係將二氧化碳氣體由第一氣體儲存裝置通入至混合溶液中，使二氧化碳氣體飽和溶解於混 合溶液中以形成一飽和溶液。前述照光步驟係將飽和溶液於光源下照射，並持續一反應時間，以生成一碳化合物。 One embodiment of the present invention provides a method for reducing carbon dioxide to produce carbon compounds, which includes providing a photocatalyst, providing a reduction reaction device, performing a mixing step, performing an aeration step, and performing an illumination step. Wherein, the aforementioned photocatalyst includes a compound represented by the following formula (i) or formula (ii): BiOX formula (i), MBiO 2 X formula (ii), where M is lead, calcium, strontium, barium, copper or iron, X is fluorine, chlorine, bromine or iodine. The aforementioned reduction reaction device includes a reactor, a light source, and a first gas storage device. The light source and the first gas storage device are connected to the reactor, and the first gas storage device is used to store a carbon dioxide gas. In the foregoing mixing step, the photocatalyst and a liquid solution are mixed in the reactor and shaken uniformly to form a mixed solution. The aforementioned aeration step is to pass carbon dioxide gas into the mixed solution from the first gas storage device, so that the carbon dioxide gas is saturated and dissolved in the mixed solution to form a saturated solution. The aforementioned illumination step is to irradiate the saturated solution under a light source for a reaction time to generate a carbon compound.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中光觸媒可更包含式(i)之化合物與式(ii)之化合物的一複合物。 According to the method for reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the photocatalyst may further comprise a complex of the compound of formula (i) and the compound of formula (ii).

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中光觸媒可更包含式(i)之化合物或式(ii)之化合物與一碳奈米材料的一複合物。 According to the method of reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the photocatalyst may further include a compound of formula (i) or a compound of a compound of formula (ii) and a carbon nanomaterial.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中碳奈米材料可為氧化石墨烯(GO)或石墨相碳氮化合物(g-C3N4)。 According to the method of reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the carbon nanomaterial can be graphene oxide (GO) or graphitic carbonitride (gC 3 N 4 ).

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中光源可為可見光、紫外光或太陽光。 According to the method for reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the light source can be visible light, ultraviolet light or sunlight.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中反應時間可為30秒至6小時。 According to the method of reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the reaction time may be 30 seconds to 6 hours.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中還原反應裝置可更包含一第二氣體儲存裝置，其與反應器連接，且第二氣體儲存裝置係用於儲存一氦氣氣體。 According to the method for reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the reduction reaction device may further include a second gas storage device connected to the reactor, and the second gas storage device is used to store a helium gas.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，可更包含一檢測步驟，其係利用一檢測裝置與反應器連接以測量碳化合物之產量。 The method for reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment may further include a detection step, which uses a detection device connected to the reactor to measure the output of carbon compounds.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中檢測裝置可為氣相層析儀。 According to the method for reducing carbon dioxide to produce carbon compounds according to the foregoing embodiment, the detection device may be a gas chromatograph.

依據前述實施方式之還原二氧化碳產製碳化合物之方法，其中碳化合物可為甲烷或甲醇。 According to the method for reducing carbon dioxide to produce a carbon compound according to the foregoing embodiment, the carbon compound can be methane or methanol.

藉此，本發明之還原二氧化碳產製碳化合物之方法是於可見光的照射下，透過鉍基材料之光觸媒以及複合光觸媒還原二氧化碳製造甲烷。鉍基材料之光觸媒具有優良的光催化性能，可提升光催化效率，以增加甲烷之產率，有效應用於二氧化碳之回收，達到永續發展的目標。 Thereby, the method for reducing carbon dioxide to produce carbon compounds of the present invention is to reduce carbon dioxide to produce methane through the photocatalyst of bismuth-based materials and the composite photocatalyst under the irradiation of visible light. The photocatalyst of bismuth-based materials has excellent photocatalytic performance, which can improve the photocatalytic efficiency to increase the yield of methane, and is effectively used in the recovery of carbon dioxide to achieve the goal of sustainable development.

100‧‧‧還原二氧化碳產製碳化合物之方法 100‧‧‧Method of reducing carbon dioxide to produce carbon compounds

110、120、130、140、150‧‧‧步驟 110, 120, 130, 140, 150‧‧‧ steps

200‧‧‧還原反應裝置 200‧‧‧Reduction reaction device

210‧‧‧反應器 210‧‧‧Reactor

220‧‧‧光源 220‧‧‧Light source

230‧‧‧第一氣體儲存裝置 230‧‧‧First gas storage device

231‧‧‧第一流量控制器 231‧‧‧First Flow Controller

240‧‧‧第二氣體儲存裝置 240‧‧‧Second gas storage device

241‧‧‧第二流量控制器 241‧‧‧Second flow controller

250‧‧‧管線 250‧‧‧Pipeline

260‧‧‧控制閥 260‧‧‧Control valve

270‧‧‧攪拌器 270‧‧‧Agitator

280‧‧‧檢測裝置 280‧‧‧Detection device

為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：第1圖係繪示依照本發明之一實施方式之一種還原二氧化碳產製碳化合物之方法的步驟流程圖；第2圖係繪示依照第1圖之還原反應裝置的示意圖；第3圖係繪示依照本發明實施例1之光觸媒的XRD繞射分析圖；第4A圖和第4B圖係繪示依照本發明實施例1之光觸媒的FESEM表面形貌；第4C圖係繪示依照本發明實施例1之光觸媒的EDS能量分散光譜圖；第5圖係繪示依照本發明實施例2之光觸媒的XRD繞射分析圖；第6A圖和第6B圖係繪示依照本發明實施例2之光觸媒的FESEM表面形貌； 第6C圖係繪示依照本發明實施例2之光觸媒的EDS能量分散光譜圖；第7圖係繪示依照本發明實施例3之光觸媒的XRD繞射分析圖；第8A圖和第8B圖係繪示依照本發明實施例3之光觸媒的FESEM表面形貌；第8C圖係繪示依照本發明實施例3之光觸媒的EDS能量分散光譜圖；第9圖係繪示依照本發明實施例6之光觸媒的XRD繞射分析圖；第10圖係繪示依照本發明實施例7之光觸媒的XRD繞射分析圖；第11圖係繪示依照本發明實施例8之光觸媒的XRD繞射分析圖；第12圖係繪示依照本發明實施例9之光觸媒的XRD繞射分析圖；第13圖係繪示依照本發明實施例10之光觸媒的XRD繞射分析圖；第14圖係繪示依照本發明實施例1及實施例11之光觸媒的XRD繞射分析圖；第15圖係繪示依照本發明實施例11之光觸媒的FESEM表面形貌；第16圖係繪示依照本發明實施例2及實施例12之光觸媒的XRD繞射分析圖； 第17A圖係繪示依照本發明實施例12之光觸媒的TEM明場圖；第17B圖係繪示依照本發明實施例12之光觸媒的擇區電子繞射圖(selected area electron diffraction)；第17C圖係繪示依照本發明實施例12之光觸媒的HR-TEM圖；第17D圖係繪示依照本發明實施例12之光觸媒的元素分布圖；第17E圖係繪示依照本發明實施例12之光觸媒的EDS能量分散光譜圖；第18圖係繪示依照本發明實施例3及實施例13之光觸媒的XRD繞射分析圖；第19圖係繪示依照本發明實施例1及實施例14之光觸媒的XRD繞射分析圖；第20A圖和第20B圖係繪示依照本發明實施例14之光觸媒的FESEM表面形貌；第20C圖係繪示依照本發明實施例14之光觸媒的TEM明場圖；第20D圖係繪示依照本發明實施例14之光觸媒的擇區電子繞射圖；第20E圖係繪示依照本發明實施例14之光觸媒的HR-TEM圖；第20F圖係繪示依照本發明實施例14之光觸媒的元素分布圖； 第20G圖係繪示依照本發明實施例14之光觸媒的EDS能量分散光譜圖；第21圖係繪示依照本發明實施例2及實施例15之光觸媒的XRD繞射分析圖；第22A圖和第22B圖係繪示依照本發明實施例15之光觸媒的FESEM表面形貌；第22C圖係繪示依照本發明實施例15之光觸媒的TEM明場圖；第22D圖係繪示依照本發明實施例15之光觸媒的擇區電子繞射圖；第22E圖係繪示依照本發明實施例15之光觸媒的HR-TEM圖；第22F圖係繪示依照本發明實施例15之光觸媒的元素分布圖；第22G圖係繪示依照本發明實施例15之光觸媒的EDS能量分散光譜圖；第23圖係繪示依照本發明實施例3及實施例16之光觸媒的XRD繞射分析圖；第24A圖和第24B圖係繪示依照本發明實施例16之光觸媒的FESEM表面形貌；第25圖係繪示依照本發明實施例17之光觸媒的XRD繞射分析圖；第26A圖係繪示依照本發明實施例17之光觸媒的TEM明場圖； 第26B圖係繪示依照本發明實施例17之光觸媒的擇區電子繞射圖；第26C圖係繪示依照本發明實施例17之光觸媒的HR-TEM圖；第26D圖係繪示依照本發明實施例17之光觸媒的元素分布圖；第26E圖係繪示依照本發明實施例17之光觸媒的EDS能量分散光譜圖；第27圖係繪示依照本發明實施例18之光觸媒的XRD繞射分析圖；第28A圖係繪示依照本發明實施例18之光觸媒的TEM明場圖；第28B圖係繪示依照本發明實施例18之光觸媒的擇區電子繞射圖；第28C圖係繪示依照本發明實施例18之光觸媒的HR-TEM圖；第28D圖係繪示依照本發明實施例18之光觸媒的EDS能量分散光譜圖；以及第29圖係繪示依照本發明實施例19之光觸媒的XRD繞射分析圖。 In order to make the above and other objectives, features, advantages and embodiments of the present invention more comprehensible, the description of the accompanying drawings is as follows: Figure 1 shows a method of reducing carbon dioxide to produce carbon according to one embodiment of the present invention The step flow chart of the compound method; Fig. 2 is a schematic diagram of the reduction reaction device according to Fig. 1; Fig. 3 is an XRD diffraction analysis diagram of the photocatalyst according to Example 1 of the present invention; Fig. 4A and Figure 4B shows the FESEM surface morphology of the photocatalyst according to the first embodiment of the present invention; Figure 4C shows the EDS energy dispersion spectrum of the photocatalyst according to the first embodiment of the present invention; Figure 5 shows the FESEM surface morphology of the photocatalyst according to the present invention. XRD diffraction analysis diagram of the photocatalyst in Example 2; Figure 6A and Figure 6B show the FESEM surface morphology of the photocatalyst in Example 2 of the present invention; Fig. 6C shows the EDS energy dispersion spectrum of the photocatalyst according to the second embodiment of the present invention; Fig. 7 shows the XRD diffraction analysis diagram of the photocatalyst according to the third embodiment of the present invention; Fig. 8A and Fig. 8B are Shows the FESEM surface morphology of the photocatalyst according to the third embodiment of the present invention; Figure 8C shows the EDS energy dispersion spectrum of the photocatalyst according to the third embodiment of the present invention; Figure 9 shows the photocatalyst according to the sixth embodiment of the present invention XRD diffraction analysis chart of the photocatalyst; Figure 10 shows the XRD diffraction analysis chart of the photocatalyst according to Embodiment 7 of the present invention; Figure 11 shows the XRD diffraction analysis chart of the photocatalyst according to Embodiment 8 of the present invention; Figure 12 shows the XRD diffraction analysis chart of the photocatalyst according to the embodiment 9 of the present invention; Figure 13 shows the XRD diffraction analysis chart of the photocatalyst according to the embodiment 10 of the present invention; Figure 14 shows the XRD diffraction analysis chart according to the present invention. XRD diffraction analysis diagrams of the photocatalyst in Example 1 and Example 11 of the invention; Figure 15 shows the FESEM surface morphology of the photocatalyst according to Example 11 of the invention; Figure 16 shows the FESEM surface topography of the photocatalyst in Example 1 and Example 11 of the invention; XRD diffraction analysis diagram of the photocatalyst of Example 12; Figure 17A shows the TEM bright field image of the photocatalyst according to Embodiment 12 of the present invention; Figure 17B shows the selected area electron diffraction diagram of the photocatalyst according to Embodiment 12 of the present invention; Figure 17C The figure shows the HR-TEM image of the photocatalyst in accordance with the twelfth embodiment of the present invention; Figure 17D shows the element distribution diagram of the photocatalyst in accordance with the twelfth embodiment of the present invention; Figure 17E shows the HR-TEM diagram in accordance with the twelfth embodiment of the present invention The EDS energy dispersion spectrum of the photocatalyst; Figure 18 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 3 and Embodiment 13 of the present invention; Figure 19 shows the analysis of the photocatalyst according to Embodiment 1 and Embodiment 14 of the present invention XRD diffraction analysis diagram of the photocatalyst; Figure 20A and Figure 20B show the FESEM surface morphology of the photocatalyst according to Example 14 of the present invention; Figure 20C shows the TEM bright field of the photocatalyst according to Example 14 of the present invention Figures; Figure 20D shows a selective area electron diffraction diagram of a photocatalyst in accordance with embodiment 14 of the present invention; Figure 20E shows an HR-TEM image of a photocatalyst in accordance with embodiment 14 of the present invention; Figure 20F shows The element distribution diagram of the photocatalyst according to embodiment 14 of the present invention; Figure 20G shows the EDS energy dispersion spectrum of the photocatalyst according to Example 14 of the present invention; Figure 21 shows the XRD diffraction analysis graph of the photocatalyst according to Example 2 and Example 15 of the present invention; Figure 22A and Figure 22B shows the FESEM surface morphology of the photocatalyst according to Example 15 of the present invention; Figure 22C shows the TEM bright field image of the photocatalyst according to Example 15 of the present invention; Figure 22D shows the implementation according to the present invention The selected area electron diffraction diagram of the photocatalyst in Example 15; Figure 22E shows the HR-TEM image of the photocatalyst in accordance with Embodiment 15 of the present invention; Figure 22F shows the element distribution diagram of the photocatalyst in accordance with Embodiment 15 of the present invention Figure 22G shows the EDS energy dispersion spectrum of the photocatalyst in accordance with Example 15 of the present invention; Figure 23 shows the XRD diffraction analysis diagram of the photocatalyst in accordance with Example 3 and Example 16 of the present invention; Figure 24A And Figure 24B shows the FESEM surface morphology of the photocatalyst according to Example 16 of the present invention; Figure 25 shows the XRD diffraction analysis diagram of the photocatalyst according to Example 17 of the present invention; TEM bright field image of the photocatalyst of Invention Example 17; Fig. 26B shows the selective electron diffraction diagram of the photocatalyst according to the embodiment 17 of the present invention; Fig. 26C shows the HR-TEM diagram of the photocatalyst according to the embodiment 17 of the present invention; Fig. 26D shows the photocatalyst according to the present invention The element distribution diagram of the photocatalyst in Example 17 of the invention; Figure 26E shows the EDS energy dispersion spectrum of the photocatalyst in accordance with Example 17 of the invention; Figure 27 shows the XRD diffraction of the photocatalyst in accordance with Example 18 of the invention Analysis diagram; Figure 28A shows a TEM bright field image of the photocatalyst in accordance with Example 18 of the present invention; Figure 28B shows a selective area electron diffraction diagram of the photocatalyst in accordance with Example 18 of the present invention; Figure 28C is a drawing Shows the HR-TEM image of the photocatalyst according to the embodiment 18 of the present invention; Figure 28D shows the EDS energy dispersion spectrum of the photocatalyst according to the embodiment 18 of the present invention; and Figure 29 shows the photocatalyst according to the embodiment 19 of the present invention XRD diffraction analysis chart of photocatalyst.

以下將參照圖式說明本發明之實施方式。為明確說明起見，許多實務上的細節將在以下敘述中一併說明。 然而，閱讀者應瞭解到，這些實務上的細節不應用以限制本發明。也就是說，在本發明部分實施方式中，這些實務上的細節是非必要的。此外，為簡化圖式起見，一些習知慣用的結構與元件在圖式中將以簡單示意的方式繪示；並且重複之元件將可能使用相同的編號表示。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. For the sake of clarity, many practical details will be explained in the following description. However, the reader should understand that these practical details should not be used to limit the present invention. That is, in some embodiments of the present invention, these practical details are unnecessary. In addition, for the sake of simplifying the drawings, some conventionally used structures and elements will be drawn in a simple schematic manner in the drawings; and repeated elements may be represented by the same number.

請參照第1圖以及第2圖，其中第1圖繪示依照本發明之一實施方式之一種還原二氧化碳產製碳化合物之方法100的步驟流程圖，第2圖繪示依照第1圖之還原反應裝置200的示意圖。還原二氧化碳產製碳化合物之方法100包含步驟110、步驟120、步驟130、步驟140以及步驟150。 Please refer to Figures 1 and 2. Figure 1 shows a flow chart of a method 100 for reducing carbon dioxide to produce carbon compounds according to an embodiment of the present invention, and Figure 2 shows the reduction in accordance with Figure 1 A schematic diagram of the reaction device 200. The method 100 for reducing carbon dioxide to produce carbon compounds includes step 110, step 120, step 130, step 140, and step 150.

步驟110為提供一光觸媒，其中光觸媒包含由下列式(i)或式(ii)所示之化合物：BiOX 式(i)、MBiO2X 式(ii)，其中M為鉛、鈣、鍶、鋇、銅或鐵，X為氟、氯、溴或碘。詳細來說，式(i)之化合物以及式(ii)之化合物皆為鉍基材料，鉍基材料因其獨特的層狀結構，有利於電子電洞分離，且在可見光下擁有高活性，使鉍基材料具有作為光觸媒材料的潛力。其中，式(i)之化合物係鹵氧化鉍系列的光觸媒，其結晶構造中含有[Bi2O2]2+的層狀結構，可與鹵素離子(X-)形成雙板交錯的特殊異相性層狀結構，此種特定層狀結構可增加其在可見光區域的吸收，並有效促進光電子的分離，然而，鹵氧化鉍之光觸媒的吸收光區大多在於紫外光區，具有電子-電洞重組率過高的問題，導致其光催化活性 常受到限制。為了改善上述問題，進而將金屬離子(M2+)摻入[Bi2O2]2+的層狀結構中，製備出式(ii)之化合物，其係類鈣鈦礦(Perovskite-like)結構之金屬鹵氧化鉍系列的光觸媒，用來修飾式(i)之化合物，提高其光催化活性。 Step 110 is to provide a photocatalyst, wherein the photocatalyst includes a compound represented by the following formula (i) or formula (ii): BiOX formula (i), MBiO 2 X formula (ii), where M is lead, calcium, strontium, barium , Copper or iron, X is fluorine, chlorine, bromine or iodine. In detail, both the compound of formula (i) and the compound of formula (ii) are bismuth-based materials. Because of their unique layered structure, bismuth-based materials facilitate the separation of electrons and holes, and have high activity under visible light. Bi-based materials have the potential as photocatalyst materials. Wherein the compound of formula (i) of the bismuth oxyhalide series based photocatalyst, the crystal structure containing a layered structure [Bi 2 O 2] 2+, and may be a halogen ion (X -) is formed of a special dual-phase interleaved plates Layered structure. This specific layered structure can increase its absorption in the visible light region and effectively promote the separation of photoelectrons. However, the absorption region of the photocatalyst of bismuth oxyhalide is mostly in the ultraviolet region, which has electron-hole recombination rate The problem of excessively high photocatalytic activity is often limited. In order to improve the above problems, metal ions (M 2+ ) were further incorporated into the layered structure of [Bi 2 O 2 ] 2+ to prepare the compound of formula (ii), which is a Perovskite-like The structure of the photocatalyst of the bismuth oxyhalide series is used to modify the compound of formula (i) to improve its photocatalytic activity.

為了增強光觸媒的效率，光觸媒可更包含式(i)之化合物與式(ii)之化合物的一複合物，其可為但不限於PbBiO2X/BiOX或BiOX/MBiO2X。另外，光觸媒可更包含式(i)之化合物或式(ii)之化合物與一碳奈米材料的一複合物，其中碳奈米材料具有優異的化學與物理性質，以及極大的比表面積，使其有良好的電子電洞傳導，因此廣泛應用於光觸媒複合材料，碳奈米材料可為但不限於碳奈米管、碳奈米纖維、碳奈米球、石墨烯、氧化石墨烯(GO)或石墨相碳氮化合物(g-C3N4)，較佳地，本發明所使用的碳奈米材料為氧化石墨烯以及石墨相碳氮化合物。 In order to enhance the efficiency of the photocatalyst, the photocatalyst may further include a complex of the compound of formula (i) and the compound of formula (ii), which may be, but not limited to, PbBiO 2 X/BiOX or BiOX/MBiO 2 X. In addition, the photocatalyst may further include a compound of formula (i) or a compound of formula (ii) and a carbon nanomaterial. The carbon nanomaterial has excellent chemical and physical properties and a large specific surface area, so that It has good electron hole conduction, so it is widely used in photocatalyst composite materials. Carbon nanomaterials can be but not limited to carbon nanotubes, carbon nanofibers, carbon nanospheres, graphene, graphene oxide (GO) Or graphitic carbonitride (gC 3 N 4 ), preferably, the carbon nanomaterials used in the present invention are graphene oxide and graphite carbonitride.

氧化石墨烯具有環氧基、氫氧基等官能基能進行還原反應，使得光觸媒與氧化石墨烯複合時，可將光催化反應產生的光電子導開，以大幅降低電子電洞的重組率，使光催化效率提高，並能夠提升光觸媒之比表面積，而式(i)之化合物或式(ii)之化合物與氧化石墨烯的複合光觸媒可為但不限於PbBiO2X/GO、BiOX/GO、BiOX/BiOY/GO或BiOX/BiOY/BiOZ/GO(X、Y、Z=F、Cl、Br、I)。石墨相碳氮化合物本身可為可見光觸媒，但是其光催化活性因光生電子電洞重組率高而受限，因此將石墨相碳氮化合物與其他光觸媒複合以製備出異質結構複合光觸媒，可加速分離光 生電子電洞，增加光催化效率，而式(i)之化合物或式(ii)之化合物與石墨相碳氮化合物的複合光觸媒可為但不限於PbBiO2X/g-C3N4、BiOX/g-C3N4、BiOX/BiOY/g-C3N4或BiOX/BiOY/BiOZ/g-C3N4(X、Y、Z=F、Cl、Br、I)。 Graphene oxide has functional groups such as epoxy and hydroxyl groups that can undergo reduction reactions, so that when the photocatalyst and graphene oxide are combined, the photoelectrons generated by the photocatalytic reaction can be guided away, so as to greatly reduce the recombination rate of electron holes and make The photocatalytic efficiency is improved and the specific surface area of the photocatalyst can be increased. The compound photocatalyst of the compound of formula (i) or the compound of formula (ii) and graphene oxide can be but not limited to PbBiO 2 X/GO, BiOX/GO, BiOX /BiOY/GO or BiOX/BiOY/BiOZ/GO (X, Y, Z=F, Cl, Br, I). Graphite carbonitride itself can be a visible light catalyst, but its photocatalytic activity is limited due to the high recombination rate of photogenerated electron holes. Therefore, the graphite phase carbonitride is compounded with other photocatalysts to prepare a heterostructure composite photocatalyst, which can accelerate separation Photo-generated electron holes increase the photocatalytic efficiency, and the compound of formula (i) or the compound of compound of formula (ii) and graphitic carbonitride can be but not limited to PbBiO 2 X/gC 3 N 4 , BiOX/gC 3 N 4 , BiOX/BiOY/gC 3 N 4 or BiOX/BiOY/BiOZ/gC 3 N 4 (X, Y, Z=F, Cl, Br, I).

步驟120為提供一還原反應裝置200，如第2圖所示，還原反應裝置200包含一反應器210、一光源220以及一第一氣體儲存裝置230，且光源220以及第一氣體儲存裝置230皆與反應器210連接，其中第一氣體儲存裝置230係用於儲存一二氧化碳氣體，另外，還原反應裝置200可更包含一第二氣體儲存裝置240，其與反應器210連接，且第二氣體儲存裝置240係用於儲存一氦氣氣體。詳細來說，第一氣體儲存裝置230與第二氣體儲存裝置240分別連接一第一流量控制器231以及一第二流量控制器241，並經由一管線250連接至反應器210，此外，各氣體儲存裝置以及各流量控制器之間皆設有控制閥260，可控制二氧化碳氣體以及氦氣氣體進入流量控制器，再通入於反應器210中。 Step 120 is to provide a reduction reaction device 200. As shown in FIG. 2, the reduction reaction device 200 includes a reactor 210, a light source 220, and a first gas storage device 230, and the light source 220 and the first gas storage device 230 are both Connected to the reactor 210, where the first gas storage device 230 is used to store a carbon dioxide gas. In addition, the reduction reaction device 200 may further include a second gas storage device 240, which is connected to the reactor 210 and stores the second gas The device 240 is used to store a helium gas. In detail, the first gas storage device 230 and the second gas storage device 240 are respectively connected to a first flow controller 231 and a second flow controller 241, and are connected to the reactor 210 via a pipeline 250. In addition, each gas A control valve 260 is provided between the storage device and each flow controller, which can control the carbon dioxide gas and helium gas to enter the flow controller, and then into the reactor 210.

步驟130為進行一混合步驟，其係將光觸媒與一液體溶液於反應器210中混合並震盪均勻以形成一混合溶液。如第2圖所示，混合溶液係將反應器210放置於一攪拌器270上混合震盪所製備而成，所述液體溶液可為鹼性氫氧化鈉水溶液，其可增加二氧化碳的溶解度。 Step 130 is a mixing step, which is to mix the photocatalyst and a liquid solution in the reactor 210 and vibrate uniformly to form a mixed solution. As shown in Figure 2, the mixed solution is prepared by placing the reactor 210 on a stirrer 270 and mixing and shaking. The liquid solution can be an alkaline sodium hydroxide aqueous solution, which can increase the solubility of carbon dioxide.

步驟140為進行一通氣步驟，其係將二氧化碳氣體由第一氣體儲存裝置230通入至混合溶液中，並維持一 小時，確保反應器210內除了二氧化碳外無其他氣體殘留，使二氧化碳氣體飽和溶解於混合溶液中以形成一飽和溶液。 Step 140 is to perform an aeration step, which is to pass carbon dioxide gas into the mixed solution from the first gas storage device 230 and maintain a It is ensured that there is no gas remaining in the reactor 210 except carbon dioxide, so that the carbon dioxide gas is saturated and dissolved in the mixed solution to form a saturated solution.

步驟150為進行一照光步驟，其係將飽和溶液於光源220下照射，並持續一反應時間，以生成一碳化合物，其中光源220可為但不限於可見光、紫外光或太陽光，且反應時間可為30秒至6小時。另外，在照光步驟後，可更包含一檢測步驟，其係利用一檢測裝置280與反應器210連接以測量碳化合物之產量，其中檢測裝置280為氣相層析儀。詳細的說，在照光反應持續30秒至6小時後，以每30分鐘使用檢測裝置280測量碳化合物以獲得各時間點反應之層析圖譜數據，以分析碳化合物之產量，而碳化合物可為甲烷或甲醇等有機物。 Step 150 is to perform an illumination step, which is to irradiate the saturated solution under the light source 220 for a reaction time to generate a carbon compound, where the light source 220 can be, but not limited to, visible light, ultraviolet light or sunlight, and the reaction time It can be 30 seconds to 6 hours. In addition, after the illumination step, a detection step may be further included, which uses a detection device 280 connected to the reactor 210 to measure the production of carbon compounds, wherein the detection device 280 is a gas chromatograph. In detail, after the light reaction lasts for 30 seconds to 6 hours, the detection device 280 is used to measure carbon compounds every 30 minutes to obtain the chromatogram data of the reaction at each time point to analyze the yield of carbon compounds, and the carbon compounds can be Organic matter such as methane or methanol.

藉此，本發明之還原二氧化碳產製碳化合物之方法係藉由鉍基材料及其複合物作為光觸媒，並應用於二氧化碳還原製造甲烷等有機物，形成碳循環，達到永續發展的目標。 Thus, the method of reducing carbon dioxide to produce carbon compounds of the present invention uses bismuth-based materials and their composites as photocatalysts, and is applied to the reduction of carbon dioxide to produce methane and other organic substances, forming a carbon cycle and achieving the goal of sustainable development.

<實施例><Example>

1. 光觸媒之合成1. Synthesis of photocatalyst

本發明之實施例1至實施例3為PbBiO2X(X=Cl、Br、I)光觸媒，其合成方法係取3mmole的硝酸鉍(Bi(NO3)3˙5H2O)溶於10mL的去離子水中攪拌均勻，隨後加入1、3、5或15mL的1M硝酸鉛(Pb(NO3)2)，並使用氫氧化鈉(NaOH)水溶液調整pH值，之後再加入1 mL的1M鹵化鉀(KX,X=Cl、Br、I)水溶液，並劇烈攪拌30分鐘，接著放入高壓釜中加熱至200℃或250℃反應12小時，之後降溫至室溫後使用去離子水過濾洗滌數次，並置入60℃烘箱烘乾12小時，研磨後即可得到實施例1至實施例3。 Examples 1 to 3 of the present invention are PbBiO 2 X (X=Cl, Br, I) photocatalysts, and the synthesis method is to take 3mmole of bismuth nitrate (Bi(NO 3 ) 3 ˙5H 2 O) dissolved in 10 mL Stir well in deionized water, then add 1, 3, 5 or 15mL of 1M lead nitrate (Pb(NO 3 ) 2 ), and use sodium hydroxide (NaOH) aqueous solution to adjust the pH, then add 1 mL of 1M potassium halide (KX, X=Cl, Br, I) aqueous solution, and vigorously stir for 30 minutes, then put it in an autoclave and heat to 200 ℃ or 250 ℃ for 12 hours, then cool to room temperature and use deionized water to filter and wash several times , And placed in a 60 ℃ oven for 12 hours to dry, after grinding to obtain Examples 1 to 3.

本發明之實施例4至實施例7為MBiO2X(M=Ca、Sr、Ba,X=Cl、Br、I)光觸媒，其合成方法係取3mmole的硝酸鉍(Bi(NO3)3˙5H2O)溶於10mL的1M硝酸(HNO3)中攪拌均勻，隨後加入1mL的1M鹵化鉀(KX,X=Cl、Br、I)攪拌30分鐘，並使用氫氧化鈉(NaOH)水溶液調整pH值，接著放入高壓釜中加熱至100℃至250℃反應24、48或72小時，之後降溫至室溫後使用去離子水過濾洗滌數次，並置入60℃烘箱烘乾12小時，以產生鹵氧化鉍。或取0.05mole的硝酸鉍溶於25mL之乙醇中配製成A液，取0.05mole的鹵化鉀溶於25mL之去離子水中配製成B液，將A液與B液混合後劇烈攪拌4小時，以抽氣過濾法過濾粉末並烘乾，使用瑪瑙研缽研磨，也可以產生鹵氧化鉍。將製備好的鹵氧化鉍與氫氧化鋇(或鈣或鍶)，以莫耳比1：1之比例磨碎混合均勻並放置坩堝中，放入高溫爐進行鍛燒(調整溫度500℃至900℃、時間12至96小時)，研磨後即可得到實施例4至實施例7。 Examples 4 to 7 of the present invention are MBiO 2 X (M=Ca, Sr, Ba, X=Cl, Br, I) photocatalyst, and the synthesis method is to take 3mmole of bismuth nitrate (Bi(NO 3 ) 3 ˙ 5H 2 O) was dissolved in 10mL of 1M nitric acid (HNO 3 ) and stirred evenly, then 1mL of 1M potassium halide (KX, X=Cl, Br, I) was added and stirred for 30 minutes, and adjusted with sodium hydroxide (NaOH) aqueous solution pH value, then put it in an autoclave and heat to 100°C to 250°C for 24, 48 or 72 hours, then cool to room temperature, filter and wash with deionized water several times, and put it in an oven at 60°C for 12 hours. To produce bismuth oxyhalide. Or dissolve 0.05 mole of bismuth nitrate in 25 mL of ethanol to prepare liquid A, and dissolve 0.05 mole of potassium halide in 25 mL of deionized water to prepare liquid B. Mix liquid A with liquid B and stir vigorously for 4 hours , The powder is filtered by suction filtration and dried, and ground with an agate mortar to produce bismuth oxyhalide. The prepared bismuth oxyhalide and barium hydroxide (or calcium or strontium) are ground and mixed uniformly in a molar ratio of 1:1, placed in a crucible, and placed in a high-temperature furnace for calcining (adjust the temperature from 500 to 900 ℃, time 12 to 96 hours), and after grinding, Example 4 to Example 7 can be obtained.

本發明之實施例8至實施例10為BiOX(X=Cl、Br、I)光觸媒，其合成方法係取3mmole的硝酸鉍(Bi(NO3)3˙5H2O)溶於10mL的1M硝酸(HNO3)中 攪拌均勻，隨後加入1mL的1M鹵化鉀(KX,X=Cl、Br、I)攪拌30分鐘，並使用氫氧化鈉(NaOH)水溶液調整pH值，接著放入高壓釜中加熱至100℃至250℃反應24、48或72小時，之後降溫至室溫後使用去離子水過濾洗滌數次，並置入60℃烘箱烘乾12小時。或取0.05mole的硝酸鉍溶於25mL之乙醇中配製成A液，取0.05mole的鹵化鉀溶於25mL之去離子水中配製成B液，將A液與B液混合後劇烈攪拌4小時，以抽氣過濾法過濾粉末並烘乾，使用瑪瑙研缽研磨，也可以產生鹵氧化鉍。研磨後即可得到實施例8至實施例10。 Examples 8 to 10 of the present invention are BiOX (X=Cl, Br, I) photocatalysts, and the synthesis method is to take 3mmole of bismuth nitrate (Bi(NO 3 ) 3 ˙5H 2 O) dissolved in 10mL of 1M nitric acid (HNO 3 ), stir evenly, then add 1mL of 1M potassium halide (KX, X=Cl, Br, I) and stir for 30 minutes, and adjust the pH value with sodium hydroxide (NaOH) aqueous solution, then put it into the autoclave to heat React at 100°C to 250°C for 24, 48, or 72 hours, then cool to room temperature, filter and wash with deionized water several times, and put it in an oven at 60°C for 12 hours. Or dissolve 0.05 mole of bismuth nitrate in 25 mL of ethanol to prepare liquid A, and dissolve 0.05 mole of potassium halide in 25 mL of deionized water to prepare liquid B. Mix liquid A with liquid B and stir vigorously for 4 hours , The powder is filtered by suction filtration and dried, and ground with an agate mortar to produce bismuth oxyhalide. After grinding, Example 8 to Example 10 can be obtained.

本發明之實施例11至實施例13為PbBiO2X/BiOX(X=Cl、Br、I)複合光觸媒，其合成方法係取3mmole的硝酸鉍(Bi(NO3)3˙5H2O)溶於10mL的1M硝酸(HNO3)中攪拌均勻，隨後加入1mL的1M鹵化鉀(KX,X=Cl、Br、I)攪拌30分鐘，再加入1、3、5或15mL的1M硝酸鉛(Pb(NO3)2)，並使用氫氧化鈉(NaOH)水溶液調整pH值，接著放入高壓釜中加熱至200℃或250℃反應12小時，之後降溫至室溫後使用去離子水過濾洗滌數次，並置入60℃烘箱烘乾12小時，研磨後即可得到實施例11至實施例13。 Examples 11 to 13 of the present invention are PbBiO 2 X/BiOX (X=Cl, Br, I) composite photocatalysts, and the synthesis method is to take 3mmole of bismuth nitrate (Bi(NO 3 ) 3 ˙5H 2 O) solution Stir well in 10mL of 1M nitric acid (HNO 3 ), then add 1mL of 1M potassium halide (KX, X=Cl, Br, I) and stir for 30 minutes, then add 1, 3, 5 or 15mL of 1M lead nitrate (Pb (NO 3 ) 2 ), and use sodium hydroxide (NaOH) aqueous solution to adjust the pH value, then put it in an autoclave and heat to 200 ℃ or 250 ℃ for 12 hours, then cool to room temperature and use deionized water to filter and wash It was placed in an oven at 60°C for 12 hours to dry, and after grinding, Example 11 to Example 13 were obtained.

本發明之實施例14至實施例16為PbBiO2X(X=Cl、Br、I)/GO複合光觸媒，其合成方法係取5mmole的硝酸鉍(Bi(NO3)3˙5H2O)溶於5mL的去離子水中攪拌均勻，形成A液，另外，取0.05克的氧化石墨烯(GO)溶於10mL的去離子水中攪拌均勻，形成B液，將A液 與B液攪拌均勻後加入5或15mL的1M硝酸鉛(Pb(NO3)2)，並使用氫氧化鈉(NaOH)水溶液調整pH值，之後加入1或3mL的5M鹵化鉀(KX,X=Cl、Br、I)水溶液，並劇烈攪拌30分鐘，接著放入高壓釜中加熱至200℃或250℃反應12小時，之後降溫至室溫後使用去離子水過濾洗滌數次，並置入60℃烘箱烘乾12小時，研磨後即可得到實施例14至實施例16。 Examples 14 to 16 of the present invention are PbBiO 2 X (X=Cl, Br, I)/GO composite photocatalyst, and its synthesis method is to take 5mmole of bismuth nitrate (Bi(NO 3 ) 3 ˙5H 2 O) solution Stir well in 5mL deionized water to form A solution. In addition, dissolve 0.05 g of graphene oxide (GO) in 10mL of deionized water and stir evenly to form B solution. Stir A and B solution evenly and add 5 Or 15mL of 1M lead nitrate (Pb(NO 3 ) 2 ), and use sodium hydroxide (NaOH) aqueous solution to adjust the pH, then add 1 or 3mL of 5M potassium halide (KX, X=Cl, Br, I) aqueous solution, Stir vigorously for 30 minutes, then put it in an autoclave and heat to 200°C or 250°C to react for 12 hours, then cool to room temperature, filter and wash with deionized water several times, and put it in a 60°C oven to dry for 12 hours, and grind Then, Example 14 to Example 16 can be obtained.

本發明之實施例17至實施例19為PbBiO2X(X=Cl、Br、I)/g-C3N4複合光觸媒，其合成方法係取5mmole的硝酸鉍(Bi(NO3)3˙5H2O)溶於5mL的去離子水中攪拌均勻，形成A液，另外，調整g-C3N4與3、5或15mL的1M硝酸鉛(Pb(NO3)2)的比例並溶於10mL的去離子水中攪拌均勻，形成B液，將A液與B液攪拌均勻後使用氫氧化鈉(NaOH)水溶液調整pH值，之後加入1或3mL的5M鹵化鉀(KX,X=Cl、Br、I)水溶液，並劇烈攪拌30分鐘，接著放入高壓釜中加熱至100℃至150℃反應12小時，之後降溫至室溫後使用去離子水過濾洗滌數次，並置入60℃烘箱烘乾12小時，研磨後即可得到實施例17至實施例19。 Examples 17 to 19 of the present invention are PbBiO 2 X (X=Cl, Br, I)/gC 3 N 4 composite photocatalyst, and the synthesis method is to take 5mmole of bismuth nitrate (Bi(NO 3 ) 3 ˙5H 2 O) Dissolve in 5mL of deionized water and stir evenly to form liquid A. In addition, adjust the ratio of gC 3 N 4 to 3, 5 or 15mL of 1M lead nitrate (Pb(NO 3 ) 2 ) and dissolve in 10mL of deionized water Stir evenly in water to form liquid B. After mixing liquid A and liquid B evenly, adjust the pH value with sodium hydroxide (NaOH) aqueous solution, and then add 1 or 3 mL of 5M potassium halide (KX, X=Cl, Br, I) aqueous solution , And stirred vigorously for 30 minutes, then put it in an autoclave and heat it to 100°C to 150°C for 12 hours, then cool to room temperature, filter and wash with deionized water several times, and put it in an oven at 60°C for 12 hours. After grinding, Example 17 to Example 19 can be obtained.

關於本發明之實施例1至實施例19的光觸媒種類如下表一所示：

Figure 108112171-A0101-12-0015-1
Figure 108112171-A0101-12-0016-2
 The types of photocatalysts in Examples 1 to 19 of the present invention are shown in Table 1 below:
Figure 108112171-A0101-12-0015-1
Figure 108112171-A0101-12-0016-2

2. 光觸媒之性質分析2. Analysis of the properties of photocatalyst

2.1 鹵氧化鉍鉛光觸媒之性質分析2.1 Property analysis of bismuth lead oxyhalide photocatalyst

請參考第3圖、第4A圖、第4B圖以及第4C圖，其中第3圖繪示依照本發明實施例1之光觸媒的XRD繞射分析圖，第4A圖和第4B圖繪示依照本發明實施例1之光觸媒的FESEM表面形貌，其中第4A圖的放大倍率為5000倍，第4B圖的放大倍率為10000倍，第4C圖繪示依照本發明實施例1之光觸媒的EDS能量分散光譜圖。由第3圖的結果可見，實施例1之光觸媒的加熱溫度為200℃，其特徵峰皆符合PbBiO2Cl之特徵峰(JCPDS card no 75-2096)，且無其 他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例1為PbBiO2Cl光觸媒。另外，由第4A圖、第4B圖以及第4C圖可知，實施例1之光觸媒呈片狀結構，且其含有Pb、Bi、O、Cl之化學元素組成，關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表二所示：

Figure 108112171-A0101-12-0017-3
Please refer to Figure 3, Figure 4A, Figure 4B, and Figure 4C. Figure 3 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 1 of the present invention. Figure 4A and Figure 4B show the The FESEM surface morphology of the photocatalyst of inventive example 1, wherein the magnification of Fig. 4A is 5000 times, the magnification of Fig. 4B is 10000 times, and Fig. 4C shows the EDS energy dispersion of the photocatalyst according to the inventive example 1 Spectrum. From the results in Figure 3, it can be seen that the heating temperature of the photocatalyst in Example 1 is 200°C, and its characteristic peaks are all consistent with the characteristic peaks of PbBiO 2 Cl (JCPDS card no 75-2096), and no other crystal phases are generated, which is a pure phase Therefore, it was confirmed by XRD diffraction analysis that Example 1 is a PbBiO 2 Cl photocatalyst. In addition, from Figures 4A, 4B, and 4C, it can be seen that the photocatalyst of Example 1 has a sheet-like structure and contains chemical elements such as Pb, Bi, O, and Cl. The weight percentage of each element (weight% ) And atomic percentage (atom%) are shown in Table 2 below:
Figure 108112171-A0101-12-0017-3

請參考第5圖、第6A圖、第6B圖以及第6C圖，其中第5圖繪示依照本發明實施例2之光觸媒的XRD繞射分析圖，第6A圖和第6B圖繪示依照本發明實施例2之光觸媒的FESEM表面形貌，其中第6A圖的放大倍率為5000倍，第6B圖的放大倍率為10000倍，第6C圖繪示依照本發明實施例2之光觸媒的EDS能量分散光譜圖。由第5圖的結果可見，實施例2之光觸媒的加熱溫度為250℃，其特徵峰皆符合PbBiO2Br之特徵峰(JCPDS card no 38-1008)，且無其他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例2為PbBiO2Br光觸媒。另外，由第6A圖、第6B圖以及第6C圖可知，實施例2之光觸媒呈板狀結構，且其含有Pb、Bi、O、Br之化學元素組成。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表三所示：

Figure 108112171-A0101-12-0017-4
Figure 108112171-A0101-12-0018-5
 Please refer to Fig. 5, Fig. 6A, Fig. 6B and Fig. 6C. Fig. 5 shows the XRD diffraction analysis diagram of the photocatalyst according to the second embodiment of the present invention. Fig. 6A and Fig. 6B show the The FESEM surface morphology of the photocatalyst in Example 2 of the invention, where the magnification of Figure 6A is 5000 times, the magnification of Figure 6B is 10000 times, and Figure 6C shows the EDS energy dispersion of the photocatalyst according to Example 2 of the invention Spectrum. From the results in Figure 5, it can be seen that the heating temperature of the photocatalyst in Example 2 is 250°C, and its characteristic peaks are in line with the characteristic peaks of PbBiO 2 Br (JCPDS card no 38-1008), and no other crystal phases are generated, which is a pure phase Therefore, XRD diffraction analysis can confirm that Example 2 is a PbBiO 2 Br photocatalyst. In addition, it can be seen from Fig. 6A, Fig. 6B, and Fig. 6C that the photocatalyst of Example 2 has a plate-like structure and contains chemical elements such as Pb, Bi, O, and Br. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 3 below:
Figure 108112171-A0101-12-0017-4
Figure 108112171-A0101-12-0018-5

請參考第7圖、第8A圖、第8B圖以及第8C圖，其中第7圖繪示依照本發明實施例3之光觸媒的XRD繞射分析圖，第8A圖和第8B圖繪示依照本發明實施例3之光觸媒的FESEM表面形貌，其中第8A圖的放大倍率為5000倍，第8B圖的放大倍率為10000倍，第8C圖繪示依照本發明實施例3之光觸媒的EDS能量分散光譜圖。由第7圖的結果可見，實施例3之光觸媒的加熱溫度為200℃，其特徵峰皆符合PbBiO2I之特徵峰(JCPDS card no 78-0521)，且無其他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例3為PbBiO2I光觸媒。另外，由第8A圖、第8B圖以及第8C圖可知，實施例3之光觸媒呈片狀結構，且其含有Pb、Bi、O、I之化學元素組成。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表四所示：

Figure 108112171-A0101-12-0018-6
Please refer to Figure 7, Figure 8A, Figure 8B, and Figure 8C. Figure 7 shows the XRD diffraction analysis diagram of the photocatalyst according to the third embodiment of the present invention. Figures 8A and 8B show the The FESEM surface morphology of the photocatalyst in Example 3 of the invention, where the magnification of Figure 8A is 5000 times, the magnification of Figure 8B is 10000 times, and Figure 8C shows the EDS energy dispersion of the photocatalyst according to Example 3 of the invention Spectrum. It can be seen from the results in Figure 7 that the heating temperature of the photocatalyst in Example 3 is 200°C, and its characteristic peaks are all consistent with the characteristic peaks of PbBiO 2 I (JCPDS card no 78-0521), and no other crystal phases are generated, which is a pure phase Therefore, XRD diffraction analysis can confirm that Example 3 is a PbBiO 2 I photocatalyst. In addition, it can be seen from Fig. 8A, Fig. 8B and Fig. 8C that the photocatalyst of Example 3 has a sheet-like structure, and it contains chemical elements such as Pb, Bi, O, and I. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 4 below:
Figure 108112171-A0101-12-0018-6

2.2 鹵氧化鉍鋇光觸媒之性質分析2.2 Analysis of the properties of bismuth barium oxyhalide photocatalyst

請參考第9圖以及第10圖，其中第9圖繪示依照本發明實施例6之光觸媒的XRD繞射分析圖，第10圖繪示依照本發明實施例7之光觸媒的XRD繞射分析圖。由第9圖的結果可見，實施例6之光觸媒的加熱溫度為600℃，加熱時間分別為24、48以及72小時，上述特徵峰皆符合BaBiO2Cl之特徵峰(JCPDS card no 83-0442)，且無其他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例6為BaBiO2Cl光觸媒。由第10圖的結果可見，實施例7之光觸媒的加熱溫度為800℃，加熱時間分別為24、48以及72小時，上述特徵峰皆符合BaBiO2Br之特徵峰(JCPDS card no 51-0266)，且無其他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例7為BaBiO2Br光觸媒。 Please refer to Figures 9 and 10. Figure 9 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 6 of the present invention, and Figure 10 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 7 of the present invention. . It can be seen from the results in Figure 9 that the heating temperature of the photocatalyst in Example 6 is 600°C, and the heating time is 24, 48, and 72 hours respectively. The above characteristic peaks are all consistent with the characteristic peaks of BaBiO 2 Cl (JCPDS card no 83-0442) , And no other crystal phases are produced, it is a pure phase compound. Therefore, XRD diffraction analysis can confirm that Example 6 is a BaBiO 2 Cl photocatalyst. It can be seen from the results in Figure 10 that the heating temperature of the photocatalyst in Example 7 is 800°C, and the heating time is 24, 48, and 72 hours respectively. The above-mentioned characteristic peaks are in line with those of BaBiO 2 Br (JCPDS card no 51-0266) , And no other crystal phases are produced, it is a pure phase compound. Therefore, XRD diffraction analysis can confirm that Example 7 is a BaBiO 2 Br photocatalyst.

2.3 鹵氧化鉍光觸媒之性質分析2.3 Analysis of the properties of bismuth oxyhalide photocatalyst

請參考第11圖、第12圖以及第13圖，其中第11圖繪示依照本發明實施例8之光觸媒的XRD繞射分析圖，第12圖繪示依照本發明實施例9之光觸媒的XRD繞射分析圖，其中第13圖繪示依照本發明實施例10之光觸媒的XRD繞射分析圖。由第11圖的結果可見，實施例8之光觸媒的特徵峰皆符合BiOCl之特徵峰(JCPDS card no 06-0249)，且無其他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例8為BiOCl光觸媒。由第12圖的結果可見，實施例9之光觸媒的特徵峰皆符合BiOBr之特徵峰(JCPDS card no 78-0348)，且無其他晶相產生，為純相化合物， 因此，由XRD繞射分析可確認實施例9為BiOBr光觸媒。由第13圖的結果可見，實施例10之光觸媒的特徵峰皆符合BiOI之特徵峰(JCPDS card no 10-0445)，且無其他晶相產生，為純相化合物，因此，由XRD繞射分析可確認實施例10為BiOI光觸媒。 Please refer to Figures 11, 12, and 13, where Figure 11 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 8 of the present invention, and Figure 12 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 9 of the present invention. Diffraction analysis diagram, wherein Figure 13 shows the XRD diffraction analysis diagram of the photocatalyst according to the tenth embodiment of the present invention. From the results in Figure 11, it can be seen that the characteristic peaks of the photocatalyst of Example 8 are all in line with the characteristic peaks of BiOCl (JCPDS card no 06-0249), and no other crystal phases are generated, and it is a pure phase compound. Therefore, the XRD diffraction analysis It can be confirmed that Example 8 is BiOCl photocatalyst. From the results in Figure 12, it can be seen that the characteristic peaks of the photocatalyst in Example 9 are all in line with the characteristic peaks of BiOBr (JCPDS card no 78-0348), and no other crystal phases are generated, so it is a pure phase compound. Therefore, XRD diffraction analysis can confirm that Example 9 is a BiOBr photocatalyst. It can be seen from the results in Fig. 13 that the characteristic peaks of the photocatalyst of Example 10 are all in line with the characteristic peaks of BiOI (JCPDS card no 10-0445), and no other crystal phases are generated. It is a pure phase compound. Therefore, it is analyzed by XRD diffraction analysis. It can be confirmed that Example 10 is a BiOI photocatalyst.

2.4鹵氧化鉍鉛/鹵氧化鉍複合光觸媒之性質分析2.4 Property analysis of bismuth lead oxyhalide/bismuth oxyhalide composite photocatalyst

請參考第14圖以及第15圖，其中第14圖繪示依照本發明實施例1及實施例11之光觸媒的XRD繞射分析圖，第15圖繪示依照本發明實施例11之光觸媒的FESEM表面形貌。由第14圖的結果可見，實施例11之光觸媒為實施例1之光觸媒與BiOCl所複合的複合光觸媒，其特徵峰皆符合PbBiO2Cl之特徵峰(JCPDS card no 75-2096)以及BiOCl之特徵峰(JCPDS card no 06-0249)，為多晶相化合物，因此，由XRD繞射分析可確認實施例11為PbBiO2Cl/BiOCl複合光觸媒。另外，由第15圖可知，實施例11之光觸媒呈片狀結構。 Please refer to Figures 14 and 15, where Figure 14 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 1 and Embodiment 11 of the present invention, and Figure 15 shows the FESEM of the photocatalyst according to Embodiment 11 of the present invention Surface topography. It can be seen from the results in Fig. 14 that the photocatalyst of Example 11 is a composite photocatalyst composed of the photocatalyst of Example 1 and BiOCl, and its characteristic peaks are in line with the characteristic peaks of PbBiO 2 Cl (JCPDS card no 75-2096) and the characteristics of BiOCl The peak (JCPDS card no 06-0249) is a polycrystalline phase compound. Therefore, XRD diffraction analysis can confirm that Example 11 is a PbBiO 2 Cl/BiOCl composite photocatalyst. In addition, it can be seen from Fig. 15 that the photocatalyst of Example 11 has a sheet-like structure.

請參考第16圖、第17A圖、第17B圖、第17C圖、第17D圖以及第17E圖，其中第16圖繪示依照本發明實施例2及實施例12之光觸媒的XRD繞射分析圖，第17A圖繪示依照本發明實施例12之光觸媒的TEM明場圖，第17B圖繪示依照本發明實施例12之光觸媒的擇區電子繞射圖，第17C圖繪示依照本發明實施例12之光觸媒的HR-TEM圖，第17D圖繪示依照本發明實施例12之光觸媒的元素分布 圖，第17E圖繪示依照本發明實施例12之光觸媒的EDS能量分散光譜圖。 Please refer to Figure 16, Figure 17A, Figure 17B, Figure 17C, Figure 17D, and Figure 17E, where Figure 16 shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 2 and Embodiment 12 of the present invention , Figure 17A shows the TEM bright field image of the photocatalyst in accordance with the twelfth embodiment of the present invention, Figure 17B shows the selective electron diffraction diagram of the photocatalyst in accordance with the twelfth embodiment of the present invention, and Figure 17C shows the implementation in accordance with the present invention The HR-TEM image of the photocatalyst of Example 12, Figure 17D shows the element distribution of the photocatalyst of Example 12 of the present invention Figure, Figure 17E shows the EDS energy dispersion spectrum of the photocatalyst according to Example 12 of the present invention.

由第16圖的結果可見，實施例12之光觸媒為實施例2之光觸媒與BiOBr所複合的複合光觸媒，其特徵峰皆符合PbBiO2Br之特徵峰(JCPDS card no 38-1008)以及BiOBr之特徵峰(JCPDS card no 78-0348)，為多晶相化合物，因此，由XRD繞射分析可確認實施例12為PbBiO2Br/BiOBr複合光觸媒。另外，由第17A圖的結果可見，其係由不同大小不同形貌的薄片組成，由第17B圖的結果可見，其為多晶相型態，與第16圖之XRD繞射分析的結果相同，由第17C圖的結果可見，其顯示兩個不同的晶格條紋，其晶格間距(d-spacing)為0.193nm和0.641nm分別對應於BiOBr的(113)繞射面和PbBiO2Br的(002)繞射面，更加確認實施例12為PbBiO2Br/BiOBr複合光觸媒，並透過第17D圖以及第17E圖可知，實施例12之光觸媒含有Pb、Bi、O、Br之化學元素組成，且皆分布於整個片狀上。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表五所示：

Figure 108112171-A0101-12-0021-7
It can be seen from the results in Figure 16 that the photocatalyst of Example 12 is a composite photocatalyst of Example 2 and BiOBr, and its characteristic peaks are in line with the characteristic peaks of PbBiO 2 Br (JCPDS card no 38-1008) and the characteristics of BiOBr The peak (JCPDS card no 78-0348) is a polycrystalline phase compound. Therefore, XRD diffraction analysis can confirm that Example 12 is a PbBiO 2 Br/BiOBr composite photocatalyst. In addition, it can be seen from the result of Figure 17A that it is composed of flakes with different sizes and different morphologies. From the result of Figure 17B, it can be seen that it is a polycrystalline phase, which is the same as the XRD diffraction analysis result of Figure 16. , As can be seen from the results in Figure 17C, it shows two different lattice fringes. The lattice spacing (d-spacing) is 0.193nm and 0.641nm, which correspond to the (113) diffraction surface of BiOBr and that of PbBiO 2 Br. (002) The diffraction surface further confirms that Example 12 is a PbBiO 2 Br/BiOBr composite photocatalyst, and it can be seen from Figure 17D and Figure 17E that the photocatalyst of Example 12 contains the chemical element composition of Pb, Bi, O, and Br, And they are all distributed on the entire sheet. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 5 below:
Figure 108112171-A0101-12-0021-7

請參考第18圖，其繪示依照本發明實施例3及實施例13之光觸媒的XRD繞射分析圖。由第18圖的結果可見，實施例13之光觸媒為實施例3之光觸媒與Bi5O7I所複合的複合光觸媒，其特徵峰皆符合PbBiO2I之特徵峰(JCPDS card no 78-0521)以及Bi5O7I之特徵峰(JCPDS card no 48-0548)，為多晶相化合物，因此，由XRD繞射分析可確認實施例13為PbBiO2I/Bi5O7I複合光觸媒。 Please refer to FIG. 18, which shows the XRD diffraction analysis diagram of the photocatalyst according to Embodiment 3 and Embodiment 13 of the present invention. It can be seen from the results in Fig. 18 that the photocatalyst of Example 13 is a composite photocatalyst of Example 3 and Bi 5 O 7 I, and its characteristic peaks are in line with the characteristic peaks of PbBiO 2 I (JCPDS card no 78-0521) And the characteristic peak of Bi 5 O 7 I (JCPDS card no 48-0548) is a polycrystalline phase compound. Therefore, XRD diffraction analysis can confirm that Example 13 is a PbBiO 2 I/Bi 5 O 7 I composite photocatalyst.

2.5 鹵氧化鉍鉛/氧化石墨烯複合光觸媒之性質分析2.5 Properties analysis of bismuth lead oxyhalide/graphene oxide composite photocatalyst

請參考第19圖、第20A圖、第20B圖、第20C圖、第20D圖、第20E圖、第20F圖以及第20G圖，其中第19圖繪示依照本發明實施例1及實施例14之光觸媒的XRD繞射分析圖，第20A圖和第20B圖繪示依照本發明實施例14之光觸媒的FESEM表面形貌，其中第20A圖的放大倍率為1000倍，第20B圖的放大倍率為3000倍，第20C圖繪示依照本發明實施例14之光觸媒的TEM明場圖，第20D圖繪示依照本發明實施例14之光觸媒的擇區電子繞射圖，第20E圖繪示依照本發明實施例14之光觸媒的HR-TEM圖，第20F圖繪示依照本發明實施例14之光觸媒的元素分布圖，第20G圖繪示依照本發明實施例14之光觸媒的EDS能量分散光譜圖。 Please refer to Figure 19, Figure 20A, Figure 20B, Figure 20C, Figure 20D, Figure 20E, Figure 20F, and Figure 20G, where Figure 19 shows Embodiment 1 and Embodiment 14 of the present invention The XRD diffraction analysis diagram of the photocatalyst. Figures 20A and 20B show the FESEM surface morphology of the photocatalyst according to Example 14 of the present invention. The magnification of Figure 20A is 1000 times, and the magnification of Figure 20B is 3000 times. Figure 20C shows the TEM bright field image of the photocatalyst according to the embodiment 14 of the present invention. Figure 20D shows the selective electron diffraction image of the photocatalyst according to the embodiment 14 of the present invention. Figure 20E shows the photocatalyst according to the present invention. The HR-TEM image of the photocatalyst in Example 14 of the present invention. FIG. 20F shows the element distribution diagram of the photocatalyst according to Embodiment 14 of the present invention. FIG. 20G shows the EDS energy dispersion spectrum of the photocatalyst according to Embodiment 14 of the present invention.

由第19圖的結果可見，實施例14之光觸媒的加熱溫度為200℃，其特徵峰皆符合PbBiO2Cl之特徵峰(JCPDS card no 75-2096)，但未觀察到GO的繞射峰，可 能是因為加入GO的含量較低，所以GO的繞射峰強度相對於PbBiO2Cl較弱。另外，由第20A圖以及第20B圖的結果可見，其由原本實施例1之片狀聚集的形貌轉變為由奈米薄片聚集形成的花球狀，而由第20C圖的結果可見，顏色較透明的部分為GO，顏色較深的為純相PbBiO2Cl光觸媒，由第20D圖的結果可見，其為多晶相(polycrystalline)結構，由第20E圖的結果可見，其顯示晶格條紋及晶格間距為0.1741nm對應於PbBiO2Cl的(131)繞射面，更加確認實施例14為PbBiO2Cl/GO複合光觸媒，並透過第20F圖以及第20G圖可知，實施例14之光觸媒含有Pb、Bi、O、Cl、C之化學元素組成，且皆均勻分布於整個片狀上。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表六所示：

Figure 108112171-A0101-12-0023-8
It can be seen from the results in Figure 19 that the heating temperature of the photocatalyst in Example 14 is 200°C, and its characteristic peaks are all consistent with the characteristic peaks of PbBiO 2 Cl (JCPDS card no 75-2096), but no diffraction peaks of GO are observed. It may be because the content of GO is low, so the diffraction peak intensity of GO is weaker than that of PbBiO 2 Cl. In addition, it can be seen from the results of Fig. 20A and Fig. 20B that the morphology of the flake-like aggregation of the original Example 1 has changed to a flower ball formed by the aggregation of nanoflake, and the result of Fig. 20C can be seen that the color is more The transparent part is GO, and the darker color is the pure phase PbBiO 2 Cl photocatalyst. It can be seen from the result of Figure 20D that it is a polycrystalline phase (polycrystalline) structure. It can be seen from the result of Figure 20E that it shows lattice fringes and lattice spacing of 0.1741nm (131) diffraction plane corresponding to PbBiO 2 Cl, and more acknowledgment Example 14 PbBiO 2 Cl / GO photocatalyst composite, and first through FIG. 20F and 20G of FIG understood, embodiments containing the photocatalyst Example 14 The chemical elements of Pb, Bi, O, Cl, and C are uniformly distributed on the entire sheet. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 6 below:
Figure 108112171-A0101-12-0023-8

請參考第21圖、第22A圖、第22B圖、第22C圖、第22D圖、第22E圖、第22F圖以及第22G圖，其中第21圖繪示依照本發明實施例2及實施例15之光觸媒的XRD繞射分析圖，第22A圖和第22B圖繪示依照本發明實施例15之光觸媒的FESEM表面形貌，其中第22A圖的放大倍率為 1000倍，第22B圖的放大倍率為3000倍，第22C圖繪示依照本發明實施例15之光觸媒的TEM明場圖，第22D圖繪示依照本發明實施例15之光觸媒的擇區電子繞射圖，第22E圖繪示依照本發明實施例15之光觸媒的HR-TEM圖，第22F圖繪示依照本發明實施例15之光觸媒的元素分布圖，第22G圖繪示依照本發明實施例15之光觸媒的EDS能量分散光譜圖。 Please refer to Figure 21, Figure 22A, Figure 22B, Figure 22C, Figure 22D, Figure 22E, Figure 22F, and Figure 22G, where Figure 21 shows Embodiment 2 and Embodiment 15 of the present invention The XRD diffraction analysis diagram of the photocatalyst. Figures 22A and 22B show the FESEM surface morphology of the photocatalyst according to Example 15 of the present invention. The magnification of Figure 22A is 1000 times, the magnification of Figure 22B is 3000 times, Figure 22C shows the TEM bright field image of the photocatalyst according to Embodiment 15 of the present invention, and Figure 22D shows the selective electron winding of the photocatalyst according to Embodiment 15 of the present invention Figure 22E shows the HR-TEM image of the photocatalyst in accordance with the fifteenth embodiment of the present invention, Figure 22F shows the element distribution diagram of the photocatalyst in accordance with the fifteenth embodiment of the present invention, and Figure 22G shows the HR-TEM diagram of the photocatalyst in accordance with the fifteenth embodiment of the present invention. EDS energy dispersion spectrum of 15 photocatalyst.

由第21圖的結果可見，實施例15之光觸媒的加熱溫度為250℃，其特徵峰皆符合PbBiO2Br之特徵峰(JCPDS card no 38-1008)，但未觀察到GO的繞射峰，可能是因為加入GO的含量較低，所以GO的繞射峰強度相對於PbBiO2Br較弱。另外，由第22A圖以及第22B圖的結果可見，其由原本實施例2之板狀聚集的形貌轉變為由奈米薄片聚集形成的花球狀，而由第22C圖的結果可見，顏色較透明的部分為GO，顏色較深的為純相PbBiO2Br光觸媒，由第20D圖的結果可見，其為多晶相結構，由第20E圖的結果可見，其顯示晶格條紋及晶格間距為0.2115nm對應於PbBiO2Br的(114)繞射面，更加確認實施例15為PbBiO2Br/GO複合光觸媒，並透過第22F圖以及第22G圖可知，實施例15之光觸媒含有Pb、Bi、O、Br、C之化學元素組成，且皆均勻分布於整個片狀上。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表七所示：

Figure 108112171-A0101-12-0024-9
Figure 108112171-A0101-12-0025-10
 It can be seen from the results in Fig. 21 that the heating temperature of the photocatalyst of Example 15 is 250°C, and its characteristic peaks are all consistent with the characteristic peaks of PbBiO 2 Br (JCPDS card no 38-1008), but no diffraction peak of GO is observed. It may be because the content of GO is low, so the diffraction peak intensity of GO is weaker than that of PbBiO 2 Br. In addition, it can be seen from the results of Figure 22A and Figure 22B that the morphology of the plate-like aggregation of the original Example 2 has changed to the flower ball formed by the aggregation of nanoflake, and the result of Figure 22C can be seen that the color is more The transparent part is GO, and the darker color is the pure phase PbBiO 2 Br photocatalyst. It can be seen from the result of Figure 20D that it is a polycrystalline phase structure. It can be seen from the result of Figure 20E that it shows lattice fringes and lattice spacing. is 0.2115nm (114) diffraction plane corresponding to PbBiO 2 Br, and more confirmation of Example 15 containing Pb PbBiO 2 Br / GO composite photocatalyst, and FIG. 22F seen through the first and second FIG. 22G, the photocatalyst of the embodiment of Example 15, Bi The chemical elements of, O, Br, and C are evenly distributed on the entire sheet. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 7 below:
Figure 108112171-A0101-12-0024-9
Figure 108112171-A0101-12-0025-10

請參考第23圖、第24A圖以及第24B圖，其中第23圖繪示依照本發明實施例3及實施例16之光觸媒的XRD繞射分析圖，第24A圖和第24B圖繪示依照本發明實施例16之光觸媒的FESEM表面形貌，其中第24A圖的放大倍率為1000倍，第24B圖的放大倍率為3000倍。由第23圖的結果可見，實施例16之光觸媒的加熱溫度為200℃，其特徵峰皆符合PbBiO2I之特徵峰(JCPDS card no 78-0521)，但未觀察到GO的繞射峰，可能是因為加入GO的含量較低，所以GO的繞射峰強度相對於PbBiO2I較弱。另外，由第24A圖以及第24B圖的結果可見，其由原本實施例3之片狀聚集的形貌轉變為由奈米薄片聚集形成的花球狀。 Please refer to Figure 23, Figure 24A, and Figure 24B. Figure 23 shows the XRD diffraction analysis of the photocatalyst in accordance with Embodiment 3 and Embodiment 16 of the present invention. Figures 24A and 24B show in accordance with this invention. The FESEM surface morphology of the photocatalyst of Inventive Example 16, wherein the magnification of Figure 24A is 1000 times, and the magnification of Figure 24B is 3000 times. It can be seen from the results in Figure 23 that the heating temperature of the photocatalyst in Example 16 is 200°C, and its characteristic peaks are all consistent with the characteristic peaks of PbBiO 2 I (JCPDS card no 78-0521), but no diffraction peaks of GO are observed. Probably because the content of GO is low, the diffraction peak intensity of GO is weaker than that of PbBiO 2 I. In addition, it can be seen from the results of Fig. 24A and Fig. 24B that the morphology of the original flake-like aggregation of Example 3 has changed to the flower-shaped sphere formed by the aggregation of nanoflake.

2.6 鹵氧化鉍鉛/石墨相碳氮化合物複合光觸媒之性質分析2.6 Property analysis of bismuth lead oxyhalide/graphite carbonitride composite photocatalyst

請參考第25圖、第26A圖、第26B圖、第26C圖、第26D圖以及第26E圖，其中第25圖繪示依照本發明實施例17之光觸媒的XRD繞射分析圖，第26A圖繪示依照本發明實施例17之光觸媒的TEM明場圖，第26B圖繪示依照本發明實施例17之光觸媒的擇區電子繞射圖，第26C圖繪示依照本發明實施例17之光觸媒的HR-TEM圖，第26D圖繪 示依照本發明實施例17之光觸媒的元素分布圖，第26E圖繪示依照本發明實施例17之光觸媒的EDS能量分散光譜圖。 Please refer to Figure 25, Figure 26A, Figure 26B, Figure 26C, Figure 26D, and Figure 26E, where Figure 25 shows the XRD diffraction analysis diagram of the photocatalyst in accordance with Embodiment 17 of the present invention, Figure 26A Shows the TEM bright field image of the photocatalyst according to the embodiment 17 of the present invention. Figure 26B shows the selective electron diffraction image of the photocatalyst according to the embodiment 17 of the present invention. Figure 26C shows the photocatalyst according to the embodiment 17 of the present invention. HR-TEM image, drawing 26D It shows the element distribution diagram of the photocatalyst according to the embodiment 17 of the present invention, and Figure 26E shows the EDS energy dispersion spectrum diagram of the photocatalyst according to the embodiment 17 of the present invention.

由第25圖的結果可見，實施例17之光觸媒由下到上為100%(純g-C3N4)、75%、50%、25%、10%、5%、0%(純PbBiO2Cl)，其特徵峰符合PbBiO2Cl之特徵峰(JCPDS card no 13-0352)，但在低的比例條件下，因為加入g-C3N4的含量較低，所以g-C3N4繞射峰強度相對於PbBiO2Cl較弱，難以觀察到g-C3N4。另外，由第26A圖的結果可見，在g-C3N4薄片上有深暗區塊為PbBiO2Cl，薄膜且具層狀結構為g-C3N4，由第26B圖的結果可見，其為多晶相結構，由第26C圖的結果可見，其顯示晶格條紋及晶格間距為0.278nm和0.308nm分別對應於PbBiO2Cl的(020)繞射面和PbBiO2Cl的(004)繞射面，而g-C3N4則為非晶排列，更加確認實施例17為PbBiO2Cl/g-C3N4複合光觸媒，並透過第26D圖以及第26E圖可知，實施例17之光觸媒含有Pb、Bi、O、Cl、C、N之化學元素組成，且皆均勻分布於多層結構上。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表八所示：

Figure 108112171-A0101-12-0026-11
Figure 108112171-A0101-12-0027-12
 It can be seen from the results in Figure 25 that the photocatalyst of Example 17 is 100% (pure gC 3 N 4 ), 75%, 50%, 25%, 10%, 5%, 0% (pure PbBiO 2 Cl ), its characteristic peak accords with the characteristic peak of PbBiO 2 Cl (JCPDS card no 13-0352), but under the condition of low ratio, because the content of gC 3 N 4 is low, the intensity of the diffraction peak of gC 3 N 4 is relatively PbBiO 2 Cl is weak, and gC 3 N 4 is difficult to observe. In addition, it can be seen from the results in Figure 26A that there are dark areas on the gC 3 N 4 sheet that are PbBiO 2 Cl, and the thin film and layered structure are gC 3 N 4. From the results in Figure 26B, it can be seen that there are more crystal structure, seen from the results of FIG. 26C, showing the lattice spacing and lattice fringes 0.308nm and 0.278nm respectively PbBiO 2 Cl corresponding to the (020) diffraction plane PbBiO 2 Cl and the (004) diffraction face, while the gC 3 N 4 was an amorphous arrangement, Example 17 is confirmed more PbBiO 2 Cl / gC 3 N 4 composite photocatalyst embodiment, and FIG. 26D seen through the first and second FIG. 26E, embodiments of the photocatalyst Example 17 containing Pb, Bi The chemical elements of, O, Cl, C, and N are uniformly distributed on the multilayer structure. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 8 below:
Figure 108112171-A0101-12-0026-11
Figure 108112171-A0101-12-0027-12

請參考第27圖、第28A圖、第28B圖、第28C圖以及第28D圖，其中第27圖繪示依照本發明實施例18之光觸媒的XRD繞射分析圖，第28A圖繪示依照本發明實施例18之光觸媒的TEM明場圖，第28B圖繪示依照本發明實施例18之光觸媒的擇區電子繞射圖，第28C圖繪示依照本發明實施例18之光觸媒的HR-TEM圖，第28D圖繪示依照本發明實施例18之光觸媒的EDS能量分散光譜圖。 Please refer to Figure 27, Figure 28A, Figure 28B, Figure 28C, and Figure 28D, where Figure 27 shows the XRD diffraction analysis diagram of the photocatalyst in accordance with Embodiment 18 of the present invention, and Figure 28A shows the XRD diffraction analysis diagram according to the present invention. The TEM bright-field image of the photocatalyst in Example 18 of the invention. Figure 28B shows the selective electron diffraction image of the photocatalyst in Example 18 of the invention. Figure 28C shows the HR-TEM of the photocatalyst in Example 18 of the invention. Fig. 28D shows the EDS energy dispersion spectrum of the photocatalyst in accordance with Example 18 of the present invention.

由第27圖的結果可見，實施例18之光觸媒由上到下為100%(純g-C3N4)、75%、50%、25%、15%、10%、5%、0%(純PbBiO2Br)，其特徵峰符合PbBiO2Br之特徵峰(JCPDS card no 38-1008)以及g-C3N4之特徵峰(JCPDS card no 87-1526)。另外，由第28A圖的結果可見，在g-C3N4薄片上有深暗區塊為PbBiO2Br，薄膜且具層狀結構為g-C3N4，由第28B圖的結果可見，其為多晶相結構，由第28C圖的結果可見，其顯示晶格條紋及晶格間距(d-spacing)為0.1662nm和0.2053nm對應於對應於PbBiO2Br的(107)繞射面和g-C3N4的(200)繞射面，更加確認實施例18為PbBiO2Br/g-C3N4複合光觸媒，並透過第28D圖可知，實施例18之光觸媒含有Pb、Bi、O、Br、C、N之化學元素組成。關於各元素的重量百分比(weight%)與原子百分比(atom%)如下表九所示：

Figure 108112171-A0101-12-0027-13
Figure 108112171-A0101-12-0028-14
 It can be seen from the results in Figure 27 that the photocatalyst of Example 18 is 100% (pure gC 3 N 4 ), 75%, 50%, 25%, 15%, 10%, 5%, 0% (pure gC 3 N 4 ) from top to bottom. PbBiO 2 Br), its characteristic peak accords with the characteristic peak of PbBiO 2 Br (JCPDS card no 38-1008) and the characteristic peak of gC 3 N 4 (JCPDS card no 87-1526). In addition, it can be seen from the results in Fig. 28A that there are dark areas on the gC 3 N 4 sheet that are PbBiO 2 Br, and the thin film and layered structure are gC 3 N 4. It can be seen from the results in Fig. 28B that there are more The crystal phase structure, as can be seen from the results in Figure 28C, shows that the lattice fringes and lattice spacing (d-spacing) of 0.1662nm and 0.2053nm correspond to the (107) diffraction plane and gC 3 N of PbBiO 2 Br (200) diffraction plane 4, Example 18 is confirmed more PbBiO 2 Br / gC 3 N 4 composite photocatalyst, and FIG. 28D through first seen, embodiments of the photocatalyst Example 18 containing Pb, Bi, O, Br, C, N The composition of chemical elements. The weight percentage (weight%) and atomic percentage (atom%) of each element are shown in Table 9 below:
Figure 108112171-A0101-12-0027-13
Figure 108112171-A0101-12-0028-14

請參考第29圖，其繪示依照本發明實施例19之光觸媒的XRD繞射分析圖。由第29圖的結果可見，實施例19之光觸媒由下到上為100%(純g-C3N4)、75%、50%、25%、10%、5%、0%(純PbBiO2I)，其特徵峰符合PbBiO2I之特徵峰(JCPDS card no 38-1007)，但在低的比例條件下，因為加入g-C3N4的含量較低，所以g-C3N4繞射峰強度相對於PbBiO2I較弱，難以觀察到g-C3N4。 Please refer to FIG. 29, which shows the XRD diffraction analysis diagram of the photocatalyst according to Example 19 of the present invention. It can be seen from the results in Figure 29 that the photocatalyst of Example 19 is 100% (pure gC 3 N 4 ), 75%, 50%, 25%, 10%, 5%, 0% (pure PbBiO 2 I ), its characteristic peak accords with the characteristic peak of PbBiO 2 I (JCPDS card no 38-1007), but under the condition of low ratio, because the content of gC 3 N 4 is low, the diffraction peak intensity of gC 3 N 4 is relatively Because PbBiO 2 I is weak, gC 3 N 4 is difficult to observe.

3. 還原二氧化碳產製甲烷3. Reduce carbon dioxide to produce methane

本發明係依照第1圖實施方式之還原二氧化碳產製碳化合物之方法100來進行，詳細來說，先將本發明之實施例1至實施例19的光觸媒0.2g加入至300mL的氫氧化鈉溶液中震盪均勻形成混合溶液，之後以每分鐘50mL的速率通入氦氣並維持30分鐘後關閉氣體使用氣相層析儀測量B1作為背景值1，以進行無光照、無二氧化碳之空白測試。接著以每分鐘10mL的速率通入二氧化碳並維持60分鐘後使用氣相層析儀B2作為背景值2，以進行無光照之空白測試。二氧化碳氣體不關閉，使其飽和溶解於混合溶液中形成飽和溶液，開啟LED光源開始照光反應4小時，並且30秒及每30分鐘使用氣相層析儀測量甲烷產量，以獲得個時間點 反應之層析圖譜數據，反應完成後將光源及氣體關閉，將反應後之溶液過濾後在相同參數下使用氣相層析儀分析。 The present invention is carried out in accordance with the method 100 for reducing carbon dioxide to produce carbon compounds according to the embodiment shown in Fig. 1. In detail, first add 0.2g of the photocatalyst of Examples 1 to 19 of the present invention to 300 mL of sodium hydroxide solution The mixed solution is uniformly formed by vortexing, and then helium gas is introduced at a rate of 50 mL per minute and maintained for 30 minutes, and then the gas is turned off. The gas chromatograph is used to measure B1 as a background value 1 to perform a blank test without light and carbon dioxide. Then carbon dioxide was introduced at a rate of 10 mL per minute and maintained for 60 minutes, and then gas chromatograph B2 was used as the background value 2 to perform a blank test without light. The carbon dioxide gas is not turned off, so that it is saturated and dissolved in the mixed solution to form a saturated solution. Turn on the LED light source to start the light reaction for 4 hours, and use the gas chromatograph to measure the methane production for 30 seconds and every 30 minutes to obtain a time point The chromatogram data of the reaction. After the reaction is completed, the light source and gas are turned off, and the solution after the reaction is filtered and analyzed by gas chromatograph under the same parameters.

本發明之實施例1至實施例10之光觸媒經由照光反應後，皆能還原二氧化碳並產製甲烷，其光源波長、觸媒量、測量時間點以及甲烷產率(μmol/g/h)如下表十所示：

Figure 108112171-A0101-12-0029-16
Figure 108112171-A0101-12-0030-17
Figure 108112171-A0101-12-0031-18
 The photocatalysts of Examples 1 to 10 of the present invention can all reduce carbon dioxide and produce methane after light reaction. The light source wavelength, catalyst amount, measurement time point and methane yield (μmol/g/h) are as follows Ten shows:
Figure 108112171-A0101-12-0029-16
Figure 108112171-A0101-12-0030-17
Figure 108112171-A0101-12-0031-18

本發明之實施例11至實施例19之複合光觸媒經由照光反應後，皆能還原二氧化碳並產製甲烷，其光源波長、觸媒量、測量時間點以及甲烷產率(μmol/g/h)如下表十一所示：

Figure 108112171-A0101-12-0031-19
Figure 108112171-A0101-12-0032-20
Figure 108112171-A0101-12-0033-21
 The composite photocatalysts of Examples 11 to 19 of the present invention can all reduce carbon dioxide and produce methane after light reaction. The light source wavelength, amount of catalyst, measurement time point and methane yield (μmol/g/h) are as follows Table 11 shows:
Figure 108112171-A0101-12-0031-19
Figure 108112171-A0101-12-0032-20
Figure 108112171-A0101-12-0033-21

綜上所述，本發明提供一種還原二氧化碳產製碳化合物之方法，透過合成有光催化效能之鉍基材料及其複合物作為光觸媒，經由照光反應，使光觸媒產生電子電洞，其不僅能還原二氧化碳，達成二氧化碳的減量，同時又可生成具有經濟價值的甲烷，以達到永續發展的目標。 In summary, the present invention provides a method for reducing carbon dioxide to produce carbon compounds. By synthesizing bismuth-based materials with photocatalytic performance and their composites as photocatalysts, the photocatalyst generates electron holes through the light reaction, which can not only reduce Carbon dioxide can reduce the amount of carbon dioxide while generating economically valuable methane to achieve the goal of sustainable development.

雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be subject to those defined in the attached patent scope.

100‧‧‧還原二氧化碳產製碳化合物之方法 100‧‧‧Method of reducing carbon dioxide to produce carbon compounds

110、120、130、140、150‧‧‧步驟 110, 120, 130, 140, 150‧‧‧ steps

Claims (10)

一種還原二氧化碳產製碳化合物之方法，包含：提供一光觸媒，其中該光觸媒包含由下列式(i)或式(ii)所示之化合物：BiOX 式(i)、MBiO2X 式(ii)，其中M為鉛、鈣、鍶、鋇、銅或鐵，X為氟、氯、溴或碘；提供一還原反應裝置，其中該還原反應裝置包含一反應器、一光源以及一第一氣體儲存裝置，該光源以及該第一氣體儲存裝置皆與該反應器連接，且該第一氣體儲存裝置係用於儲存一二氧化碳氣體；進行一混合步驟，其係將該光觸媒與一液體溶液於該反應器中混合並震盪均勻以形成一混合溶液；進行一通氣步驟，其係將該二氧化碳氣體由該第一氣體儲存裝置通入至該混合溶液中，使該二氧化碳氣體飽和溶解於該混合溶液中以形成一飽和溶液；進行一照光步驟，其係將該飽和溶液於該光源下照射，並持續一反應時間，以生成一碳化合物。 A method for reducing carbon dioxide to produce carbon compounds, comprising: providing a photocatalyst, wherein the photocatalyst comprises a compound represented by the following formula (i) or (ii): BiOX formula (i), MBiO 2 X formula (ii), Wherein M is lead, calcium, strontium, barium, copper or iron, and X is fluorine, chlorine, bromine or iodine; a reduction reaction device is provided, wherein the reduction reaction device includes a reactor, a light source and a first gas storage device , The light source and the first gas storage device are both connected to the reactor, and the first gas storage device is used to store a carbon dioxide gas; a mixing step is performed, which is to place the photocatalyst and a liquid solution in the reactor Mix and vibrate uniformly to form a mixed solution; perform an aeration step, which is to pass the carbon dioxide gas into the mixed solution from the first gas storage device, so that the carbon dioxide gas is saturated and dissolved in the mixed solution to form A saturated solution; a step of illuminating is carried out, which is to irradiate the saturated solution under the light source for a reaction time to generate a carbon compound. 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，其中該光觸媒更包含式(i)之化合物與式(ii)之化合物的一複合物。 The method for reducing carbon dioxide to produce carbon compounds as described in item 1 of the scope of patent application, wherein the photocatalyst further comprises a compound of the compound of formula (i) and the compound of formula (ii). 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，其中該光觸媒更包含式(i)之化合物或式(ii)之化合物與一碳奈米材料的一複合物。 The method for reducing carbon dioxide to produce carbon compounds as described in the first item of the scope of patent application, wherein the photocatalyst further comprises a compound of formula (i) or a compound of formula (ii) and a carbon nanomaterial. 如申請專利範圍第3項所述之還原二氧化碳產製碳化合物之方法，其中該碳奈米材料為氧化石墨烯或石墨相碳氮化合物。 The method for reducing carbon dioxide to produce carbon compounds as described in item 3 of the scope of patent application, wherein the carbon nanomaterial is graphene oxide or graphitic carbonitride. 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，其中該光源為可見光、紫外光或太陽光。 The method for reducing carbon dioxide to produce carbon compounds as described in item 1 of the scope of patent application, wherein the light source is visible light, ultraviolet light or sunlight. 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，其中該反應時間為30秒至6小時。 The method for reducing carbon dioxide to produce carbon compounds as described in item 1 of the scope of patent application, wherein the reaction time is 30 seconds to 6 hours. 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，其中該還原反應裝置更包含一第二 氣體儲存裝置，其與該反應器連接，且該第二氣體儲存裝置係用於儲存一氦氣氣體。 The method for reducing carbon dioxide to produce carbon compounds as described in item 1 of the scope of patent application, wherein the reduction reaction device further includes a second A gas storage device is connected to the reactor, and the second gas storage device is used to store a helium gas. 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，更包含一檢測步驟，其係利用一檢測裝置與該反應器連接以測量該碳化合物之產量。 The method for reducing carbon dioxide to produce carbon compounds as described in item 1 of the scope of patent application further includes a detection step, which uses a detection device connected to the reactor to measure the output of the carbon compounds. 如申請專利範圍第8項所述之還原二氧化碳產製碳化合物之方法，其中該檢測裝置為氣相層析儀。 The method for reducing carbon dioxide to produce carbon compounds as described in item 8 of the scope of patent application, wherein the detection device is a gas chromatograph. 如申請專利範圍第1項所述之還原二氧化碳產製碳化合物之方法，其中該碳化合物為甲烷或甲醇。 The method for reducing carbon dioxide to produce carbon compounds as described in item 1 of the scope of patent application, wherein the carbon compound is methane or methanol.
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