KR20100113442A - Ring type palladium nano structure body and the catalyst for decomposition of volatile organic compound using the palladium nano structure body - Google Patents
Ring type palladium nano structure body and the catalyst for decomposition of volatile organic compound using the palladium nano structure body Download PDFInfo
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Abstract
Description
본 발명은 나노크기의 Pd나노 제조와 Pd나노의 형상제어를 통해 제조한 고리형 Pd나노구조체 및 그 휘발성 유기화합물 분해용 촉매에 관한 기술이다.The present invention relates to a cyclic Pd nanostructure prepared through the production of nano-sized Pd nano and the shape control of Pd nano and a catalyst for decomposition of volatile organic compounds.
형상제어된 나노입자를 촉매로 응용하는 연구는 아직 초기단계로서 개념 입증 단계에 머물러 있다.Research into the application of shape-controlled nanoparticles as a catalyst is still in its infancy and proof of concept.
또한, 고순도의 형상제어된 나노입자를 대량 생산할 수 있는 기술이 필수적으로 요구되나 합성이 까다롭고 재현성이 부족하여 연구실에서 수 mg단위의 합성이 전부였다.In addition, the technology to mass-produce high-purity shape-controlled nanoparticles is indispensable, but the synthesis is difficult and the reproducibility is lacking.
이에 본 발명은 고순도의 형상이 제어된 고리형 Pd나노구조체를 대량생산함으로써 휘발성 유기화합물을 분해하는 촉매로 사용할 수 있다.Accordingly, the present invention can be used as a catalyst for decomposing volatile organic compounds by mass-producing cyclic Pd nanostructures of high purity controlled shape.
본 발명은 입방형 Pd나노입자가 수소 흡장된 후 분자자기조립된 고리형 Pd나노구조체를 제공한다.The present invention provides a molecular self-assembled cyclic Pd nanostructure after the cubic Pd nanoparticles are hydrogen occluded.
또한, 본 발명은 상기 고리형 Pd나노구조체를 수질 또는 대기오염 배출억제 또는 방지시설에서 휘발성 유기화합물 분해용 촉매로서 사용하는 것을 특징으로 하는 고리형 Pd나노구조체를 제공한다.The present invention also provides a cyclic Pd nanostructure using the cyclic Pd nanostructure as a catalyst for decomposing volatile organic compounds in water or air pollution emission suppression or prevention facilities.
또한, 본 발명은 상기 고리형 Pd나노구조체를 포함하는 것을 특징으로 하는 휘발성 유기화합물 분해용 촉매를 제공한다.The present invention also provides a catalyst for decomposing volatile organic compounds comprising the cyclic Pd nanostructure.
상술한 바와 같이 고리형 Pd나노구조체는 그 구조체 자체의 높은 에너지와 표면적이 크고, 화학적으로 물리적 특성을 조절할 수 있고, 구조적으로 매우 안정한 물질이라는 나노의 특이한 작용으로 인해 휘발성 유기화합물 분해에 따른 수질 및 공기정화용 촉매로의 응용 등 다양한 분야에 탁월한 효과를 나타낸다.As described above, the cyclic Pd nanostructure has a high energy and surface area of the structure itself, can control chemical properties physically, and is a structurally very stable material. Excellent effect in various fields such as application as a catalyst for air purification.
아울러, 낮은 에너지인 상온, 상압에서 간단하게 나노구조체 형성을 할 수 있어 대량생산이 가능한 고순도 초정밀의 Pd나노구조체를 생산할 수 있다.In addition, the nanostructures can be easily formed at room temperature and atmospheric pressure, which is low energy, so that high-purity ultra-precision Pd nanostructures can be produced.
본 발명은 입방형 Pd나노입자가 수소 흡장된 후 분자자기조립된 고리형 Pd나노구조체로서 입경 1~30nm로 형상 제어된 상기 입방형 Pd나노입자의 단위 입자간에 거리를 조절하여 고리형 Pd나노구조체를 형성하게 하는 기술이다.The present invention provides a cyclic Pd nanostructure by controlling the distance between the unit particles of the cubic Pd nanoparticles shape-controlled to a particle diameter of 1 ~ 30nm as a self-assembled cyclic Pd nanostructure after hydrogen occluded cubic Pd nanoparticles It is a technique to form.
여기서, 본 발명은 Pd금속을 나노미터크기인 Pd나노입자로 만들면서 분자 재조립과정 중 상기 Pd나노입자의 형상 제어를 통해 고리형 Pd나노구조체를 형성하게 하는 기술이다. 이 방법은 Pd나노금속의 결정성장 방향 및 속도를 pH로 조절함으로써 환원속도를 제어하여 상기 고리형 Pd나노구조체를 제조한 것이다. Here, the present invention is a technique for forming a cyclic Pd nanostructure through the shape control of the Pd nanoparticles during the molecular reassembly process while making the Pd metal nanoparticle sized Pd nanoparticles. In this method, the cyclic Pd nanostructure is prepared by controlling the rate of reduction by adjusting the direction and rate of crystal growth of Pd nanometal to pH.
본 발명의 1 ~ 30nm의 입방형 Pd나노입자와 Pd나노구조체 제조방법은 수소 흡장된 Pd봉을 사용하여 전해질속에서 전기분해하여 1 ~ 30nm의 입방형 나노입자인 100% 순도의 Pd나노입자를 생산하고, 수소이온농도를 조절하여 생산된 Pd나노입자가 자기조립이 된 일정한 형상 즉 고리형으로 형상이 제어된 10 ~ 300nm의 크기를 갖는 고리형 Pd구조체를 생산하는 것이다.1 to 30nm cubic Pd nanoparticles and Pd nanostructure manufacturing method of the present invention using a hydrogen-absorbed Pd rod electrolysis in the electrolyte to 100% pure Pd nanoparticles of 1 ~ 30nm cubic nanoparticles It is to produce a cyclic Pd structure having a size of 10 ~ 300nm that is produced, and the Pd nanoparticles produced by controlling the hydrogen ion concentration is self-assembled, that is, a ring-shaped shape.
이렇게 합성된 각자 하나의 Pd나노입자(1~30nm)는 넓은 비표면적을 가지며, 형성된 나노구조체(10~300nm)는 특별한 높은 에너지로 기존의 상용 광촉매보다 높은 광활성을 가진다.Each Pd nanoparticle (1 ~ 30nm) synthesized in this way has a large specific surface area, and the formed nanostructure (10 ~ 300nm) has a high optical activity than the conventional commercial photocatalyst with a special high energy.
이때, 나노 물질은 벌크(bulk) 상태와 다른 성질을 나타내며 100nm 이하의 크기에서 물질의 크기와 조성 및 형태 등 화학적 물성을 조절하면 물질의 광 특성, 전기적 특성, 자기적 특성 등 물리적 물성을 자유롭게 변화시킬 수 있다. 이러한 나노 물질을 이용하여 형성한 나노 구조체는 여러가지 특성을 가지게 되는데 그 첫째는 크기가 작기 때문에 아주 큰 표면을 가지며, 둘째는 화학적으로 물리적 특성을 조절할 수 있다는 것, 셋째는 우수한 타켓 결합 특성을 가지며 구조적으로 매우 안정한 물질이라는 것이다. 이러한 나노구조체 자체의 특별히 높은 에너지와 상기 나노의 특이한 작용으로 인해 여러분야에서 다양한 작용을 할 수 있다.In this case, nanomaterials exhibit different properties from the bulk state, and if the chemical properties such as the size, composition, and shape of the material are controlled at a size of 100 nm or less, the physical properties such as optical properties, electrical properties, and magnetic properties of the materials can be freely changed. You can. Nanostructures formed using these nanomaterials have various characteristics. First, they have a very large surface because of their small size. Second, they can control physical properties chemically. Third, they have excellent target binding properties. It is a very stable substance. The extraordinary high energy of these nanostructures themselves and the unique action of the nanostructures can cause a variety of functions in all of you.
상기 나노구조체의 형상은 도 1에 나타나 있다. 도 1은 Pd원소의 면심입방격자(Face Centered Cubic; FCC)상으로 분석한 것들이다. The shape of the nanostructures is shown in FIG. 1. 1 is an analysis of the face centered cubic (FCC) of the Pd element.
도 1의 경우는 그 Pd는 순수 Pd 금속으로 그 결정구조가 거의 완벽하게 배열된 상태를 보여주는 주사투과전자현미경(scanning transmission electron microscopy;STEM) 사진이다. 이러한 Pd나노입자들은 다시 집적화되며 이는 분자자기조립에 의한 것으로 이야기되기도 하는데, 집적화된 후에도 고리모양으로 가운데가 빈 형태를 띠게 된다. 이러한 집적화가 계속되더라도 어느 정도까지는 계속하여 고리형태를 보이게 되는데 마치 프랙탈과 같은 경향을 가진다. 결국은 이는 Pd이 원자 수준에서 높은 결정화가 이루어졌음을 의미하는 것으로 이를 통해 높은 반응성과 선택성을 갖는 것으로 짐작하고 있다.In the case of FIG. 1, the Pd is a pure Pd metal, and a scanning transmission electron microscopy (STEM) photograph showing the state in which the crystal structure is almost perfectly arranged. These Pd nanoparticles are re-integrated, which may be said to be due to molecular self-assembly, and even after they are integrated, they have an annular hollow shape. Even if this integration continues, it continues to show a ring shape to some extent, which is like a fractal. In the end, this means that Pd has high crystallization at the atomic level, and it is assumed that it has high reactivity and selectivity.
상기 Pd나노구조체는 수소흡착력이 대단히 높아지게 된다. 특히 이러한 수소흡착력은 “실험실상 통상의 온도와 압력(이하 본 명세서에서는 “통상 온도와 압력”이라한다, 여기서 “통상의 온도와 압력”이라 함은 물이 액체상태를 유지하는 온도와 1기압은 물론 1기압을 초과하는 경우도 포함한다)”에서도 대단히 효율적으로 나타나는데 대체로 부피대비 약 100배 이상이 되는 것으로 나타났다. 본 반응은 1기압 하에서도 반응이 가능하며 압력이 이를 초과할 경우에도 당연히 반응 가능하다. The Pd nanostructure has a very high hydrogen adsorption force. In particular, the hydrogen adsorption force is referred to as "normal temperature and pressure in the laboratory" (hereinafter, "normal temperature and pressure", where "normal temperature and pressure" means the temperature and 1 atmosphere of water to maintain a liquid state Of course, it also appears to be more than 100 times the volume. The reaction can be carried out even under 1 atm, and of course, even when the pressure exceeds this.
또한, 상기 Pd나노구조체는 유기물을 분해하는데도 탁월한 효과를 나타내었다. 과거에도 Pd이 나노분말 형태로 유기물 분해에 사용되기도 했다. 그러나 본 발명의 Pd 나노구조체는 대단히 높은 수소흡착력을 이용한 것으로 유기물 내의 수소를 흡착하여 분해하는 원리를 이용하고 있다. In addition, the Pd nanostructures showed an excellent effect in decomposing organic matter. In the past, Pd has been used to decompose organic matter in the form of nanopowders. However, the Pd nanostructure of the present invention utilizes a very high hydrogen adsorption force and uses the principle of adsorbing and decomposing hydrogen in an organic material.
본 발명에서는 Pd나노구조체를 알코올이 함유된 용기에 넣어둘 경우 알코올이 분해되어 사라지는 것을 확인할 수 있었다. 이러한 현상은 다른 유기물에 있어서도 동일하게 작용할 수 있고 그 효율도 대단히 높다. In the present invention, when the Pd nanostructure is placed in a container containing alcohol, it was confirmed that the alcohol is decomposed and disappeared. This phenomenon can work the same in other organic matters, and its efficiency is very high.
상기 Pd나노구조체는 다음과 같이 제작된다. The Pd nanostructure is manufactured as follows.
본 발명의 나노구조체 제조방법은 Pd봉을 사용하여 전해질속에서 전기분해하여 1 ~ 30nm의 입방형 나노입자인 100% 순도의 Pd나노입자를 생산하고, 수소이온농도를 조절하여 생산된 Pd나노입자가 자기조립이 된 일정한 형상 즉 고리형으로 형상이 제어된 10 ~ 300nm의 크기를 갖는 고리형 Pd구조체를 대량으로 생산하는 것이 다.In the nanostructure manufacturing method of the present invention, Pd nanoparticles are 100% pure Pd nanoparticles, which are 1-30 nm cubic nanoparticles by electrolysis in an electrolyte using Pd rods, and Pd nanoparticles are produced by controlling hydrogen ion concentration. It is to mass produce a cyclic Pd structure having a size of 10 ~ 300nm in which a self-assembled shape is controlled to a ring shape.
이때, Pd봉을 전극으로 사용하여 전해질 속에서 전극과 물을 전기분해한다.At this time, the electrode and water are electrolyzed in the electrolyte using a Pd rod as an electrode.
여기서, 전해질은 여러 가지를 사용할 수 있으나 염화나트륨(NaCl)을 기준으로 농도는 0.01%~5%로 하며, 전류와 전압은 0.01A~10A, 2V~40V 사이를 교대로 조절하여 양극에서는 염화이온(Cl-)이 팔라듐(Pd)과 결합하여 Pd와 Cl의 금속염을 생성시킨다.Here, the electrolyte may be used in various ways, but the concentration is 0.01% to 5% based on sodium chloride (NaCl), and the current and voltage are alternately controlled between 0.01A to 10A and 2V to 40V, so that the chloride ion Cl − ) combines with palladium (Pd) to form metal salts of Pd and Cl.
이러한 공정은 생성된 Pd나노입자와 전해질을 고르게 교반시키는 과정에서 이루어진다. This process is performed in the process of evenly stirring the generated Pd nanoparticles and the electrolyte.
생성된 Pd와 Cl의 금속염 염화팔라듐(PdCl2)은 음극 주변에서 생성되는 수소이온(H+)에 의해 염화이온(Cl-)이 떨어지고 1 ~ 30nm의 입방형 Pd나노입자인 팔라듐(Pd)원자가 생성된다. 곧 생성된 팔라듐(Pd)원자는 분자자기조립(응집)을 하면서 Pd나노구조체가 형성되어 생산 용기의 바닥으로 침전된다. 침전된 Pd내에는 염화팔라듐과 Pd나노구조체가 혼재되어 있게 된다. 여기서, 바닥으로 침전된 Pd나노구조체 또는 서서히 바닥으로 가라앉는 침전이 덜된 Pd나노구조체를 염화나트륨 용액과 분리하여 순수한 Pd나노구조체를 얻는다. 이때, 염화이온(Cl-)은 염소기체(Cl2)가 되어 날아가거나 염화나트륨(NaCl) 용액에 다시 들어가고, 상기 수소이온(H+)은 전자를 받아 수소기체(H2)가 된다. 여기서, 용액의 pH 조절이 대단히 중요한데, 이는 pH가 Pd나노구조체의 응집형태와 관련이 크기 때문이다. 통상 pH 6~10에서 원활한 응집이 일어나는 것을 알 수 있다. 이때, 용액의 pH 조절은 전압과 전류를 조절하여 수소이온(H+)과 수산화이온(OH-)의 양을 조절하는 것으로서 pH가 조절된다. Pd and Cl metal salts of palladium chloride (PdCl 2 ) are formed by the palladium (Pd) atom, which is a cubic Pd nanoparticle of 1 to 30 nm, with the chloride ion (Cl − ) dropping by hydrogen ions (H + ) generated around the cathode. Is generated. The resulting palladium (Pd) atoms undergo molecular self-assembly (aggregation) to form Pd nanostructures and settle to the bottom of the production vessel. In the precipitated Pd, palladium chloride and Pd nanostructures are mixed. Here, the Pd nanostructure precipitated to the bottom or the Pd nanostructure gradually precipitated to the bottom is separated from the sodium chloride solution to obtain a pure Pd nanostructure. At this time, the chloride ion (Cl − ) is a chlorine gas (Cl 2 ) to fly or re-enter the sodium chloride (NaCl) solution, the hydrogen ion (H + ) receives the electron becomes a hydrogen gas (H 2 ). Here, the pH control of the solution is very important because the pH is related to the aggregation form of the Pd nanostructure. It can be seen that smooth aggregation usually occurs at pH 6-10. In this case, pH adjustment of the solution has a hydrogen ion (H +) and hydroxide ions (OH -) to adjust the voltage and current, the pH is adjusted as to control the amount of.
본 발명의 또 다른 성과는 상기의 Pd나노구조체를 획득하는 방법을 또다시 크게 개선했다는 점이다.Another achievement of the present invention is that the method of obtaining the Pd nanostructures is again greatly improved.
상기 공정에서 전극으로 사용하는 Pd봉(순수 Pd금속 덩어리)을 전극으로 사용 전에 수소를 흡장(흡수하여 저장)하도록 하여 사용할 경우 Pd나노구조체 생산 효율을 획기적으로 상승시킬 수 있었다. 여기서 흡장이라 함은 Pd격자 사이로 수소를 주입하는 것을 말한다.When the Pd rod (pure Pd metal mass) used as an electrode in the process was used to absorb (storage and store) hydrogen before using as an electrode, the production efficiency of Pd nanostructures could be significantly increased. Here, occlusion refers to the injection of hydrogen between the Pd lattice.
Pd금속에 수소를 흡장하는 방법은 널리 알려진 것으로 그 어떤 방법이라도 사용할 수 있다. 그 중 하나의 수소흡장법은 Pd금속을 수소 기체 분위기에서 압력과 온도를 올리면 수소가 Pd에 흡장되는 것이다. 이때 수소 흡장량은 압력과 온도와 시간에 비례한다.The method of occluding hydrogen in Pd metal is widely known, and any method may be used. One of the hydrogen occlusion methods is that hydrogen is occluded in Pd when the Pd metal is raised in pressure and temperature in a hydrogen gas atmosphere. At this time, the hydrogen storage amount is proportional to the pressure, temperature and time.
또한, 수소의 흡장량은 물속에서 지속적으로 수소를 배출하는 것이 중요하므로 가능한 많은 양의 수소를 흡장시키는 것이 필요하다.In addition, since the storage amount of hydrogen is important to continuously discharge hydrogen in water, it is necessary to occlude as much hydrogen as possible.
이후의 공정은 상기 수소를 흡장하지 않은 Pd를 사용하는 것과 유사하며 다음과 같다. The subsequent process is similar to using Pd without occluding hydrogen, as follows.
수소를 흡장한 Pd를 전극으로 사용하여 전해질 속에서 전극과 물을 전기분해 한다.Electrodes and water are electrolyzed in electrolyte using Pd absorbed hydrogen.
이때, 전해질은 여러 가지를 사용할 수 있으나 염화나트륨(NaCl)을 기준으로 농도는 0.01%~5%로 하며, 전류와 전압은 0.01A~10A, 2V~40V 사이를 교대로 조절하여 양극에서는 염화이온(Cl-)이 팔라듐(Pd)과 결합하여 Pd와 Cl의 금속염을 생성시킨다.In this case, various electrolytes may be used, but the concentration is 0.01% to 5% based on sodium chloride (NaCl), and the current and voltage are alternately controlled between 0.01A to 10A and 2V to 40V to allow chloride ion ( Cl − ) combines with palladium (Pd) to form metal salts of Pd and Cl.
이러한 공정은 생성된 나노입자와 전해질을 고르게 교반시키는 과정에서 이루어진다. This process is performed in the process of evenly stirring the resulting nanoparticles and the electrolyte.
생성된 Pd와 Cl의 금속염 염화팔라듐(PdCl2)은 음극 주변에서 생성되는 수소이온(H+)에 의해 염화이온(Cl-)이 떨어지기도 하나 대부분은 흡장된 수소가 방출되어 염화이온(Cl-)을 분리시키고 1 ~ 30nm의 입방형 Pd나노입자인 팔라듐(Pd)원자가 생성된다. 곧 생성된 팔라듐(Pd)원자는 분자자기조립(응집)을 하면서 Pd나노구조체가 형성되어 생산 용기의 바닥으로 침전된다. 침전된 Pd내에는 염화팔라듐과 Pd나노구조체가 혼재되어 있게 된다. 여기서, 바닥으로 침전된 Pd나노구조체 또는 서서히 바닥으로 가라앉는 침전이 덜된 Pd나노구조체를 염화나트륨 용액과 분리하여 순수한 Pd나노구조체를 얻는다. 이때, 염화이온(Cl-)은 염소기체(Cl2)가 되어 날아가거나 염화나트륨(NaCl) 용액에 다시 들어가고, 상기 수소이온(H+)은 전자를 받아 수소기체(H2)가 된다. 여기서, 용액의 pH 조절이 대단히 중요한데, 이는 pH가 Pd나노 구조체의 응집형태와 관련이 크기 때문이다. 통상 pH 6~10에서 원활한 응집이 일어나는 것을 알 수 있다. 이때, 용액의 pH 조절은 전압과 전류를 조절하여 수소이온(H+)과 수산화이온(OH-)의 양을 조절하는 것으로서 pH가 조절된다.Pd and Cl metal salts of palladium chloride (PdCl 2 ) are formed by the hydrogen ions (H + ) generated around the cathode, and the chloride ions (Cl − ) are dropped. However, most of the stored hydrogen is released and the chloride ions (Cl − ) And palladium (Pd) atoms, which are cubic Pd nanoparticles of 1 to 30 nm, are produced. The resulting palladium (Pd) atoms undergo molecular self-assembly (aggregation) to form Pd nanostructures and settle to the bottom of the production vessel. In the precipitated Pd, palladium chloride and Pd nanostructures are mixed. Here, the Pd nanostructure precipitated to the bottom or the Pd nanostructure gradually precipitated to the bottom is separated from the sodium chloride solution to obtain a pure Pd nanostructure. At this time, the chloride ion (Cl − ) is a chlorine gas (Cl 2 ) to fly or re-enter the sodium chloride (NaCl) solution, the hydrogen ion (H + ) receives the electron becomes a hydrogen gas (H 2 ). Here, the pH control of the solution is very important because the pH is related to the aggregation form of the Pd nanostructure. It can be seen that smooth aggregation usually occurs at pH 6-10. In this case, pH adjustment of the solution has a hydrogen ion (H +) and hydroxide ions (OH -) to adjust the voltage and current, the pH is adjusted as to control the amount of.
특히 수소를 흡장한 Pd를 사용할 경우 수시간에 걸쳐 다량의 Pd나노구조체를 생산할 수 있는데 이는 수소를 흡장하지 않은 Pd를 사용할 경우 Pd나노구조체의 생산이 수분 이내에 멈추는 것과 비교하면 획기적이라 하지 않을 수 없다. Particularly, when Pd containing hydrogen is used, a large amount of Pd nanostructures can be produced over several hours. When Pd without hydrogen is used, production of Pd nanostructures can be inferior compared to stopping production within minutes. .
또한, 수소를 흡장하지 않은 Pd봉을 사용할 경우 침전된 Pd 내에는 염화팔라듐과 Pd나노구조체가 혼재되어 있으나 수소를 흡장한 Pd봉을 사용할 경우 순수한 Pd나노구조체를 얻을 수 있는 점도 큰 차이라 할 수 있다. In addition, when using Pd rods that do not occlude hydrogen, palladium chloride and Pd nanostructures are mixed in the precipitated Pd. However, when Pd rods that occupy hydrogen are used, pure Pd nanostructures can be obtained. have.
여기서, 상기 수소를 흡장한 Pd봉을 사용하여 전기분해에서 1 ~ 30nm의 입방형 나노입자인 100% 순도의 Pd나노입자를 생산하고, 생산된 Pd나노입자가 수소를 흡장함으로써 자기조립이 된 일정한 형상 즉 고리형으로 형상이 제어된 10 ~ 300nm의 크기를 갖는 고리형 Pd구조체로 된다.Here, the hydrogen-containing Pd rod produces 100% purity Pd nanoparticles, which are 1-30 nm cubic nanoparticles in electrolysis, and the Pd nanoparticles produced are self-assembled by occluding hydrogen. It has a cyclic Pd structure having a size of 10 to 300 nm whose shape is cyclically controlled.
또한, Pd나노구조체를 형상의 변화를 최소화하기 위하여 고정하는 과정을 수행할 수 있다. In addition, the process of fixing the Pd nanostructure to minimize the change in shape can be performed.
상기 고리형 Pd나노구조체는 온도 10℃~200℃로 유지하면서 압력 10~100기압으로 60분~120분 동안 산소를 제거한 분위기에서 처리하여 구조체의 형상이 고정된 것을 특징으로 한다.The cyclic Pd nanostructure is characterized in that the shape of the structure is fixed by treatment in an atmosphere from which oxygen is removed for 60 minutes to 120 minutes at a pressure of 10 to 100 atmospheres while maintaining the temperature 10 ℃ ~ 200 ℃.
이때, Pd가 PdO로 산화가 일어나지 않게 산소를 제거한 후 불활성기체인 아르곤과 질소등을 가하고 상기 압력을 가하여 상기 고리형 Pd나노 구조체의 형상을 고정한다. At this time, after removing oxygen to prevent oxidation of Pd into PdO, argon and nitrogen, which are inert gases, are added, and the pressure is applied to fix the shape of the cyclic Pd nanostructure.
즉, 생성된 나노구조체를 고정하기 위해서는 온도를 10℃~200℃로 유지한 채 압력 10~100기압으로 60~120분 동안 산소를 제거한 분위기에서 처리한다. That is, in order to fix the generated nanostructures, the temperature is maintained at 10 ° C. to 200 ° C., and then treated in an atmosphere from which oxygen is removed for 60 to 120 minutes at a pressure of 10 to 100 atm.
이렇게 처리된 Pd는 주로 고리형 Pd나노구조체로 형성이 된다.The treated Pd is mainly formed of a cyclic Pd nanostructure.
이렇게 생성된 나노구조체는 광민감성 촉매(photosensitivity catalyst)로 탁월한 효과가 있는 것으로 판명되었다.The nanostructures thus produced proved to have excellent effects as photosensitivity catalysts.
이 촉매의 구조체는 일반적으로 물을 산화 또는 환원시키는데 필요한 원칙적 에너지인 약 1.23eV 이상의 에너지를 가시광선 영역의 햇빛으로 증폭시킬 수 있는 구조체를 가지며 실험결과 단결정표면상에서 얻어졌던 많은 연구결과보다 실제로 더 높은 반응성과 선택성을 갖는 촉매가 됨을 알 수 있다.The structure of this catalyst generally has a structure capable of amplifying more than about 1.23 eV of energy, which is the principle energy required to oxidize or reduce water, to sunlight in the visible range, and is actually higher than many studies obtained on single crystal surfaces. It can be seen that it is a catalyst having reactivity and selectivity.
이렇게 형상이 제어된 나노입자의 독특한 촉매적 특성은 나노입자 간의 거리를 변화시킴으로써 광학적 특성을 조절할 수 있으며 나노입자의 큰 표면반응뿐만 아니라, 나노구조체가 가지는 양자점(Quantum dot) 에너지로 큰 반응을 나타낸다.The unique catalytic properties of the shape-controlled nanoparticles can control the optical properties by varying the distance between the nanoparticles, and show not only the large surface response of the nanoparticles, but also the quantum dot energy of the nanostructures. .
이 때문에 본 발명의 기술은 전 세계가 하고자 하는 인공 광시스 템(artifical photosystem)의 핵심기술이 될 수 있는 잠재력을 가지는 것이다.For this reason, the technology of the present invention has the potential to be the core technology of the artificial photosystem (artifical photosystem) that the world wants.
본 발명에 의하면 간단한 방법으로 큰 에너지를 증폭시킬 수 있는 Pd나노구조체를 생산할 수 있으며 이렇게 생성된 나노구조체로 유기화합물 분해실험을 실시하여 탁월한 성능을 입증하였다. According to the present invention, it is possible to produce a Pd nanostructure that can amplify a large energy by a simple method, and demonstrated the excellent performance by performing organic compound decomposition experiments with the nanostructures thus produced.
또한, 본 발명은 상기 고리형 Pd나노구조체를 포함하는 것을 특징으로 하는 휘발성 유기화합물 분해용 촉매를 제공한다.The present invention also provides a catalyst for decomposing volatile organic compounds comprising the cyclic Pd nanostructure.
또한, 본 발명은 상기 고리형 Pd나노구조체를 수질 또는 대기오염 배출억제 또는 방지시설에서 휘발성 유기화합물 분해용 촉매로서 사용하는 것을 특징으로 한다.In addition, the present invention is characterized in that the cyclic Pd nanostructures are used as catalysts for the decomposition of volatile organic compounds in water or air pollution emission suppression or prevention facilities.
이때, 수질 또는 대기오염 배출억제 또는 방지시설은 석유정제시설, 석유화학제품, 제조시설, 정유소, 주유소 또는 세탁시설을 포함한다.At this time, water or air pollution emission suppression or prevention facilities include petroleum refining facilities, petrochemical products, manufacturing facilities, refineries, gas stations or laundry facilities.
여기서, 휘발성 유기화합물(Volatile Organic Compounds; VOC)이란 탄소와 수소(CxHy)를 포함하는 유기화합물로 물리적으로 대기중에서는 0.02psi 이상의 증기압을 갖거나 끓는점이 100℃ 미만인 유기화합물로 대기중에 쉽게 증발된다.Here, volatile organic compounds (VOCs) are organic compounds containing carbon and hydrogen (CxHy), and are physically evaporated into the air as organic compounds having a vapor pressure of 0.02 psi or more in the air or having a boiling point of less than 100 ° C. .
휘발성 유기화합물(VOC)은 주로 도장, 인쇄, 세탁시설, 유기합성공업 및 석유정제공업 등에 사용되는 용제류에 많이 포함되어 있으며, 차량배기가스로도 발생되는 벤젠, 톨루엔, 크실렌 등과 같이 방향족 화합물들이다. 우리 생활주변에서 흔 하게 사용되는 유기물은 대부분 VOCs에 포함되며 이러한 VOC는 자연의 환경에서도 배출된다.Volatile organic compounds (VOCs) are mainly included in solvents used in painting, printing, laundry facilities, organic synthesis industry and petroleum refining industry, and are aromatic compounds such as benzene, toluene and xylene, which are also generated from vehicle exhaust gas. Most of the organic substances commonly used around our lives are contained in VOCs, which are also emitted in the natural environment.
이러한 VOCs는 각각의 성분이나 대기중 반응형태에 따라 대류권 오존오염, 성층권 파괴, 오존층파괴 및 지구 온난화 등 지구 환경파괴의 원인이 되며, 대류권오존, 산성비의 원인으로 산림피해에도 영향을 준다.These VOCs cause global environmental destruction such as tropospheric ozone pollution, stratospheric destruction, ozone layer destruction and global warming, depending on the individual components and reaction patterns in the atmosphere, and also affect forest damage due to tropospheric ozone and acid rain.
또한, 대기중에서 질소화합물과 함께 광화학 반응에 참여하며, 인체 및 동식물에 유해한 오존 등 2차오염 물질은 광화학 산화물을 형성하는 전구물질로 작용하여 각종질병의 원인 및 발암물질의 함유로 환경 및 건강에 영향을 끼치는 물질이다. 현재 휘발성유기화합물의 감소를 대기관리의 중요한 정책 수단으로 이용하는 국가가 증가하며 국내에는 관련 법규가 제정되어 VOC 처리의 규제가 강화되고 있다.In addition, it participates in photochemical reactions with nitrogen compounds in the atmosphere, and secondary pollutants such as ozone, which are harmful to humans and animals and plants, act as precursors to form photochemical oxides, causing various diseases and containing carcinogens. It is a substance that affects. At present, the number of countries using the reduction of volatile organic compounds as an important policy means of air management is increasing. In Korea, relevant regulations are enacted to strengthen the regulation of VOC treatment.
또한, 상기 고리형 Pd나노구조체 분석은 TEM(transmission electron microscope; 투과형 전자현미경), HREM(High-resolution transmission electron microscopy; 고 분해능 투과형 전자현미경), STEM(Scanning Transmission Electron Microscopy; 주사 투과 전자 현미경)로 분석하였다.In addition, the cyclic Pd nanostructure analysis may be performed using a transmission electron microscope (TEM), a high-resolution transmission electron microscopy (HREM), and a scanning transmission electron microscope (STEM). Analyzed.
도 2에 고리형 Pd나노구조체의 금속분말 시편의 TEM 분석 결과를 나타내었다.Figure 2 shows the results of TEM analysis of the metal powder specimen of the cyclic Pd nanostructures.
도 2와 같이, Pd나노입자가 붙어서 고리형을 형성하는 고리형 Pd나노구조체 의 크기는 10nm 정도이고 A 영역 (대부분의 영역)은 거의 Pd 원소로 구성된다.As shown in FIG. 2, the size of the cyclic Pd nanostructure to which the Pd nanoparticles are attached to form a ring is about 10 nm, and the A region (most regions) is almost composed of Pd elements.
도 3에 고리형 Pd나노구조체의 금속분말 시편의 STEM 분석 결과를 나타내었다.3 shows the results of STEM analysis of the metal powder specimen of the cyclic Pd nanostructure.
도 3은 Pd나노입자가 고리형 Pd나노구조체로 완전한 구조체를 형성한 것을 나타낸다. 즉, 도 3은 Pd나노입자의 면심입방격자(Face Centered Cubic; FCC)상으로 분석한 것으로서, 그 Pd나노입자는 순수 Pd 금속으로 그 결정구조가 거의 완벽하게 배열된 상태를 보여주는 주사투과전자현미경(scanning transmission electron microscopy;STEM) 사진이다. 여기서, 불빛이 링 모양으로 있는 것은 나노 입자 하나 하나가 정확하게 결정체가 되었다는 것을 보여준다.3 shows that the Pd nanoparticles form a complete structure with a cyclic Pd nanostructure. That is, Figure 3 is a face centered cubic (FCC) analysis of the Pd nanoparticles, the Pd nanoparticles are pure Pd metal scanning electron microscope showing the state that the crystal structure is almost perfectly arranged (scanning transmission electron microscopy; STEM). Here, the ringing of the light shows that every single nanoparticle is exactly a crystal.
도 4는 고리형 Pd나노구조체의 금속분말 시편의 HREM(High-resolution transmission electron microscopy; 고 분해능 투과형 전자현미경) 사진으로서 투과된 전자빔에 의한 대조이미지(contrast image)를 분석한 것을 나타낸다.FIG. 4 is a high-resolution transmission electron microscopy (HREM) photograph of a metal powder specimen of a cyclic Pd nanostructure, showing analysis of a contrast image by a transmitted electron beam.
도 4와 같이, 본 발명의 Pd나노구조체는 고리형임을 나타낸다.As shown in FIG. 4, the Pd nanostructure of the present invention is cyclic.
도 5는 고리형 Pd나노구조체의 금속분말 시편의 STEM(Scanning Transmission Electron Microscopy; 주사 투과 전자 현미경) 사진으로서 좌측 사진은 BF 즉, STEM의 명시야(z-contrast)이고, 우측 사진은 HAADF 즉, STEM의 암시야(z-contrast)를 나타내는 사진이다.FIG. 5 is a Scanning Transmission Electron Microscopy (STEM) picture of the metal powder specimen of the cyclic Pd nanostructure, the left picture is BF, that is, the Z-contrast of STEM, and the right picture is HAADF, The picture shows the z-contrast of STEM.
도 5와 같이, 본 발명의 Pd나노구조체는 고리형임을 나타낸다.As shown in FIG. 5, the Pd nanostructure of the present invention is cyclic.
이하, 본 발명을 실시예에 의해 상세히 설명한다. Hereinafter, the present invention will be described in detail by way of examples.
단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 의해 한정되는 것은 아니다.However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
실시예 1Example 1
Pd봉 250g을 2기압과 50℃의 온도의 수소 기체 분위기에서 Pd격자 사이로 수소를 주입하는 수소흡장을 하였다. 그런 다음, 수소기체가 흡장된 Pd봉 300g을 전극으로 사용하여 3% 농도의 염화나트륨 전해질 500g속에서 전극과 물을 전기분해하여 1 ~ 30nm의 입방형 나노입자인 100% 순도의 Pd나노입자를 150g 생산하였다. 이때, 전류와 전압은 0.01A~10A, 2V~40V 사이를 교대로 조절하여 pH를 8로 조절하여 양극에서는 염화이온(Cl-)이 팔라듐(Pd)과 결합하여 Pd와 Cl의 금속염인 염화팔라듐(PdCl2)을 380g 생성시켰다. 염화팔라듐(PdCl2)은 음극 주변에서 생성되는 수소이온(H+)에 의해 염화이온(Cl-)이 떨어지고 1 ~ 30nm의 입방형 Pd나노입자인 팔라듐(Pd)원자가 생성되었다. 곧 생성된 팔라듐(Pd)원자는 분자자기조립(응집)을 하면서 Pd나노구조체가 형성되어 생산 용기의 바닥으로 침전되었다. 바닥으로 침전된 Pd나노구조체 또는 서서히 바닥으로 가라앉는 침전이 덜된 Pd나노구조체를 염화나트륨 용액과 분리하여 수소이온농도를 조절하여 생산된 Pd나노입자가 자기조립이 된 일정한 형상 즉 고리형으로 형상이 제어된 10 ~ 300nm의 크기를 갖는 고리형 Pd구조체를 90g 생산하였다.250 g of Pd rods were hydrogenated to inject hydrogen between Pd grids in a hydrogen gas atmosphere at a temperature of 2 atmospheres and a temperature of 50 ° C. Then, using 300g of hydrogen-containing Pd rod as electrode, electrolysis of electrode and water in 500g of 3% sodium chloride electrolyte, 150g of 100% pure Pd nanoparticles, 1 ~ 30nm cubic nanoparticles Produced. At this time, the current and voltage are alternately adjusted between 0.01A ~ 10A and 2V ~ 40V to adjust the pH to 8. At the positive electrode, chloride ion (Cl − ) is combined with palladium (Pd), which is a metal salt of Pd and Cl. 380 g of (PdCl 2 ) was produced. The palladium chloride (PdCl 2 ) is ions (Cl − ) drop by the hydrogen ions (H + ) generated around the cathode and a palladium (Pd) atom, a cubic Pd nanoparticle of 1 to 30nm was produced. The resulting palladium (Pd) atoms were molecularly assembled (aggregated) to form Pd nanostructures and settled to the bottom of the production vessel. The Pd nanostructures precipitated to the bottom or Pd nanostructures gradually settled to the bottom are separated from the sodium chloride solution to control the hydrogen ion concentration, and the Pd nanoparticles produced by self-assembly are uniformly shaped, that is, the shape is controlled. 90 g of a cyclic Pd structure having a size of 10 to 300 nm was produced.
실시예 2Example 2
실시예 1에서 생산된 고리형 Pd나노구조체를 이용하여 휘발성 유기화합물 분해시험을 실시하였다. 먼저 3cmⅹ7cm 일반 종이위에 상기 고리형 Pd나노구조체를 0.01mm 코팅을 하여 고리형 Pd 나노코팅종이를 형성하였다.Volatile organic compound decomposition test was carried out using the cyclic Pd nanostructure produced in Example 1. First, cyclic Pd nano-coated paper was formed by coating 0.01 mm of the cyclic Pd nanostructure on a 3 cmⅹ7 cm plain paper.
그런 다음, 200cc 밀폐유리용기에 벤젠을 0.5cc 넣고 여기에 상기 고리형 Pd 나노코팅종이를 넣었다.Then, 0.5 cc of benzene was put in a 200 cc hermetic glass container, and the cyclic Pd nano-coated paper was put therein.
그 후, 상기 용기를 태양광, 광반응기, 실내에서 수시간 ~ 수십시간 노출시켜 휘발성 유기화합물 분해 정도를 측정하여 하기 그래프 1 내지 그래프 3을 얻었다.Thereafter, the vessel was exposed to sunlight, a photoreactor, and indoors for several hours to several tens of hours to measure the degree of decomposition of volatile organic compounds, thereby obtaining Graphs 1 to 3 below.
실시예 3Example 3
실시예 1에서 생산된 고리형 Pd나노구조체를 이용하여 휘발성 유기화합물 분해시험을 실시하였다. 먼저 3cmⅹ7cm 일반 종이위에 상기 고리형 Pd나노구조체를 0.01mm 코팅을 하여 고리형 Pd 나노코팅종이를 형성하였다.Volatile organic compound decomposition test was carried out using the cyclic Pd nanostructure produced in Example 1. First, cyclic Pd nano-coated paper was formed by coating 0.01 mm of the cyclic Pd nanostructure on a 3 cmⅹ7 cm plain paper.
그런 다음, 200cc 밀폐유리용기에 톨루엔을 0.5cc 넣고 여기에 상기 고리형 Pd 나노코팅종이를 넣었다.Then, 0.5 cc of toluene was put in a 200 cc hermetic glass container, and the cyclic Pd nano-coated paper was put therein.
그 후, 상기 용기를 태양광, 광반응기, 실내에서 수시간 ~ 수십시간 노출시 켜 휘발성 유기화합물 분해 정도를 측정하여 하기 그래프 1 내지 그래프 3을 얻었다.Thereafter, the vessel was exposed to sunlight, a photoreactor, and indoors for several hours to several tens of hours to measure the degree of decomposition of volatile organic compounds, thereby obtaining Graphs 1 to 3 below.
비교예 1Comparative Example 1
200cc 밀폐유리용기에 벤젠을 0.5cc 넣고 여기에 Pd나노구조체를 코팅하지 않은 종이를 넣었다.0.5cc of benzene was placed in a 200cc sealed glass container, and a Pd nanostructure-coated paper was put therein.
그 후, 상기 용기를 태양광, 광반응기, 실내에서 수시간 ~ 수십시간 노출시켜 휘발성 유기화합물 분해 정도를 측정하여 하기 그래프 1 내지 그래프 3을 얻었다.Thereafter, the vessel was exposed to sunlight, a photoreactor, and indoors for several hours to several tens of hours to measure the degree of decomposition of volatile organic compounds, thereby obtaining Graphs 1 to 3 below.
비교예 2Comparative Example 2
200cc 밀폐유리용기에 톨루엔을 0.5cc 넣고 여기에 Pd나노구조체를 코팅하지 않은 종이를 넣었다.0.5 cc of toluene was put into a 200 cc sealed glass container, and paper without Pd nanostructure was put therein.
그 후, 상기 용기를 태양광, 광반응기, 실내에서 수시간 ~ 수십시간 노출시켜 휘발성 유기화합물 분해 정도를 측정하여 하기 그래프 1 내지 그래프 3을 얻었다.Thereafter, the vessel was exposed to sunlight, a photoreactor, and indoors for several hours to several tens of hours to measure the degree of decomposition of volatile organic compounds, thereby obtaining Graphs 1 to 3 below.
실험예 1 Experimental Example 1
휘발성 유기화합물 분해 실험의 분석Analysis of Volatile Organic Compound Degradation Experiments
상기 실시예 2 또는 실시예 3, 비교예 1 내지 비교예 2의 휘발성 유기화합물 분해 실험의 분석에는 Agilent GC 6890이 사용되었다.Agilent GC 6890 was used to analyze the decomposition of the volatile organic compounds of Example 2 or Example 3 and Comparative Examples 1 to 2.
실험결과Experiment result
그래프 1Graph 1
그래프 2Graph 2
그래프 3Graph 3
벤젠, 톨루엔으로 실험해 본 결과 휘발성 유기화합물(VOC)을 고리형 Pd나노구조체가 분해할 수 있는 것으로 나타났으며 분해속도는 태양광 > 광반응기> 실내의 순으로 감소하는 것으로 나타났다.Experiments with benzene and toluene showed that the volatile Pd nanostructures could decompose volatile organic compounds (VOC), and the degradation rate decreased in the order of solar> photoreactor> room.
이상의 설명은 본 발명의 기술 사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.
도 1은 본 발명에 의해 제조된 고리형 Pd나노입자구조체의 주사투과전자현미경(scanning transmission electron microscopy;STEM) 사진이다.1 is a scanning transmission electron microscopy (STEM) photograph of the cyclic Pd nanoparticle structure prepared by the present invention.
도 2는 고리형 Pd나노구조체의 금속분말 시편의 TEM 분석 결과를 나타낸 사진이다.Figure 2 is a photograph showing the results of TEM analysis of the metal powder specimen of the cyclic Pd nanostructures.
도 3은 고리형 Pd나노구조체의 금속분말 시편의 결정구조가 거의 완벽하게 배열된 상태를 나타내는 STEM 분석 결과를 나타낸 사진이다.3 is a photograph showing the results of STEM analysis showing a state in which the crystal structures of the metal powder specimens of the cyclic Pd nanostructure are almost perfectly arranged.
도 4는 고리형 Pd나노구조체의 금속분말 시편의 HREM(High-resolution transmission electron microscopy; 고 분해능 투과형 전자현미경) 사진으로서 투과된 전자빔에 의한 대조이미지(contrast image)를 분석한 것을 나타낸다.FIG. 4 is a high-resolution transmission electron microscopy (HREM) photograph of a metal powder specimen of a cyclic Pd nanostructure, showing analysis of a contrast image by a transmitted electron beam.
도 5는 고리형 Pd나노구조체의 금속분말 시편의 STEM(Scanning Transmission Electron Microscopy; 주사 투과 전자 현미경) 사진으로서 좌측 사진은 BF 즉, STEM의 명시야(z-contrast)이고, 우측 사진은 HAADF 즉, STEM의 암시야(z-contrast)를 나타내는 사진이다.FIG. 5 is a Scanning Transmission Electron Microscopy (STEM) picture of the metal powder specimen of the cyclic Pd nanostructure, the left picture is BF, that is, the Z-contrast of STEM, and the right picture is HAADF, The picture shows the z-contrast of STEM.
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