KR20240046324A - Re-stacked hybrid nanosheets and method for preparing the same - Google Patents
Re-stacked hybrid nanosheets and method for preparing the same Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 177
- 238000000034 method Methods 0.000 title claims description 14
- 239000002356 single layer Substances 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052741 iridium Inorganic materials 0.000 abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
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- 238000004458 analytical method Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 6
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- 238000011160 research Methods 0.000 description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000012153 distilled water Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- 239000010970 precious metal Substances 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 238000000733 zeta-potential measurement Methods 0.000 description 1
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Abstract
본 발명은 박리된 2차원 단일층의 나노시트 간의 재조합을 통한 혼성나노시트의 다공성 및 표면활성자리의 극대화로 비표면적을 현격히 향상시킬 수 있고 이를 통해 현격히 우수한 촉매 효율을 달성할 수 있어서 종래 상용화된 촉매로서의 루테늄/이리듐계 귀금속물질을 대체할 수 있는 전기화학촉매를 제조할 수 있다.The present invention can significantly improve the specific surface area by maximizing the porosity and surface active sites of hybrid nanosheets through recombination between exfoliated two-dimensional single-layer nanosheets, and through this, significantly superior catalytic efficiency can be achieved. It is possible to manufacture an electrochemical catalyst that can replace ruthenium/iridium-based noble metal materials as catalysts.
Description
본 발명은 재적층된 혼성나노시트 및 이의 제조방법에 관한 것으로, 보다 상세하게는 박리된 나노시트의 재조합을 통한 나노시트의 다공성 및 표면활성자리의 극대화로 인해 현격히 우수한 촉매 효율을 달성할 수 있어서 종래 상용화된 촉매로서의 루테늄/이리듐계 귀금속물질을 대체할 수 있는 재적층된 혼성나노시트 및 이의 제조방법에 관한 것이다.The present invention relates to restacked hybrid nanosheets and a method for manufacturing the same. More specifically, it is possible to achieve significantly superior catalytic efficiency by maximizing the porosity and surface active sites of the nanosheet through recombination of exfoliated nanosheets. The present invention relates to a restacked hybrid nanosheet that can replace ruthenium/iridium noble metal materials as conventionally commercialized catalysts and a method for manufacturing the same.
최근 화석연료의 고갈과 환경오염으로 인해 이를 해결하기 위한 신재생에너지분야 연구가 많이 진행이 되고 있다. 그 중에서도 물 전해조 및 금속 공기전지를 포함한 다양한 에너지 저장/생산 장치가 미래의 에너지장치로 주목 받고 있다. 그러나 이러한 장치를 효과적으로 사용하기 위해서는 촉매물질이 필요한데 현재 상용화 되고 있는 촉매물질은 자원이 한정되어 있으며 고가의 이리듐/루테늄과 같은 귀금속계 물질이 사용되고 있다. 이에 따라 귀금속 촉매를 대체하기 위해서 경제성과 더불어 높은 촉매활성 및 안정성을 가지는 효율적인 촉매물질에 대한 연구가 시급하다. 이와 같은 노력의 일환으로 최근 저렴하면서도 자원이 풍부한 이중층 수산화물 구조체(Layered Double Hydroxide; LDH)가 특히 주목받고 있다.Recently, due to the depletion of fossil fuels and environmental pollution, a lot of research is being conducted in the field of new and renewable energy to solve this problem. Among them, various energy storage/production devices, including water electrolyzers and metal-air batteries, are attracting attention as future energy devices. However, in order to use these devices effectively, catalyst materials are needed. Currently commercialized catalyst materials have limited resources and expensive precious metal materials such as iridium/ruthenium are used. Accordingly, in order to replace precious metal catalysts, research on efficient catalyst materials that are economical and have high catalytic activity and stability is urgently needed. As part of such efforts, layered double hydroxide (LDH), which is inexpensive and resource-rich, has recently received particular attention.
이중층 수산화물 구조체는 하이드로탈사이트(Hydrotalcite)형 물질로도 알려져 있으며 평면 구조의 음이온성 점토의 한 종류로서 양이온 층과 이온교환이 가능한 음이온의 이중층으로 구성되어 있다. 최근 LDH 구조체가 다양한 종류의 금속의 도입과 조성의 변화가 가능하여 흡착제와 불균일계 촉매 및 전 구체로의 활용 방안이 대두되어 큰 주목을 받고 있다. The double-layer hydroxide structure, also known as hydrotalcite-type material, is a type of anionic clay with a flat structure and consists of a double layer of anions capable of ion exchange with a cation layer. Recently, the LDH structure has received great attention as it allows the introduction of various types of metals and changes in composition, and its use as an adsorbent, heterogeneous catalyst, and precursor has emerged.
다만, 이와 같은 이중층 수산화물 구조체는 저렴한 가격과 우수한 촉매활성을 가지는 것은 별론으로, 낮은 전기전도도로 인해 촉매활성을 극대화하고 안정성을 유지하는데에는 한계가 있어서 실제 고가의 귀금속 촉매를 대체하기에는 제한이 있다. However, apart from being inexpensive and having excellent catalytic activity, such a double-layer hydroxide structure has limitations in maximizing catalytic activity and maintaining stability due to low electrical conductivity, making it difficult to replace expensive noble metal catalysts.
이에 따라, 이중층 수산화물 구조체의 안정성과 촉매활성을 보완하고 이중층 수산화물 구조체가 가지고 있는 내재적인 장점을 극대화함으로써 이중층 수산화물 구조체의 특성을 충분히 이용할 수 있도록 상술한 문제점을 개선하여 촉매로서의 활용도를 극대화시킬 수 있는 연구가 시급한 실정이다.Accordingly, by improving the stability and catalytic activity of the double-layer hydroxide structure and maximizing the inherent advantages of the double-layer hydroxide structure, the above-mentioned problems can be improved to fully utilize the characteristics of the double-layer hydroxide structure, thereby maximizing its utility as a catalyst. Research is urgently needed.
본 발명은 상술한 문제를 극복하기 위해 안출된 것으로, 본 발명의 해결하고자 하는 과제는 박리된 2차원 단일층의 나노시트 간의 재조합을 통한 혼성나노시트의 다공성 및 표면활성자리의 극대화로 비표면적을 현격히 향상시킬 수 있는 재적층된 혼성나노시트 및 이의 제조방법을 제공하는 것이다.The present invention was developed to overcome the above-mentioned problems, and the problem to be solved by the present invention is to increase the specific surface area by maximizing the porosity and surface active sites of the hybrid nanosheet through recombination between the exfoliated two-dimensional single-layer nanosheets. The aim is to provide restacked hybrid nanosheets and a manufacturing method thereof that can be significantly improved.
또한 본 발명은 이를 통해 현격히 우수한 촉매 효율을 달성할 수 있어서 종래 상용화된 촉매로서의 루테늄/이리듐계 귀금속물질을 대체할 수 있는 전기화학촉매를 제공하는 것이다.In addition, the present invention provides an electrochemical catalyst that can achieve significantly superior catalytic efficiency and can replace ruthenium/iridium noble metal materials as conventionally commercialized catalysts.
본 발명은 상술한 과제를 해결하기 박리화된 단일층의 이중층 수산화물 (Layered Double Hydroxide, LDH) 나노시트를 제조하는 제1단계, 박리화된 단일층의 전도성 금속 탄화물 나노시트를 제조하는 제2단계 및 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트를 혼성화하는 제3단계를 포함하는 재적층된 혼성나노시트의 제조방법을 제공한다The present invention solves the above-described problems by providing a first step of manufacturing a exfoliated single-layer layered double hydroxide (LDH) nanosheet and a second step of manufacturing an exfoliated single-layer conductive metal carbide nanosheet. and a third step of hybridizing the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet.
또한, 본 발명의 일 실시예에 의하면 상기 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트는, 박리화된 단일층의 CoFe-LDH 나노시트인 것을 특징으로 할 수 있다.Additionally, according to one embodiment of the present invention, the exfoliated single-layer double-layer hydroxide nanosheet of the first step may be characterized as an exfoliated single-layer CoFe-LDH nanosheet.
또한, 상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트는, MXene 나노시트인 것을 특징으로 할 수 있다.Additionally, the exfoliated single-layer conductive metal carbide nanosheet in the second step may be an MXene nanosheet.
또한, 상기 제3단계는 정전기적 인력으로 재조합하여 재적층함으로써 혼성나노시트의 다공성이 극대화되는 것을 특징으로 할 수 있다.In addition, the third step may be characterized by maximizing the porosity of the hybrid nanosheets by recombining and re-stacking using electrostatic attraction.
또한, 상기 제3단계는 상기 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트가 1: 0.01 내지 0.1의 중량비로 혼성화되는 것을 특징으로 할 수 있다.Additionally, the third step may be characterized in that the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet are hybridized at a weight ratio of 1:0.01 to 0.1.
또한, 상기 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트는 +30mV ~ +50mV의 양전하를 띠고, 상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트는 -43mV ~ -63mV의 음전하를 띠며, 상기 제3단계에서 전하평형을 맞추기 위하여 Na2CO3를 첨가하는 것을 특징으로 할 수 있다.In addition, the exfoliated single-layer double-layer hydroxide nanosheet of the first step has a positive charge of +30mV to +50mV, and the exfoliated single-layer conductive metal carbide nanosheet of the second step has a positive charge of -43mV to -63mV. It has a negative charge, and in the third step, Na 2 CO 3 may be added to balance the charge.
또한, 본 발명은 박리화된 단일층의 이중층 수산화물 (Layered Double Hydroxide, LDH) 나노시트 및 박리화된 단일층의 전도성 금속 탄화물 나노시트가 정전기적 인력으로 재적층된 혼성나노시트를 제공한다.In addition, the present invention provides a hybrid nanosheet in which exfoliated single-layer layered double hydroxide (LDH) nanosheets and exfoliated single-layer conductive metal carbide nanosheets are re-stacked by electrostatic attraction.
또한, 본 발명의 일 실시예에 의하면 상기 박리화된 단일층의 이중층 수산화물 나노시트의 두께는 0.5 ~ 1.0 nm이며, 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트의 두께는 1.0 ~ 1.6 nm인 것을 특징으로 할 수 있다.In addition, according to one embodiment of the present invention, the thickness of the exfoliated single-layer double-layer hydroxide nanosheet is 0.5 to 1.0 nm, and the thickness of the exfoliated single-layer conductive metal carbide nanosheet is 1.0 to 1.6 nm. It can be characterized as:
또한, 상기 박리화된 단일층의 이중층 수산화물 나노시트는 CoFe-LDH 나노시트이며, 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트는 MXene 나노시트인 것을 특징으로 할 수 있다.In addition, the exfoliated single-layer double-layer hydroxide nanosheet may be a CoFe-LDH nanosheet, and the exfoliated single-layer conductive metal carbide nanosheet may be an MXene nanosheet.
또한, 본 발명은 상술한 재적층된 혼성나노시트를 포함하는 전기화학촉매를 제공한다.Additionally, the present invention provides an electrochemical catalyst comprising the above-described restacked hybrid nanosheets.
본 발명은 박리된 2차원 단일층의 나노시트 간의 재조합을 통한 혼성나노시트의 다공성 및 표면활성자리의 극대화로 비표면적을 현격히 향상시킬 수 있고 이를 통해 현격히 우수한 촉매 효율을 달성할 수 있어서 종래 상용화된 촉매로서의 루테늄/이리듐계 귀금속물질을 대체할 수 있는 전기화학촉매를 제조할 수 있다.The present invention can significantly improve the specific surface area by maximizing the porosity and surface active sites of hybrid nanosheets through recombination between exfoliated two-dimensional single-layer nanosheets, and through this, significantly superior catalytic efficiency can be achieved. It is possible to manufacture an electrochemical catalyst that can replace ruthenium/iridium-based noble metal materials as catalysts.
도 1은 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 비표면적 분석실험을 나타내는 그래프이다.
도 2는 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 전자주사현미경이미지이다.
도 3은 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 투과전자현미경-원소매핑 데이터이다.
도 4는 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 이미지 및 전위 데이터이다.
도 5는 본 발명의 일 실시예에 따라 박리화된 나노시트들의 AFM 이미지이다.
도 6운 발명의 일 실시예에 따른 재적층된 혼성나노시트의 oxygen evolution reaction (OER) 실험 결과를 나타내는 그래프이다.Figure 1 is a graph showing a specific surface area analysis experiment of restacked hybrid nanosheets according to an embodiment of the present invention.
Figure 2 is a scanning electron microscope image of restacked hybrid nanosheets according to an embodiment of the present invention.
Figure 3 shows transmission electron microscopy-element mapping data of restacked hybrid nanosheets according to an embodiment of the present invention.
Figure 4 shows images and potential data of restacked hybrid nanosheets according to an embodiment of the present invention.
Figure 5 is an AFM image of nanosheets exfoliated according to an embodiment of the present invention.
Figure 6 is a graph showing the results of an oxygen evolution reaction (OER) experiment of restacked hybrid nanosheets according to an embodiment of the invention.
이하 본 발명의 실시예에 대하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in many different forms and is not limited to the embodiments described herein.
상술한 것과 같이 종래 이중층 수산화물 구조체를 이용한 촉매는 안정성 문제와 촉매효율을 극대화시킬 수 없는 문제 등이 있어 실제 활용에 제한이 있다.As described above, catalysts using conventional double-layer hydroxide structures have stability problems and the inability to maximize catalytic efficiency, which limits their practical use.
이에 따라, 본 발명은 박리화된 단일층의 이중층 수산화물 (Layered Double Hydroxide, LDH) 나노시트를 제조하는 제1단계, 박리화된 단일층의 전도성 금속 탄화물 나노시트를 제조하는 제2단계 및 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트를 혼성화하는 제3단계를 포함하는 재적층된 혼성나노시트의 제조방법을 제공하여 상술한 문제의 해결을 모색하였다.Accordingly, the present invention includes a first step of producing an exfoliated single-layer layered double hydroxide (LDH) nanosheet, a second step of producing an exfoliated single-layer conductive metal carbide nanosheet, and exfoliation. A solution to the above-described problem was sought by providing a method for manufacturing restacked hybrid nanosheets, which includes a third step of hybridizing the single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet. .
이를 통해, 본 발명은 박리된 2차원 단일층의 나노시트 간의 재조합을 통한 혼성나노시트의 다공성 및 표면활성자리의 극대화로 비표면적을 현격히 향상시킬 수 있고 이를 통해 현격히 우수한 촉매 효율을 달성할 수 있어서 종래 상용화된 촉매로서의 루테늄/이리듐계 귀금속물질을 대체하여 산업적/경제적 활용도를 극대화시킬 수 있다.Through this, the present invention can significantly improve the specific surface area by maximizing the porosity and surface active sites of the hybrid nanosheet through recombination between the exfoliated two-dimensional single-layer nanosheets, and through this, significantly excellent catalytic efficiency can be achieved. Industrial/economic utility can be maximized by replacing ruthenium/iridium-based precious metal materials as conventionally commercialized catalysts.
이하 도면을 참조하여 본 발명에 따른 재적층된 혼성나노시트의 제조방법에 대해 설명한다.Hereinafter, a method for manufacturing restacked hybrid nanosheets according to the present invention will be described with reference to the drawings.
본 발명에 따른 재적층된 혼성나노시트의 제조방법 제1단계는 박리화된 단일층의 이중층 수산화물 (Layered Double Hydroxide, LDH) 나노시트를 제조하는 단계이다.The first step of the method for manufacturing restacked hybrid nanosheets according to the present invention is the step of manufacturing exfoliated single-layer layered double hydroxide (LDH) nanosheets.
상기 이중층 수산화물 구조체는 하이드로탈사이트(Hydrotalcite)형 물질로도 알려져 있으며 평면 구조의 음이온성 점토의 한 종류로서 양이온 층과 이온교환이 가능한 음이온의 이중층으로 구성되어 있다. 최근 LDH 구조체가 다양한 종류의 금속의 도입과 조성의 변화가 가능하여 흡착제와 불균일계 촉매 및 전 구체로의 활용 방안이 대두되어 큰 주목을 받고 있다. 이에 본 발명은 상기 이중층 수산화물 구조체로 본 발명의 목적에 부합하는 공지의 통상적인 물질이 사용될 수 있으며, 예를 들어 CuFe, NiCo, NiFe, ZnFe, NiAl, CoAl, MgAl, CuCr, ZnCr 로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있고 보다 바람직하게는 이중층 수산화물 구조체로서 CoFe-LDH를 사용할 수 있다.The double-layer hydroxide structure, also known as hydrotalcite-type material, is a type of anionic clay with a flat structure and is composed of a double layer of anions capable of ion exchange with a cation layer. Recently, the LDH structure has received great attention as it allows the introduction of various types of metals and changes in composition, and its use as an adsorbent, heterogeneous catalyst, and precursor has emerged. Accordingly, in the present invention, known and common materials suitable for the purpose of the present invention can be used as the double-layer hydroxide structure, for example, from the group consisting of CuFe, NiCo, NiFe, ZnFe, NiAl, CoAl, MgAl, CuCr, and ZnCr. Any one selected can be used, and more preferably, CoFe-LDH can be used as the double layer hydroxide structure.
종래 대부분의 이중층 수산화물 구조체를 이용한 촉매물질 개발연구에서는 이중층 수산화물 구조체를 결정성장시키는 방법으로 합성하여 이중층 수산화물 구조체가 매우 두껍게 쌓였으며 그 성능향상에 한계가 있었다. 이에 본 발명은 상기 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트를 후술할 전도성 금속탄화물 나노시트에 혼성화물질로 사용함으로써 정전기적으로 재조합하여 다공성이 훨씬 극대화된 촉매물질을 합성함으로써 종래 촉매 효율의 한계를 극복할 수 있다.In most of the conventional research on the development of catalyst materials using double-layer hydroxide structures, the double-layer hydroxide structures were synthesized by crystal growth, so the double-layer hydroxide structures were stacked very thickly, and there was a limit to improving performance. Accordingly, the present invention uses the exfoliated single-layer double-layer hydroxide nanosheet of the first step as a hybridization material with a conductive metal carbide nanosheet to be described later, thereby electrostatically recombining to synthesize a catalyst material with greatly maximized porosity, compared to conventional catalysts. Limitations in efficiency can be overcome.
보다 구체적으로 도 1을 참조하면, 질소 흡탈착 비표면적 분석 결과를 통해 본 발명에 따른 재적층된 혼성나노시트는 박리화된 단일층의 이중층 수산화물 나노시트 대비 더 큰 비표면적을 갖는 것을 알 수 있다. 상기 제1단계에서 제조한 이중층 수산화물 나노시트에 후술할 제2단계의 전도성 금속탄화물 나노시트를 혼성화 하면서 이중층 수산화물 구조체 간의 적층을 최소화시켜 다공성이 극대화되기 때문이다.More specifically, referring to Figure 1, the nitrogen adsorption/desorption specific surface area analysis results show that the restacked hybrid nanosheets according to the present invention have a larger specific surface area compared to the exfoliated single-layer double-layer hydroxide nanosheets. . This is because porosity is maximized by minimizing stacking between the double-layer hydroxide structures while hybridizing the conductive metal carbide nanosheet of the second step, which will be described later, to the double-layer hydroxide nanosheet prepared in the first step.
이를 위해 상기 제1단계의 이중층 수산화물 나노시트의 제조는, 본 발명의 목적에 부합하는 한 공지의 통상적인 제법을 통해 제조할 수 있다. 예를 들어 본 발명의 바람직한 실시예에 따라 상기 이중층 수산화물 나노시트가 CoFe-LDH 나노시트인 경우 Co(NO3)2·6H2O 및 Fe(NO3)3·9H2O과 증류수 그리고 formamide 용액이 들어 있는 혼합 용액에 NaOH 용액과 metal nitrate 용액을 반응시켜 원심분리를 이용하여 고체만 얻고 상기 고체를 과량의 증류수를 이용하여 세척 과정을 거친 후 분산시켜 박리화된 LDH 나노시트를 제조할 수 있다.To this end, the double-layer hydroxide nanosheet in the first step can be manufactured through a known conventional manufacturing method as long as it meets the purpose of the present invention. For example, according to a preferred embodiment of the present invention, when the double-layer hydroxide nanosheet is a CoFe-LDH nanosheet, Co(NO 3 ) 2 ·6H 2 O and Fe(NO 3 ) 3 ·9H 2 O, distilled water, and formamide solution NaOH solution and metal nitrate solution are reacted in the mixed solution containing this to obtain only a solid using centrifugation. The solid can be washed with an excess of distilled water and then dispersed to produce exfoliated LDH nanosheets. .
다음, 본 발명에 따른 재적층된 혼성나노시트의 제조 방법 제2단계는 박리화된 단일층의 전도성 금속 탄화물 나노시트를 제조하는 단계이다.Next, the second step of the method for manufacturing restacked hybrid nanosheets according to the present invention is the step of manufacturing exfoliated single-layer conductive metal carbide nanosheets.
상기 전도성 금속 탄화물 상술한 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트를 혼성화물질로 하여 전기화학적 촉매로 활용될 수 있는 촉매활성을 가지는 물질을 사용할 수 있으며, 바람직하게 상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트는 박리화된 단일층의 MXene 나노시트일 수 있다.A material having catalytic activity that can be used as an electrochemical catalyst can be used as a hybridization material using the conductive metal carbide and the exfoliated single-layer double-layer hydroxide nanosheet of the first step described above, preferably in the second step. The exfoliated single-layer conductive metal carbide nanosheets may be exfoliated single-layer MXene nanosheets.
상기 MXene은 Mn+1AXn (n은 1 내지 3)상으로부터 얻어지는 2차원 물질로, 여기서 M은 3족부터 7족 사이의 전이금속일 수 있고, A는 13 또는 14족 원소일 수 있으며, X는 탄소 또는 질소를 의미할 수 있다. 이와 같은 MXene은 구조적으로 층을 이룬 hexagonal 형태로 M 층은 A 그룹의 원자층과 교차적으로 배치되어 있고 X 원자는 이들 사이를 정팔면체 형태로 채우고 있다. 이때, Mn+1Xn은 공유결합으로 강하게 결합되어 있는 반면, A 층은 상대적으로 약한 금속 결합이므로 다른 물질과 반응성이 높은 특징이 있다.The MXene is a two-dimensional material obtained from the M n+1 AX n (n is 1 to 3) phase, where M may be a transition metal from Group 3 to Group 7, and A may be a Group 13 or 14 element. , X may mean carbon or nitrogen. Such MXene is structurally layered in a hexagonal form, where the M layer is arranged alternately with the atomic layer of the A group, and the X atoms fill the space between them in the form of a regular octahedron. At this time, M n+ 1
이를 위해 상기 제2단계의 박리화된 단일층의 MXene 나노시트는 본 발명의 목적에 부합하는 통상적인 Mn+1AXn (n은 1 내지 3)형태로 표현되는 MXene 나노시트 전구체를 사용할 수 있으며, 보다 바람직하게는 티타늄 카바이드(Ti3C2Tx)나노시트 전구체를 사용할 수 있다. For this purpose, the exfoliated single-layer MXene nanosheet of the second step can use an MXene nanosheet precursor expressed in the form of a typical M n + 1 AX n (n is 1 to 3) that meets the purpose of the present invention. And, more preferably, titanium carbide (Ti 3 C 2 T x ) nanosheet precursor can be used.
본 발명의 바람직한 실시예에 따라 상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트가 박리화된 단일층의 티타늄 카바이드(Ti3C2Tx) 나노시트일 경우, 불소 에칭 공정을 이용한 티타늄 카바이드 나노시트 제조방법이 일반적으로 이용될 수 있다. 예를 들어, 티타늄 카바이드 나노시트를 제조하기 위해, Ti3AlC 전구체 물질 층간에 존재하는 Al을 염산, 불산 등을 포함하는 혼합용액에 넣고 10 내지 50℃에서 2 내지 48 시간동안 교반할 수 있다. 이후 반응한 샘플은 pH가 6 내지 7이 되도록 과량의 물로 씻어낸 후 얻은 샘플은 염소를 포함하는 물질(LiCl) 등과 2 내지 48시간 동안 반응을 시키고 다시 과량이 물로 워싱하고 상등액을 취함으로써 박리화된 단일층의 티타늄 카바이드를 제조할 수 있다.According to a preferred embodiment of the present invention, when the exfoliated single-layer conductive metal carbide nanosheet of the second step is an exfoliated single-layer titanium carbide (Ti 3 C 2 T x ) nanosheet, a fluorine etching process is performed. The titanium carbide nanosheet manufacturing method used can be generally used. For example, to manufacture titanium carbide nanosheets, Al present between layers of Ti 3 AlC precursor material may be added to a mixed solution containing hydrochloric acid, hydrofluoric acid, etc. and stirred at 10 to 50° C. for 2 to 48 hours. Afterwards, the reacted sample was washed with an excess of water so that the pH reached 6 to 7. The sample was reacted with a chlorine-containing substance (LiCl) for 2 to 48 hours, washed again with water, and the supernatant was taken to remove the sample. A single layer of titanium carbide can be manufactured.
다음, 본 발명에 따른 재적층된 혼성나노시트의 제조 방법 제3단계는 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트를 혼성화하는 단계이다.Next, the third step of the method for producing restacked hybrid nanosheets according to the present invention is a step of hybridizing the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet.
상술한 것과 같이 종래 대부분의 이중층 수산화물 구조체를 이용한 촉매물질 개발연구에서는 이중층 수산화물 구조체를 나노시트 등에 결정성장시키는 방법으로 합성하기 때문에 이중층 수산화물 구조체의 두께를 용이하게 제어할 수 없고, 이로 인한 촉매 효율 향상에 제한에 있다.As mentioned above, in most conventional catalyst material development studies using double-layer hydroxide structures, the thickness of the double-layer hydroxide structure cannot be easily controlled because the double-layer hydroxide structure is synthesized by growing crystals in nanosheets, etc., which results in improved catalyst efficiency. There is a limit to
그러나 본 발명은 단일층 간의 혼성화, 즉 본 발명에 따른 재적층된 혼성나노시트의 제조방법 제3단계를 통해 상기 박리화된 단일층의 서로 다른 나노시트를 정전기적 인력으로 재적층함으로써 혼성나노시트의 다공성이 극대화시킬 수 있고, 비표면적을 크게 향상시킴으로써 종래 이중층 수산화물 구조체를 이용한 연구의 한계를 극복할 수 있다.However, the present invention hybridizes between single layers, that is, hybrid nanosheets are made by re-stacking different nanosheets of the exfoliated single layer by electrostatic attraction through the third step of the manufacturing method of restacked hybrid nanosheets according to the present invention. The porosity can be maximized, and the specific surface area can be greatly improved, thereby overcoming the limitations of research using the conventional double-layer hydroxide structure.
보다 구체적으로 도 2를 참조하면, 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 전자주사현미경 이미지(FE-SEM)를 통해 Co-Fe-LDH와 MXene 나노시트가 재적층된 혼성나노시트는 모두 2차원 나노시트 모양을 가지는 것을 알 수 있고, 나아가 이들 모두 다공성 구조를 가지는 것을 확인할 수 있다.More specifically, referring to FIG. 2, a scanning electron microscope image (FE-SEM) of the restacked hybrid nanosheet according to an embodiment of the present invention shows a hybrid nanosheet in which Co-Fe-LDH and MXene nanosheets are restacked. It can be seen that all of the sheets have a two-dimensional nanosheet shape, and furthermore, it can be seen that they all have a porous structure.
또한 도 3을 참조하면, 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 투과전자현미경-원소분석 이미지를 통해, Co, Fe, O, Ti, C는 CFM5혼성체에서 매우 골고루 분포되어 있는 것을 알 수 있는데 이는 Co-Fe-LDH와 MXene 나노시트가 재적층시 골고루 혼성화 되었음을 의미한다.Also, referring to Figure 3, through a transmission electron microscope-elemental analysis image of the restacked hybrid nanosheet according to an embodiment of the present invention, Co, Fe, O, Ti, and C are very evenly distributed in the CFM5 hybrid. It can be seen that the Co-Fe-LDH and MXene nanosheets were evenly hybridized when re-stacked.
이와 같이 본 발명은 상기 제3단계를 통해 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트를 정전기적 인력으로 재적층함으로써 혼성나노시트의 다공성이 극대화시킴으로써 촉매효율을 크게 향상시킬 수 있다.As such, the present invention maximizes the porosity of the hybrid nanosheet by re-stacking the single-layer double-layer hydroxide nanosheet exfoliated through the third step and the exfoliated single-layer conductive metal carbide nanosheet using electrostatic attraction. Catalytic efficiency can be greatly improved.
이를 위해 상기 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트가 1: 0.01 내지 0.1의 중량비로 혼성화될 수 있다. 이때 만일 상기 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트가 1: 0.01 미만의 중량비로 혼합되는 경우 전도성 나노시트 비율이 낮아 촉매성능이 충분히 향상되지 않는 문제가 있을 수 있고, 또한 만일 상기 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트가 1: 0.1의 중량비를 초과하여 혼합되면 부피당 촉매성능이 우수한 이중층 수산화물 나노시트 함량이 낮아서 혼성체물질의 전체적인 촉매성능이 낮아질 수 있다.For this purpose, the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet may be hybridized at a weight ratio of 1:0.01 to 0.1. At this time, if the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet are mixed at a weight ratio of less than 1: 0.01, the catalytic performance is not sufficiently improved due to the low conductive nanosheet ratio. There may be a problem, and if the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet are mixed in a weight ratio exceeding 1: 0.1, the double-layer hydroxide has excellent catalytic performance per volume. Because the nanosheet content is low, the overall catalytic performance of the hybrid material may be lowered.
또한, 상기 제3단계는 정전기적 인력으로 박리화된 단일층의 이중층 수산화물 나노시트 및 박리화된 단일층의 전도성 금속 탄화물 나노시트를 재적층하는 단계이기 때문에, 상기 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트는 +30mV ~ +50mV의 양전하를 띠고, 상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트는 -43mV ~ -63mV의 음전하를 띠며, 이에 상기 제3단계에서 전하평형을 맞추기 위하여 Na2CO3를 첨가할 수 있다. In addition, since the third step is a step of restacking the single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet by electrostatic attraction, the exfoliated single layer of the first step The double-layer hydroxide nanosheets in the layer have a positive charge of +30mV to +50mV, and the exfoliated single-layer conductive metal carbide nanosheets in the second step have a negative charge of -43mV to -63mV, and thus in the third step. Na 2 CO 3 can be added to balance the charge.
보다 구체적으로 도 4를 참조하면, 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 Zeta potential 측정을 통해 박리화된 Co-Fe-LDH 나노시트는 표면에 +40mV를 띠고 있고 박리화된 MXene 나노시트는 표면에 -53mV를 띠고 있는 것을 알 수 있다. 이에 따라 첨가하는 Na2CO3의 은 전하평형을 위해 적절히 선택될 수 있으므로 특별히 제한하지 않는다. More specifically, referring to FIG. 4, through measuring the Zeta potential of the restacked hybrid nanosheet according to an embodiment of the present invention, the exfoliated Co-Fe-LDH nanosheet shows +40 mV on the surface, and the exfoliated Co-Fe-LDH nanosheet shows +40 mV on the surface. It can be seen that the MXene nanosheet has -53mV on its surface. Accordingly, the added Na 2 CO 3 can be appropriately selected for charge balance and is therefore not particularly limited .
다음, 본 발명에 따른 재적층된 혼성나노시트에 대하여 설명한다. 다만 중복을 피하기 위하여 상술한 재적층된 혼성나노시트의 제조방법과 기술적 사상이 동일한 부분에 대하여는 설명을 생략한다.Next, the restacked hybrid nanosheets according to the present invention will be described. However, to avoid duplication, description will be omitted for parts that have the same technical idea as the manufacturing method of the restacked hybrid nanosheets described above.
본 발명에 따른 재적층된 혼성나노시트는 박리화된 단일층의 이중층 수산화물 (Layered Double Hydroxide, LDH) 나노시트 및 박리화된 단일층의 전도성 금속 탄화물 나노시트가 정전기적 인력으로 혼성화됨으로써 구현된다.The restacked hybrid nanosheet according to the present invention is realized by hybridizing exfoliated single-layer layered double hydroxide (LDH) nanosheets and exfoliated single-layer conductive metal carbide nanosheets through electrostatic attraction.
이때, 본 발명의 바람직한 실시예에 따라 상기 박리화된 단일층의 이중층 수산화물 나노시트는 CoFe-LDH 나노시트이며, 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트는 MXene 나노시트일 경우 상기 박리화된 단일층의 이중층 수산화물 나노시트의 두께는 0.5 ~ 1.0 nm일 수 있으며, 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트의 두께는 1.0 ~ 1.6 nm일 수 있다. 보다 구체적으로 도 5를 참조하면, 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 AFM 분석을 통해 박리화된 LDH 나노시트는 0.6nm의 두께를 가지고 있고 박리화된 MXene 나노시트는 1.3nm의 두께를 갖고 있는 것을 통해 모두 단일층의 나노시트로 합성이 되었음을 알 수 있다.At this time, according to a preferred embodiment of the present invention, the exfoliated single-layer double-layer hydroxide nanosheet is a CoFe-LDH nanosheet, and the exfoliated single-layer conductive metal carbide nanosheet is an MXene nanosheet. The thickness of the single-layer double-layer hydroxide nanosheet may be 0.5 to 1.0 nm, and the thickness of the exfoliated single-layer conductive metal carbide nanosheet may be 1.0 to 1.6 nm. More specifically, referring to Figure 5, through AFM analysis of the restacked hybrid nanosheets according to an embodiment of the present invention, the exfoliated LDH nanosheets have a thickness of 0.6 nm and the exfoliated MXene nanosheets have a thickness of 1.3 nm. It can be seen that they were all synthesized as single-layer nanosheets, as they have a thickness of nm.
한편, 본 발명은 상술한 재적층된 혼성나노시트를 포함하는 전기화학촉매를 제공한다. 도 6은 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 Oxygen evolution reaction (OER) 촉매활성 결과데이터이다. 측정결과 재적층된 혼성 나노시트는 모두 전구체인 Co-Fe-LDH와 Ti3C-2Tx 보다 훨씬 높은 전류값과 낮은 과전압을 갖는 것을 알 수 있다. 이는 혼성화를 통해 synergistic effect로 산소발생촉매성능이 향상됨을 확인 할 수 있다.Meanwhile, the present invention provides an electrochemical catalyst including the above-described restacked hybrid nanosheets. Figure 6 shows Oxygen evolution reaction (OER) catalytic activity result data of restacked hybrid nanosheets according to an embodiment of the present invention. As a result of the measurement, it can be seen that all of the restacked hybrid nanosheets have much higher current values and lower overvoltage than the precursors Co-Fe-LDH and Ti 3 C- 2 T x . It can be confirmed that oxygen generation catalyst performance is improved through hybridization through a synergistic effect.
이하에서는 실시예를 통하여 본 발명을 더욱 구체적으로 설명하기로 하지만, 하기 실시예가 본 발명의 범위를 제한하는 것은 아니며, 이는 본 발명의 이해를 돕기 위한 것으로 해석되어야 할 것이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples do not limit the scope of the present invention, and should be interpreted to aid understanding of the present invention.
실시예 1 - 재적층된 혼성나노시트의 제조Example 1 - Preparation of restacked hybrid nanosheets
Co(NO3)2·6H2O (0.003 mol) and Fe(NO3)3·9H2O (0.001 mol) 혼합 용액 50 ml와 0.025 mol NaOH 용액 50 mL을 만들었다. 50 ml of a mixed solution of Co(NO 3 ) 2 ·6H 2 O (0.003 mol) and Fe(NO 3 ) 3 ·9H 2 O (0.001 mol) and 50 ml of 0.025 mol NaOH solution were prepared.
이후 35 mL 증류수와 15 mL의 formamide 용액이 들어 있는 혼합 용액에 위에서 만든 NaOH 용액과 metal nitrate 용액을 적정하고, 반응 온도는 80도로 유지하였다. pH가 10으로 되면 5분정도 반응을 더 하다가 멈추고 이후, 원심분리를 이용하여 고체만 얻고 상기 고체를 과량의 증류수를 이용하여 세척 과정을 거친 후 50
다음 Ti3C2Tx(MXene) 나노시트는 아래와 같은 방법으로 합성한다. 우선 층간의 Al을 에칭하기 위해 1g Ti3AlC2을 20 mL 혼합용액 (12mL 12M HCl, 6mL 물, 2mL 50 wt% HF)에 넣고 35 ℃에서 24시간동안 교반하였다. 반응한 샘플은 pH가 ~6이 되도록 과량의 물로 산을 씻어낸 후, 얻은 샘플은 0.5 M LiCl 50mL와 24시간 동안 반응을 시켰다. 반응후 다시 과량이 물로 워싱하고 4-8번째 워싱되었을때의 상등액을 취함으로써 Ti3C2Tx(MXene) 나노시트를 수득하였다.Next, Ti 3 C 2 T x (MXene) nanosheets are synthesized as follows. First, to etch Al between layers, 1 g Ti 3 AlC 2 was added to 20 mL of mixed solution (12 mL 12M HCl, 6 mL water, 2 mL 50 wt% HF) and stirred at 35°C for 24 hours. After washing away the acid from the reacted sample with excess water to bring the pH to ~6, the obtained sample was reacted with 50 mL of 0.5 M LiCl for 24 hours. After the reaction, the excess was washed with water again, and the supernatant from the 4th to 8th wash was taken to obtain a Ti 3 C 2 T x (MXene) nanosheet.
재적층된 LDH-MXene 나노시트 혼성체의 합성방법은 표면에 양전하를 띠는 LDH 나노시트 콜로이드와 표면에 음전하를 띠는 MXene 나노시트 콜로이드를 정전기적으로 결합하여 혼성화 하였다. MXene/Co-Fe-LDH 비율 2.5wt%로 혼성체를 합성하였고 CFM2.5이라 명명하였다. 합성과정에서 전하 평형을 맞추기 위해 소량의 0.02 M Na2CO3 용액을 추가하였다.The method for synthesizing the restacked LDH-MXene nanosheet hybrid was hybridization by electrostatically combining LDH nanosheet colloids with a positive charge on the surface and MXene nanosheet colloids with a negative charge on the surface. A hybrid was synthesized with an MXene/Co-Fe-LDH ratio of 2.5 wt% and named CFM2.5. During the synthesis process, a small amount of 0.02 M Na 2 CO 3 solution was added to balance the charge.
실시예 2 및 3Examples 2 and 3
상기 실시예 1과 동일하게 제조하되, MXene/Co-Fe-LDH 비율 각각 5wt% 및 7.5 wt%로 달리하여 재적층된 혼성나노시트를 제조하고 각각 CFM5 및 CFM7.5로 명명하였다.Re-stacked hybrid nanosheets were prepared in the same manner as in Example 1, except that the MXene/Co-Fe-LDH ratios were changed to 5 wt% and 7.5 wt%, respectively, and were named CFM5 and CFM7.5, respectively.
비교예 1Comparative Example 1
비교예 1로 상기 실시예 1에서 제조한 이중층 수산화물 구조체 단독으로 CoFe-LDH을 선정하였다.As Comparative Example 1, CoFe-LDH was selected as the double-layer hydroxide structure prepared in Example 1.
실험예 1 - 질소 흡탈착 비표면적 분석 데이터 (기기: BELSORP-miniX)Experimental Example 1 - Nitrogen adsorption/desorption specific surface area analysis data (Instrument: BELSORP-miniX)
상기 실시예 1 내지 3 및 비교예 1에 대하여 비표면적 분석을 수행하고 이를도 1에 나타내었다.Specific surface area analysis was performed on Examples 1 to 3 and Comparative Example 1 and is shown in Figure 1.
도 1을 참조하면, 본 발명에 따라 재적층된 혼성나노시트인 실시예 들의경우(CFM2.5-224m2/g, CFM5-249m2/g, CFM7.5-295m2/g)는 LDH 나노시트(189m2/g)보다 더 큰 비표면적을 갖는걸 확인했는데 이는 LDH에 나노시트에 MXene 나노시트를 혼성화 하면서 LDH끼리의 적층을 막아주어 다공성이 극대화되어서 더 큰 비표면적을 갖는 것으로 확인된다.Referring to Figure 1, in the examples of hybrid nanosheets restacked according to the present invention (CFM2.5-224m 2 /g, CFM5-249m 2 /g, CFM7.5-295m 2 /g), LDH nano It was confirmed that it has a larger specific surface area than the sheet (189m 2 /g), which is confirmed to have a larger specific surface area because porosity is maximized by preventing stacking of LDHs while hybridizing MXene nanosheets to LDH nanosheets.
실험예 2 - 전자주사현미경이미지 (Field Emission-Scanning Electron Microscopy-회사: JEOL JSM-7001F).Experimental Example 2 - Scanning Electron Microscope Image (Field Emission-Scanning Electron Microscopy-Company: JEOL JSM-7001F).
상기 실시예 1 내지 3에 대하여 FE-SEM 이미지 분석을 수행하고 이를 도 2에 나타내었다.FE-SEM image analysis was performed on Examples 1 to 3 and is shown in Figure 2.
도 2를 참조하면, Co-Fe-LDH와 MXene 나노시트를 재적층한 본 발명에 따른 혼성화 나노시트는 모두 2차원 나노시트 모양을 가지는 것을 확인하였고 모두 porous한 구조를 갖는 것을 확인할 수 있다.Referring to Figure 2, it can be seen that the hybridized nanosheets according to the present invention obtained by re-stacking Co-Fe-LDH and MXene nanosheets all have a two-dimensional nanosheet shape, and all have a porous structure.
실험예 3 - 투과전자현미경-원소매핑 데이터 (Transmission electron microscopy, 회사: JEOL F200)Experimental Example 3 - Transmission electron microscope-element mapping data (Transmission electron microscopy, company: JEOL F200)
상기 실시예 1 내지 3에 대하여 TEM 이미지 분석을 수행하고 이를 도 3에 나타내었다.TEM image analysis was performed on Examples 1 to 3 and is shown in Figure 3.
도 3을 참조하면, 원소매핑 결과에서 알수 있듯이 Co, Fe, O, Ti, C는 CFM5혼성체에서 매우 골고루 분포되어 있는 것을 통해 Co-Fe-LDH와 MXene 나노시트가 재적층시 골고루 혼성화 되었음을 알 수 있다.Referring to Figure 3, as can be seen from the element mapping results, Co, Fe, O, Ti, and C are very evenly distributed in the CFM5 hybrid, showing that Co-Fe-LDH and MXene nanosheets were evenly hybridized when re-stacked. You can.
실험예 4 - 이미지 및 전위 데이터 (Zeta potential-회사: Malvern Zetasizer Nano ZS).Experimental Example 4 - Image and potential data (Zeta potential - Company: Malvern Zetasizer Nano ZS).
본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 전위 데이터를 분석하고 이를 도 4에 나타내었다.Potential data of the restacked hybrid nanosheets according to an embodiment of the present invention were analyzed and shown in FIG. 4.
도 4를 참조하면, 본 발명의 일 실시예에 따른 재적층된 혼성나노시트의 Zeta potential 측정을 통해 박리화된 Co-Fe-LDH 나노시트는 표면에 +40mV를 띠고 있고 박리화된 MXene 나노시트는 표면에 -53mV를 띠고 있는 것을 알 수 있다.Referring to Figure 4, through Zeta potential measurement of the restacked hybrid nanosheet according to an embodiment of the present invention, the exfoliated Co-Fe-LDH nanosheet shows +40 mV on the surface, and the exfoliated MXene nanosheet shows +40 mV. It can be seen that it is -53mV on the surface.
실험예 5 - 원자현미경 이미지 (Atomic force microscopy-회사: Park Systems NX-10).Experimental Example 5 - Atomic force microscope image (Atomic force microscopy - Company: Park Systems NX-10).
상기 실시예 1에서 제조한 혼성나노시트의 원자현미경 이미지를 분석하고 이를 도 5에 나타내었다.The atomic force microscope image of the hybrid nanosheet prepared in Example 1 was analyzed and shown in FIG. 5.
도 5를 참조하면, AFM 분석을 통해 알 수 있듯이 박리화된 LDH 나노시트는 0.6nm의 두께를 가지고 있고 박리화된 MXene 나노시트는 1.3nm의 두께를 갖고 있는 것을 통해 모두 단일층의 나노시트로 합성이 되었음을 알 수 있다.Referring to Figure 5, as can be seen through AFM analysis, the exfoliated LDH nanosheets have a thickness of 0.6 nm and the exfoliated MXene nanosheets have a thickness of 1.3 nm, indicating that they are all single-layer nanosheets. You can see that it was synthesized.
실험예 6 - oxygen evolution reaction (OER) 활성 데이터.Experimental Example 6 - Oxygen evolution reaction (OER) activity data.
상기 실시예 1 내지 3 및 비교예 1에 대하여 촉매활성 분석을 수행하고 이를도 6에 나타내었다. 합성한 샘플들은 1M KOH 용액에서 측정을 하였고 scan rate는 5mV/s로 하였다.Catalytic activity analysis was performed on Examples 1 to 3 and Comparative Example 1 and is shown in Figure 6. The synthesized samples were measured in 1M KOH solution and the scan rate was set to 5mV/s.
도 6을 참조하면, 측정결과 본 발명의 실시예들의 경우 모두 Co-Fe-LDH와 Ti3C2Tx 나노시트 각각 보다 훨씬 높은 전류값과 낮은 과전압을 갖는 것을 알 수 있다. 이는 혼성화를 통해 synergistic effect로 산소발생촉매성능이 향상됨을 확인할 수 있다.Referring to FIG. 6, it can be seen from the measurement results that all of the examples of the present invention have much higher current values and lower overvoltages than Co-Fe-LDH and Ti 3 C 2 T x nanosheets, respectively. It can be confirmed that oxygen generation catalyst performance is improved through hybridization through a synergistic effect.
Claims (10)
박리화된 단일층의 전도성 금속 탄화물 나노시트를 제조하는 제2단계; 및
상기 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트를 혼성화하는 제3단계; 를 포함하는 재적층된 혼성나노시트의 제조방법.
A first step of manufacturing an exfoliated single-layer layered double hydroxide (LDH) nanosheet;
A second step of producing exfoliated single-layer conductive metal carbide nanosheets; and
A third step of hybridizing the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet; Method for manufacturing restacked hybrid nanosheets comprising.
상기 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트는,
박리화된 단일층의 CoFe-LDH 나노시트인 것을 특징으로 하는 재적층된 혼성나노시트의 제조방법.
According to paragraph 1,
The exfoliated single-layer double-layer hydroxide nanosheet of the first step is,
A method of manufacturing restacked hybrid nanosheets, characterized in that they are exfoliated single-layer CoFe-LDH nanosheets.
상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트는,
MXene 나노시트인 것을 특징으로 하는 재적층된 혼성나노시트의 제조방법.
According to paragraph 1,
The second-stage exfoliated single-layer conductive metal carbide nanosheet is,
Method for manufacturing restacked hybrid nanosheets characterized as MXene nanosheets.
상기 제3단계는 정전기적 인력으로 재적층함으로써 혼성나노시트의 다공성이 극대화되는 것을 특징으로 하는 재적층된 혼성나노시트의 제조 방법.
According to paragraph 1,
The third step is a method of manufacturing restacked hybrid nanosheets, wherein the porosity of the hybrid nanosheets is maximized by restacking them using electrostatic attraction.
상기 제3단계는 상기 박리화된 단일층의 이중층 수산화물 나노시트 및 상기 박리화된 단일층의 전도성 금속 탄화물 나노시트가 1: 0.01 내지 0.1의 중량비로 혼성화되는 것을 특징으로 하는 혼성나노시트의 제조방법.
According to paragraph 1,
In the third step, the exfoliated single-layer double-layer hydroxide nanosheet and the exfoliated single-layer conductive metal carbide nanosheet are hybridized at a weight ratio of 1:0.01 to 0.1. .
상기 제1단계의 박리화된 단일층의 이중층 수산화물 나노시트는 +30mV ~ +50mV의 양전하를 띠고,
상기 제2단계의 박리화된 단일층의 전도성 금속 탄화물 나노시트는 -43mV ~ -63mV의 음전하를 띠며,
상기 제3단계에서 전하평형을 맞추기 위하여 Na2CO3를 첨가하는 것을 특징으로 하는 혼성나노시트의 제조방법.
According to paragraph 1,
The exfoliated single-layer double-layer hydroxide nanosheet in the first step has a positive charge of +30mV to +50mV,
The second-stage exfoliated single-layer conductive metal carbide nanosheet has a negative charge of -43mV to -63mV,
A method of producing a hybrid nanosheet, characterized in that Na 2 CO 3 is added to balance the charge in the third step.
A restacked hybrid nanosheet in which exfoliated single-layer layered double hydroxide (LDH) nanosheets and exfoliated single-layer conductive metal carbide nanosheets are hybridized through electrostatic attraction.
상기 박리화된 단일층의 이중층 수산화물 나노시트의 두께는 0.5 ~ 1.0 nm이며,
상기 박리화된 단일층의 전도성 금속 탄화물 나노시트의 두께는 1.0 ~ 1.6 nm인 것을 특징으로 하는 재적층된 혼성나노시트.
In clause 7,
The thickness of the exfoliated single-layer double-layer hydroxide nanosheet is 0.5 to 1.0 nm,
A restacked hybrid nanosheet, characterized in that the thickness of the exfoliated single-layer conductive metal carbide nanosheet is 1.0 ~ 1.6 nm.
상기 박리화된 단일층의 이중층 수산화물 나노시트는 CoFe-LDH 나노시트이며,
상기 박리화된 단일층의 전도성 금속 탄화물 나노시트는 MXene 나노시트인 것을 특징으로 하는 재적층된 혼성나노시트.
In clause 7,
The exfoliated single-layer double-layer hydroxide nanosheet is a CoFe-LDH nanosheet,
A restacked hybrid nanosheet, wherein the exfoliated single-layer conductive metal carbide nanosheet is an MXene nanosheet.
An electrochemical catalyst comprising the restacked hybrid nanosheets according to any one of claims 7 to 9.
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