저자는 마틴 스미스, 코린 돌, 및 국방 과학 기술 연구소 (DSTL)의 콜린 윌리스 저압 플라즈마 기술에 대한 전문 지식, 그리고 마태 복음 Browe과의 웨슬리 고든, 프로젝트 번호 BA07PRO104에서 자금의 국방 위협 감소 기관 감사 각각 microbreakthrough 테스트 및 접촉각 측정을위한 엣지 화학 생물학 센터 (ECBC).

1. CU-BTC 합성 및 준비 <ol><li> 약 5 분 동안 뚜껑 항아리 나사의 탈 이온수 12.5 ㎖ 및 100 ㎖의 디메틸 포름 아미드 12.5 ㎖를 저어. </li><li> 0.87 g (3.6 mmol)을 항아리에 솔루션에 메스 산 0.50 g (2.4 mmol)을 다음에 구리 (II) 질산 삼수화물을 추가하고 약 5 분 동안 교반 하였다. 이 솔루션은 색상에 파란색으로 바뀝니다. 약 24 시간 동안 120 ° C로 예열 된 오븐에 덮인 항아리를 놓습니다. </li><li> 오븐에서 항아리를 제거합니다. 용기는 실온까지 냉각되면,보다 크거나 2.5 μM 같은지 결정을 회수하는 미 여과지를 사용하여 진공 여과를 통해의 Cu-BTC 결정을 회수. 궁극적으로 디클로로 메탄의 새로운 솔루션의 결정을 배치, 디클로로 메탄으로 생성 된 결정을 씻어. </li><li> 용매마다 24 시간을 교환하고 구리 -의 기공에서 덜 휘발성 용매의 제거에 도움이 앞으로 3 일 동안 신선한 디클로로 메탄으로 대체BTC. </li><li> 진공 오븐에서 또는 재료로부터 잔류 게스트 분자를 제거하기 쉬 렌크 라인을 통해 170 ° C까지의 Cu-BTC 결정을 가열한다. 완전 활성화 된 구리 - BTC 색상 보라색에 파란색 깊은해야한다. </li><li> 분말 X-선 회절과 푸리에 변환 적외선 분광기, 각각을 통해 잘라 내기 - BTC의 구조 및 화학 메이크업을 확인합니다. </li></ol> 2. 구리 - BTC 14 퍼플 루오의 플라즈마 화학 기상 증착 <ol><li> 이전에 각 실험에 플라즈마 리액터 및 적어도 30 분 동안 50 W에서 공기 플라즈마로 플라즈마 처리에 사용되는 어떠한 유리를 청소. 이는 반응 챔버 또는 이전 실험에서 유리의 내부 표면 상에 형성 할 수있는 어떤 퍼플 루오 필름을 제거한다. </li><li> 250 ㎖의 파이렉스 병 및 균일 한 치료를 보장하기 위해 옆으로 병으로 확산 활성화의 Cu-BTC의 알려진 양을 넣습니다. 투과성 천의 주위에 배치해야진공을 적용시 손실되는 시료의 양을 최소화하기 위해 고무 밴드와 병의 목. </li><li> 플라즈마 챔버에 병을 놓습니다. 챔버는 샘플에 흡착 할 수있는 어떤 물을 제거하기 위해 적어도 30 분 동안 0.20 밀리바 ≤ 압력에 도달 할 때까지 진공을 적용합니다. </li><li> 퍼플 루오로 가스를 연결하고 질량 유량 제어기의 사양에 압력 조절기를 조정합니다. </li><li> 실험의 원하는 압력을 유지하기 위해 퍼플 루오 가스의 적당량을 반응 챔버를 채우기 위해 질량 흐름 제어기를 조정한다. 분말의보다 균일 한 처리를 만들 수 PECVD 장치 내 병을 돌립니다. </li><li> 13.56 MHz의 RF 발생기, 및 반사율을 최소화하면서 전력을 최대화하기위한 LC 매칭 유닛과 함께 조정 무선 주파수를 가진 플​​라즈마를 켜지. 치료를 통해 주기적으로 다시 튜닝. </li><li> 처리가 완료되면, 임의의 챔버 대피잔류 퍼플 루오 가스 후 대기압 벤트. PECVD 장치로부터 샘플을 제거하고 병의 측면에서 처리 된 자료를 복구 할 수 있습니다. 대전 장치는 재료의 최대 양을 복구하는 데 사용한다. </li><li> 반응하지 않은 퍼플 루오로 가스를 제거하기 위해 120 ° C의 오븐에서 처리 된 재료를 넣습니다. 이어서 대기로부터 물 흡착을 방지하기 위해 데시 케이 처리 재료를 배치. </li><li> 병에 남아있는 잔류 물질을 씻어하고 적절한 처리를위한 폐기물을 복구하기 위해 필터링합니다. </li><li> 20 F 매직 앵글은 핵 자기 공명을 회전하는 처리의 Cu-BTC 특성화, 적외선 분광법을 푸리에 - 변환 및 x-선 광전자 분광법. </li></ol> 3. 습한 조건에서 구리 - BTC의 노화 <ol><li> 원하는 온도와 환경 챔버의 상대 습도를 설정하고 평형을 할 수 있습니다. </li><li> 에 균등하게 샘플을 확산원하는 시간에 대한 환경 챔버의 뚜껑이없는 용기와 장소. </li><li> 열화의 정도를 확인하기 위하여 77 K에서 x-선 회절 및 질소 등온선으로의 Cu-BTC 샘플을 특성화. </li></ol> 4. 암모니아 Microbreakthrough 실험 2 <ol><li> 첫 번째 깔끔한 암모니아 210 ㎖로 빈 안정기를 주입하여 5,000 ㎎ / m 3에서 암모니아의 14.6 L 밸러스트를 준비합니다. 그런 다음 15 PSI의 압력으로 제로 공기와 안정기를 입력합니다. microbreakthrough 장치에 맞춰 안정기를 연결합니다. </li><li> 공급 신호를 결정하기 위해 microbreakthrough 장치에 빈 튜브를 실행합니다. 20 ㎖ / 분 ㎎ / m 3 암모니아 2,000의 흐름을 만들기 위해, 각각 13 및 12 ㎖ / 분으로 암모니아 및 건조 공기를위한 질량 흐름 제어기를 설정한다. 유출 물에 암모니아의 공급 신호를 결정하기 위하여 가스 크로마토 그래프 및 광 이온화 검출기를 제어하는​​ 프로그램을 실행하는 방법. 습기가 시스템에 추가 될 수있다요구되는 상대 습도를 달성하기 위해 필요한 속도로 온도 제어 포화 셀을 통해 희석 스트림의 일부를 실행하여 원하는 경우. </li><li> 공칭 4mm 아이디 유리 튜브 유리 프릿 아래 유리 섬유의 작은 금액을 놓습니다. 튜브에 재료의 약 10 ~ 15 mg의 무게. 사용되는 질량은 약 0.15 초 침대 체류 시간의 결과로, 약 55mm 3 흡착제 볼륨을 초래할 것이다. </li><li> 어떤 흡착 물을 제거하기 위해 1 시간 동안 150 ° C로 가열로 유리 튜브를 통해 건조한 공기 흐름. 재생 후 시료의 무게를 측정. </li><li> 라인에 샘플을 넣고 25 ℃로 설정 수욕 똑바로 고정 </li><li> 공급 가스와 함께 충전 라인에 샘플을 우회하는 동안 2,000 ㎎ / m 3 암모니아 20 ㎖ / 분의 흐름을 만들기 위해, 각각 13 및 12 ㎖ / 분으로 암모니아 및 건조 공기를위한 질량 흐름 제어기를 설정한다. </li><li> 샘플을 통해 암모니아 스트림을 흐름 및 프로그램시켜 실행할유출 물에 암모니아의 농도를 모니터링하기 위하여 가스 크로마토 그래프 및 광 이온화 검출기를 제어하는​​ 방법. </li><li> 유출 농도가 공급 농도에 도달하면, 암모니아 스트림을 끄고 강하게 샘플에 흡착되지 않은 오프 - 가스 암모니아에 샘플을 수 있습니다. </li><li> x-선 회절 및 푸리에 변환 적외선 분석을 통해 노광 후 분석을 위해 수조로부터 샘플을 제거한다. </li><li> 시료 암모니아 로딩을 결정하기 위하여 시간 데이터 대 가스 크로마토 신호를 통합한다. </li></ol>

<ol>
	<li>Montoro, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Capture+of+Nerve+Agents+and+Mustard+Gas+Analogues+by+Hydrophobic+Robust+MOF-5+Type+Metal-Organic+Frameworks.">Capture of Nerve Agents and Mustard Gas Analogues by Hydrophobic Robust MOF-5 Type Metal-Organic Frameworks.</a> J. Am. Chem. Soc. 133, 11888-11891 (2011).</li><li>Glover, T. G., Peterson, G. W., Schindler, B. J., Britt, D., Yaghi, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=MOF-74+building+unit+has+a+direct+impact+on+toxic+gas+adsorption.">MOF-74 building unit has a direct impact on toxic gas adsorption.</a> Chem. Eng. Sci. 66, 163-170 (2011).</li><li>Britt, D., Tranchemontagne, D., Yaghi, O. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Metal-organic+frameworks+with+high+capacity+and+selectivity+for+harmful+gases.">Metal-organic frameworks with high capacity and selectivity for harmful gases.</a> Proc. Natl. Acad. Sci. U.S.A. 105, 11623-11627 (2008).</li><li>Peterson, G. W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia+Vapor+Removal+by+Cu(3)(BTC)(2)+and+Its+Characterization+by+MAS.">Ammonia Vapor Removal by Cu(3)(BTC)(2) and Its Characterization by MAS.</a> NMR. J. Phys. Chem. Nanomater. Interfaces. 113 (3), 13906-13917 (2009).</li><li>Gul-E-Noor, F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effects+of+varying+water+adsorption+on+a+Cu(3)(BTC)(2)+metal-organic+framework+(MOF)+as+studied+by+(1)H+and+(13)C+solid-state+NMR+spectroscopy.">Effects of varying water adsorption on a Cu(3)(BTC)(2) metal-organic framework (MOF) as studied by (1)H and (13)C solid-state NMR spectroscopy.</a> Phys. Chem. Chem. Phys. 13 (3), 7783-7788 (2011).</li><li>DeCoste, J. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+effect+of+water+adsorption+on+the+structure+of+the+carboxylate+containing+metal-organic+frameworks+Cu-BTC,+Mg-MOF-74,+and+UiO-66.">The effect of water adsorption on the structure of the carboxylate containing metal-organic frameworks Cu-BTC, Mg-MOF-74, and UiO-66.</a> J. Mater. Chem. , (2013).</li><li>K&#252;sgens, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterization+of+metal-organic+frameworks+by+water+adsorption.">Characterization of metal-organic frameworks by water adsorption.</a> Microporous and Mesoporous Mater. 120, 325-330 (2009).</li><li>Cavka, J. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+New+Zirconium+Inorganic+Building+Brick+Forming+Metal+Organic+Frameworks+with+Exceptional+Stability.">A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability.</a> J. Am. Chem. Soc. 130, 13850-13851 (2008).</li><li>DeCoste, J. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Stability+and+degradation+mechanisms+of+metal-organic+frameworks+containing+the+Zr6O4(OH)4+secary+building+unit.">Stability and degradation mechanisms of metal-organic frameworks containing the Zr6O4(OH)4 secary building unit.</a> J. Mater. Chem. A. 1, 5642-5650 (2013).</li><li>Yang, S. J., Park, C. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+Highly+Moisture-Resistant+Black-Colored+Metal+Organic+Frameworks.">Preparation of Highly Moisture-Resistant Black-Colored Metal Organic Frameworks.</a> Adv. Mater. 24, 4010-4013 (2012).</li><li>Li, H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+Hydrostability+in+Ni-Doped+MOF-5.">Enhanced Hydrostability in Ni-Doped MOF-5.</a> Inorg. Chem. 51, 9200-9207 (2012).</li><li>Jasuja, H., Huang, Y. -. g., Walton, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Adjusting+the+Stability+of+Metal+-+Organic+Frameworks+under+Humid+Conditions+by+Ligand+Functionalization.">Adjusting the Stability of Metal - Organic Frameworks under Humid Conditions by Ligand Functionalization.</a> Langmuir. 28, 16874-16880 (2012).</li><li>Jasuja, H., Burtch, N. C., Huang, Y. -. g., Cai, Y., Walton, K. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+Water+Stability+of+an+Isostructural+Family+of+Zinc-Based+Pillared+Metal+-+Organic+Frameworks.">Kinetic Water Stability of an Isostructural Family of Zinc-Based Pillared Metal - Organic Frameworks.</a> Langmuir. 29, 633-642 (2012).</li><li>Decoste, J. B., Peterson, G. W., Smith, M. W., Stone, C. A., Willis, C. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+Stability+of+Cu-BTC+MOF+via+Perfluorohexane+Plasma-Enhanced+Chemical+Vapor+Deposition.">Enhanced Stability of Cu-BTC MOF via Perfluorohexane Plasma-Enhanced Chemical Vapor Deposition.</a> J. Am. Chem. Soc. 134, 1486-1489 (2012).</li><li>Bradley, R. H., Smith, M. W., Andreu, A., Falco, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+studies+of+novel+hydrophobic+active+carbons.">Surface studies of novel hydrophobic active carbons.</a> Appl. Surf. Sci. 257, 2912-2919 (2011).</li><li>Poire, E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Modification+of+active+carbon+by+hydrophobic+plasma+plymers.">Modification of active carbon by hydrophobic plasma plymers.</a> Plasma Deposition of Polymeric Thin Films. 54, 185-196 (1994).</li><li>Hozumi, A., Takai, O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+ultra+water-repellent+films+by+microwave+plasma-enhanced+CVD.">Preparation of ultra water-repellent films by microwave plasma-enhanced CVD.</a> Thin Solid Films. 303 (97), 222-225 (1997).</li><li>Dolbier, W. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Guide to Fluorine NMR for Organic Chemists. , (2009).</li><li>Maricq, M. M., Waugh, J. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=NMR+IN+ROTATING+SOLIDS.">NMR IN ROTATING SOLIDS.</a> J. Chem. Phys. 70, 3300-3316 (1979).</li><li>Kim, M., Cahill, J. F., Su, Y., Prather, K. A., Cohen, S. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Postsynthetic+ligand+exchange+as+a+route+to+functionalization+of+'inert'+metal-organic+frameworks.">Postsynthetic ligand exchange as a route to functionalization of 'inert' metal-organic frameworks.</a> Chem. Sci. 3, 126-130 (2012).</li><li>d'Agostino, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Advanced Plasma Technology. , (2008).</li><li>DeCoste, J. B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=+The+effect+of+water+adsorption+on+the+structure+of+the+carboxylate+containing+metal-organic+frameworks+Cu-BTC,+Mg-MOF-74,+and+UiO-66."> The effect of water adsorption on the structure of the carboxylate containing metal-organic frameworks Cu-BTC, Mg-MOF-74, and UiO-66.</a> J. Mater. Chem. A. , (2013).</li></ol>

저자는 더 경쟁 재정적 이익이 없다는 것을 선언합니다.

의 Cu-BTC의 합성은 대부분의 MOFs에서와 같이 사용되는 반응물의 비율은 합성에서 수행되는 온도에 크게 의존 할 수있다. 합성에 사용 온도 나 용매 MOF 구조체 (20)의 상이한 모폴로지를 생성하기 위하여 도시 한 내용이 다른. 따라서 어떤 MOF를 합성 것에 대해 문헌에 명시된 절차에 따라 강한 중요하다. 합성을 수행 할 수있는 용기를 선택할 때 한층 한 반응물, 용매 및 합성 조건을 고려해야...

금속 - 유기 프레임 워크 (MOFs와는) 유독 가스 제거 1-3 다공성 물질의 주요 클래스가되었습니다. MOFs와는 대상 화학 물질의 상호 작용에 대한 기능을 조정할 수있는 전례없는 능력을 가지고. 이전에 매우 높은 암모니아 로딩이 밝혀졌다 (도 2 HKUST-1 또는 3의 Cu (BTC)라고도 함)의 Cu-BTC가되지만,이 물질의 구조적 안정성 (4)의 비용이다. 구리 - BTC에 대한 자세한 연구는 수분 자체가 많은 잠재적 인 응용 프로그램 5,6,21에 대한 효과를 렌더링, MOF 구조를 분해 할 수 있음을 지적했다. 액체 상태의 물이나 습도의 존재의 MOFs를 포함하는 특정 카르 복실 레이트의 구조적 불안정성은 상업용 또는 산업용으로 응용 프로그램을 7에서 사용할 수있는 주요 제지하고있다. 이는 습도의 존재하에 본래의 안정성을 갖도록 화학적 제거에 사용 MOFs와 가장 이상적 일 것이다. 그러나, 많은 MOMOF-74 및 잘라 내기 - BTC 같은 개방형 금속 사이트와 많은 MOFs와 우수한 화학적 제거 기능 2,4,8,9가있는 동안 같은 UIO-66와 같은 뛰어난 안정성과 FS는,,,별로 화학 물질 제거 기능이 있습니다. MOF-74 및 잘라 내기 - BTC에서 열린 금속 사이트는 암모니아와 같은 독성 가스의 흡수를 강화하지만,이 사이트는 또한, 물을 결합 활성 부위 중독 많은 경우에 구조 분석에 이르는에 감염 될 수 있습니다. 물 불안정 MOF의 화학적 성질을 유지하기 위해, MOFs와의 물 안정성을 향상시키기 위해 다양한 시도가 만들어져왔다. MOF-5 MOF 주변의 탄소 층을 생성함으로써, 열처리시에 방습성 향상을 갖도록 도시되어 있으나, 소수성이 증가 된 표면적을 희생하고 궁극적으로 (10) 기능성. MOF-5는 또한 hydrostability 니켈 2 + (11)를 이온으로 도핑을 통해 증가한 것으로 나타났다. 또한, 1,4 - 디아 자비 시클로 [2.2.2] 옥탄이 포함(또한 DMOFs라고도 함) 보내고으로 MOFs는 1,4 - 벤젠 디카 르 복실 레이트 링커 12,13에 다양 펜던트 기의 혼입을 통해 물 안정성의 조정을 표시하는 데 사용되었다. MOFs와 특정의 hydrostability의 부족, 높은 독성 가스 흡수와 함께 구체적 것들은 그 소수성 (14)을 증가 MOF의 표면에 불소화 그룹을 만들 수있는 퍼플 루오로 알칸의 플라즈마 강화 화학 기상 증착 (PECVD)에 사용되었다. 이 기술은 방향족 수소뿐만 아니라으로 MOFs의 내면에 다른 잠재적 인 작용기를 함유하는 임의의 MOF를 변경하는데 사용될 수 있다는 특유의 효과를 제공한다. 그러나, 기술에 의한 플라즈마 중의 반응성이 높은 라디칼의 형성을 제어하기 어려울 수있다. 라디칼은 방향족 수소 원자와 반응뿐만 아니라 CF X 그룹과 이미 MOF 표면에 반응뿐만 아니라. 절차의주의 깊은 제어는 기공 BLO을 보장 할 필요가있다ckage은 MOF 효과, 렌더링이 발생하지 않습니다. 이 기술은 탄소 재료의 습윤 특성을 변경하기 위해 다른 사람이 사용되었습니다 있지만, 우리의 지식은 이전에 미세 다공성 물질의 hydrostability을 향상하는 데 사용 된 적이 있었다 (15, 16)..

<table border="1">
	<tbody>
		<tr>
			<td>Name of Material/ Equipment</td>
			<td>Company</td>
			<td>Catalog Number</td>
			<td>Comments/Description</td>
		</tr>
		<tr>
			<td>Copper (II) Nitrate Trihydrate</td>
			<td>Sigma-Aldrich</td>
			<td>61194</td>
			<td></td>
		</tr>
		<tr>
			<td>Trimesic acid</td>
			<td>Sigma-Aldrich</td>
			<td>482749</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol</td>
			<td>Sigma-Aldrich</td>
			<td>130147</td>
			<td></td>
		</tr>
		<tr>
			<td>Dimethyl Formamide</td>
			<td>Sigma-Aldrich</td>
			<td>319937</td>
			<td></td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Sigma-Aldrich</td>
			<td>187332</td>
			<td></td>
		</tr>
		<tr>
			<td>Hexafluoroethane</td>
			<td>Synquest Labs</td>
			<td>1100-2-05</td>
			<td></td>
		</tr>
		<tr>
			<td>Femto-Plasma System</td>
			<td>Diener Electronic</td>
			<td>Basic unit type B</td>
			<td></td>
		</tr>
		<tr>
			<td>Plasma Generator</td>
			<td>Diener Electronic</td>
			<td>Type D</td>
			<td>0-100 W at 13.56 MHz</td>
		</tr>
		<tr>
			<td>Rotary Vane Pump for Plasma System</td>
			<td>Leybold</td>
			<td>D16BCS PFPE</td>
			<td>Appropriate for corrosive gases</td>
		</tr>
		<tr>
			<td>Powder Treatment Device</td>
			<td>Diener Electronic</td>
			<td>Option 5.9</td>
			<td>Glass bottle and rotating devise within plasma system</td>
		</tr>
		<tr>
			<td>Environmental Chamber</td>
			<td>Associated Environmental Systems</td>
			<td>HD-205</td>
			<td></td>
		</tr>
		<tr>
			<td>Gas Chromatograph</td>
			<td>Hewlet Packard</td>
			<td>HP5890 Series II</td>
			<td></td>
		</tr>
		<tr>
			<td>Photoionization Detector</td>
			<td>O-I Analytical</td>
			<td>4430/5890</td>
			<td></td>
		</tr>
		<tr>
			<td>Photoionization Detector Lamp</td>
			<td>Excilitis</td>
			<td>FK-794U</td>
			<td></td>
		</tr>
		<tr>
			<td>Water bath</td>
			<td>NESLAB</td>
			<td>RTE-111</td>
			<td></td>
		</tr>
		<tr>
			<td>Fritted glass tubes</td>
			<td>CDA Analytical</td>
			<td>MX062101</td>
			<td>Dynatherm sampling tubes</td>
		</tr>
	</tbody>
</table>

preparation of hydrophobic metal-organic frameworks via plasma enhanced chemical vapor deposition of perfluoroalkanes for the removal of ammonia

퍼플 루오로 알칸의 플라즈마 강화 화학 기상 증착 (PECVD)은 긴 표면의 습윤성을 조정하기 위해 연구되었다. 금속 - 유기 프레임 워크 (MOFs와) 같은 표면적 다공성 물질의 경우, 고유 한 문제는 PECVD 트리트먼트의 자신을 제시한다. 여기에 조건을 습 이전 불안정 MOF의 개발을위한 프로토콜이 제공됩니다. 이 프로토콜은 (또한 HKUST-1이라고도 함)의 Cu-BTC, 퍼플 루오의 PECVD, 습기가 많은 조건에서 재료의 노화 및 미세 다공성 물질의 밀리그램 수량에 대한 후속 암모니아 microbreakthrough 실험과 구리 - BTC의 치료의 합성을 설명합니다. 이전에 PECVD 방법에 의해 치료 된 대부분의 물질 또는 표면과 비교했을 때의 Cu-BTC가 매우 높은 표면적 (~ 1천8백미터 ㎟ / g)을 갖는다. 이러한 챔버 압력 및 처리 시간 등의 매개 변수는 퍼플 루오로 플라즈마가 침투 확인하고 반응하는 것이 매우 중요하다내부 MOF 표면의. 또한, 여기에 기재된 설정 암모니아 microbreakthrough 실험을위한 프로토콜 시험 가스 및 미다 다양한 재료를 위해 이용 될 수있다.

<html> 대표적인 결과 내에서 저자는 4 0.30 밀리바의 압력에서 시간과 처리 50 W. MOFs와의 플라즈마 전원에 대한 (C 2 F 6) 헥사 플루오로 치료의 Cu-BTC의 0.50 g 샘플의 특성을 표시하기로 결정했습니다 적절한 조건에서 퍼플 루오로 플라즈마 강화 된 소수성을 표시해야합니다. 이는 액체 상태의 물 위에 분말을 놓고 샘플 수레 또는 가압 펠릿에 접촉각 물 측정은도 1에 도시 ?...

Watch this Scientific Journal Video about Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia at JoVE.com

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

여기서 같은 그들의 안정성 및 소수성을 향상시키기 위해 금속 - 유기 프레임 워크와 같은 미세 다공성 물질에 퍼플 루오로 알칸의 플라즈마 강화 화학 기상 증착을위한 절차가 설명된다. 또한, 샘플의 밀리그램 양의 돌파 테스트를 상세히 설명한다.

플라즈마 통해 소수성 유기 금속 프레임 워크의 제조 암모니아의 제거에 대한 퍼플 루오로 알칸의 화학 증착을 강화

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

preparation-hydrophobic-metal-organic-frameworks-via-plasma-enhanced

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Chemistry

15.4K 조회수.  Science Applications International Corporation (SAIC).  여기서 같은 그들의 안정성 및 소수성을 향상시키기 위해 금속 - 유기 프레임 워크와 같은 미세 다공성 물질에 퍼플 루오로 알칸의 플라즈마 강화 화학 기상 증착을위한 절차가 설명된다. 또한, 샘플의 밀리그램 양의 돌파 테스트를 상세히 설명한다. 

비디오: Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

기능화의 합성 및 특성 금속 - 유기 프레임 워크

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

연구

화학

Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at &#60;60 &#176;C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

We present the synthesis of the organic-based ferrimagnet vanadium tetracyanoethylene (V[TCNE]x, x~2) via low temperature chemical vapor deposition (CVD). This optimized recipe yields an increase in Curie temperature from 400 K to over 600 K and a dramatic improvement in magnetic resonance properties.

자석의 유기 화학 기상 증착, 바나듐 테트라시

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in ...

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process.
The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

A procedure for the preparation of porous hybrid separation media composed of a macroporous polymer monolith internally coated by a high surface area microporous coordination polymer is presented.

포스 포의 향상된 농축을위한 거대 다공성 고분자 모노리스에 다공성 조정 폴리머 코팅의 제조

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr2+ act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

A protocol is presented for the preparation of piezoelectric macroporous epitaxial films of quartz on silicon by solution chemistry using dip-coating and thermal treatments in air.

화학 용액 증착에 의해 실리콘에 거대 다공성 에피 택셜 석영 필름의 제조

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

원자 층 증착을 통해 게르마늄에 페 로브 스카이 스트론튬 티탄의 에피 택셜 성장

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

Aerosol-assisted Chemical Vapor Deposition of Metal Oxide Structures: Zinc Oxide Rods

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, their high cost production and/or incompatibility with microfabrication technologies, due to the use of pre-deposited catalyst-seeds and/or high processing temperatures exceeding 900 &#176;C, represent a drawback for a widespread use of these methods. Here, however, we report the synthesis of ZnO rods via a non-catalyzed vapor-solid mechanism enabled by using an aerosol-assisted chemical vapor deposition (CVD) method at 400 &#176;C with zinc chloride (ZnCl2) as the precursor and ethanol as the carrier solvent. This method provides both single-step formation of ZnO rods and the possibility of their direct integration with various substrate types, including silicon, silicon-based micromachined platforms, quartz, or high heat resistant polymers. This potentially facilitates the use of this method at a large-scale, due to its compatibility with state-of-the-art microfabrication processes for device manufacture. This report also describes the properties of these structures (e.g., morphology, crystalline phase, optical band gap, chemical composition, electrical resistance) and validates its gas sensing functionality towards carbon monoxide.

Columnar zinc oxide structures in the form of rods are synthesized via aerosol-assisted chemical vapor deposition without the use of pre-deposited catalyst-seed particles. This method is scalable and compatible with various substrates based on either silicon, quartz or polymers.

에 어로 졸 기반 구조 금속 산화물의 화학 증기 증 착: 산화 아연 막대

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

향상 된 수 분 저항 금속-유기 프레임 워크의 표면 기능화

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of the reaction site in metal-organic framework (MOF)&#8211;based catalysts in an enantioselective catalytic reaction system. Therefore, a method of validating the reaction site of MOF-based catalysts is necessary to investigate this issue. Substrate size discrimination by pore size was accomplished by comparing the substrate size versus the reaction rate in two different types of carbonyl-ene reactions with two kinds of MOFs. The MOF catalysts were used to compare the performance of the two reaction types (Zn-mediated stoichiometric and Ti-catalyzed carbonyl-ene reactions) in two different media. Using the proposed method, it was observed that the entire MOF crystal participated in the reaction, and the interior of the crystal pore played an important role in exerting chiral control when the reaction was stoichiometric. Homogeneity of the chiral environment of MOF catalysts was established by the size control method for a particle used in the Zn-mediated stoichiometric reaction system. The protocol proposed for the catalytic reaction revealed that the reaction mainly occurred on the catalyst surface regardless of the substrate size, which reveals the actual reaction sites in MOF-based heterogeneous catalysts. This method for reaction site validation of MOF catalysts suggests various considerations for developing heterogeneous enantioselective MOF catalysts.

Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs

Here, we present a protocol for active site validation of metal-organic framework catalysts by comparing stoichiometric and catalytic carbonyl-ene reactions to find out whether a reaction takes place on the inner or outer surface of metal-organic frameworks.

키랄 금속-유기 프레임워크(MOF)를 이용한 이기종 에난티오 선택적 촉매 개발

Substrate size discrimination by the pore size and homogeneity of the chiral environment at the reaction sites are important issues in the validation of ...

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. However, the synthesis of single-crystalline core-shell MOFs is very challenging, and thus a limited number of examples have been reported. Here, we suggest a method of synthesizing single-crystalline HKUST-1@MOF-5 core-shells, which is HKUST-1 at the center of MOF-5. Through the computational algorithm, this pair of MOFs was predicted to have the matched lattice parameters and chemical connection points at the interface. To construct the core-shell structure, we prepared the octahedral- and cubic-shaped HKUST-1 crystals as a core MOF, in which the (111) and (001) facets were mainly exposed, respectively. Via the sequential reaction, the MOF-5 shell was well-grown on the exposed surface, showing a seamless connect interface, which resulted in the successful synthesis of single-crystalline HKUST-1@MOF-5. Their pure phase formation was proved by optical microscopic images and powder X-ray diffraction (PXRD) patterns. This method presents the potential of and insights into the single-crystalline core-shell synthesis with different kinds of MOFs.

Here, we demonstrate a protocol for the two-step synthesis of single-crystalline core-shells using a non-isostructural metal-organic framework (MOF) pair, HKUST-1 and MOF-5, which have well-matched crystal lattices.

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. ...

A Technical Guide for Performing Spectroscopic Measurements on Metal-Organic Frameworks

Metal-organic frameworks (MOFs) offer a unique platform to understand light-driven processes in solid-state materials, given their high structural tunability. However, the progression of MOF-based photochemistry has been hindered by the difficulty in spectrally characterizing these materials. Given that MOFs are typically larger than 100 nm in size, they are prone to excessive light scatter, thereby rendering data from valuable analytical tools like transient absorption and emission spectroscopy nearly uninterpretable. To gain meaningful insights of MOF-based photo-chemical and physical processes, special consideration must be taken toward properly preparing MOFs for spectroscopic measurements, as well as the experimental setups that garner higher quality data. With these considerations in mind, the present guide provides a general approach and set of guidelines for the spectroscopic investigation of MOFs. The guide addresses the following key topics: (1) sample preparation methods, (2) spectroscopic techniques/measurements with MOFs, (3) experimental setups, (3) control experiments, and (4) post-run stability characterization. With appropriate sample preparation and experimental approaches, pioneering advancements toward the fundamental understanding of light-MOF interactions are significantly more attainable.

Here, we use a polymer stabilizer to prepare metal-organic framework (MOF) suspensions that exhibit markedly decreased scatter in their ground-state and transient absorption spectra. With these MOF suspensions, the protocol provides various guidelines to characterize the MOFs spectroscopically to yield interpretable data.