Name: hkust-1 as a heterogeneous catalyst for the synthesis of vanillin
Uploaded: 2016-07-23T14:00:00.000+00:00
Duration: 11 min 15 s
Description: Watch this Scientific Journal Video about HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin at JoVE.com

The authors thank Dr. A. Tejeda-Cruz (X-ray; IIM-UNAM). R.Y. thanks CINVESTAV, Mexico for technical support. M.S.S acknowledges the financial support by Spanish Government, MINECO (MAT2012-31127). I.A.I thanks CONACyT (212318) and PAPIIT UNAM (IN100415), Mexico for financial support. E.G-Z. thanks CONACyT (156801 and 236879), Mexico for financial support. Thanks to U. Winnberg (ITAM and ITESM) for scientific discussions.

주의 :이 촉매 적 절차에서 사용되는 화학 물질의 독성 및 비 - 발암 성이 비교적 낮다. 이러한 안전 안경, 장갑, 실험실 코트, 전체 길이 바지와 폐쇄 발가락 신발로이 실험 절차를 수행 할 때 모든 적절한 안전 예방 조치를 사용하십시오. 다음 절차 중 한 부분은 표준 공기가없는 처리 기술을 포함한다. 카탈리스트 1. 활성화 (HKUST-1) <ol><li> 카탈리스트의 결정의 특성 참고 HKUST-1 시판되는 다공성 배위 고분자 (촉매)이다. 촉매의 결정 성을 확증하기 위해, HKUST-1의 시료는 분말 X 선 회절 (PXRD)을 특징으로 할 필요가있다. <ol><li> 브래그-Brentano 기하학에서의 Cu-Kα 1 방사선 (λ = 1.5406 Å)에 대한 (160 W (40 kV의, 40mA)에서 작동하는 회절에) HKUST-1의 0.1 g 샘플의 PXRD 패턴을 수집합니다. 0.02 # 60 ° (2θ) 5 °에서 PXRD 패턴을 녹음(176); 단계 시간 44 카운트 1 초. </li></ol></li><li> HKUST-1의 탈 용매 <ol><li> 촉매 (HKUST-1) 0.05 g을 달아. </li><li> 스탠드에 250 ml의 두 구 둥근 바닥 플라스크를 고정하고 둥근 바닥 플라스크에 자기 교반 막대를 삽입합니다. </li><li> 둥근 바닥 플라스크에 콘덴서를 연결합니다. </li><li> 완벽한 밀봉을 생성하기 위해 플라스크 및 콘덴서의 관절 사이에 진공 그리스 또는 테프론 테이프를 사용합니다. </li><li> (호스에 꼭지를 통해) 진공 펌프로, 상단에서, 콘덴서를 연결합니다. </li><li> 펌프에 의해 생성 된 진공은 약 10-2 바 있는지 확인합니다. 참고의 편의를 위해,이 실험은 활성화 시스템으로 지칭 될 것이다 (진공 펌프에 접속되는 응축기에 연결된 두 구 둥근 바닥 플라스크)를 설정한다. </li><li> 250 ml의 두 구 둥근 바닥 플라스크 내부의 촉매 (0.05 g)을 놓습니다. </li><li> 의 두 번째 목에 고무 격막을 삽입둥근 바닥 플라스크는 (맞는)를 적절하게 밀봉해야합니다. </li><li> 조심스럽게, 모래 목욕으로 기동 시스템을 배치합니다. </li><li> 진공 펌프를 시작하고 완전히 열릴 때까지 조심스럽게 꼭지를 켭니다. 핫 플레이트로, 1 시간 동안 100 ° C에 정품 인증 시스템을 가열한다. </li><li> 환저 플라스크의 바닥에 균일하게 촉매를 분배하기 위해 핫 플레이트의 낮은 속도로 교반한다. </li><li> 난방 1 시간 후 열 (핫 플레이트)를 끄고 (진공)가 상온이되도록 기동 시스템을 할 수 있습니다. </li><li> 기동 시스템을 실온으로 냉각되면, 콕을 해제 (즉, 활성화 시스템은 수동 진공 하에서 것) 및 펌프를 끄지. </li><li> 두 구 둥근 바닥 플라스크에, 격벽을 통하여 질소로 채워진 벌룬 (N 2)를 연결하고 평형 압력에 도달 잠시 기다린다. 주 : 촉매의 활성화 후, 그것을 U두고파인더 불활성 분위기 (N 2) 조정되지 않은 금속 사이트 (또는 열린 금속 자리)에 접근하기 때문에 활성 촉매를 얻을 수있는 열쇠입니다. </li><li> 평형 압력이 달성 된 N 2, 가득 풍선을 제거합니다. 참고 : 청록색에서 컬러 변화를 (그대로 받아 HKUST-1) (정품 인증시) 짙은 파란색으로 관찰된다. </li></ol></li></ol> 이기종 촉매를 통해 바닐린 2. 합성 <ol><li> 유기 용매의 탈기 <ol><li> 5 분 동안 N이 버블 링에 의해 탈기 에탄올 약 70 ㎖에. </li></ol></li><li> 촉매 반응의 제조 <ol><li> 두 구 둥근 바닥 플라스크에 탈기 된 에탄올 10 ㎖를 첨가하고 부드럽게 핫 플레이트에서 현탁액을 교반 하였다. </li><li> 정지에 (H 2 O 30 %) H 5 ml의 2 O 2를 추가합니다. </li><li> 현탁액에 아세토 니트릴 0.25 ML을 추가합니다. </li><li> 페룰 산 0.50 g을 달아에 용해비커에 탈기 에탄올 20 ㎖. </li><li> 현탁액에 용해 된 페룰 산을 추가합니다. </li><li> 탈기 에탄올 20 mL로 비커를 씻고 정지에 추가합니다. </li></ol></li><li> 바닐린에 트랜스 페룰 산의 산화 <ol><li> 진공 펌프에 콘덴서를 연결하는 호스를 분리합니다. </li><li> 응축기를 통과 수돗물을 켭니다. 바람직하게는, 물 펌프를 사용한다. </li><li> 1 시간 동안 100 ° C (환류)에 서스펜션까지 가열한다. </li><li> 열 교반을 끕니다. 조심스럽게 (응축기에 부착 된) 두 구 둥근 바닥 플라스크를 들어 올려 실내 온도가 식지. </li></ol></li><li> 반응 작업 업 <ol><li> 반응 혼합물을 촉매 (HKUST-1), 복구 (흐너 깔때기 및 플라스크를 사용) 및 에틸 아세테이트 200 ㎖로 씻어 여과 해. 참고 : 빨리 복구합니다 (흐너 플라스크에 연결된)의 진공을 사용하여, 여과 과정을 단축하고, C를 세척하기 위해서는atalyst. </li><li> 제 1과 PXRD에 의해 촉매의 프레임 워크 결정의 유지를 확증. </li><li> (로타리 증발기로 감압 하), 합쳐진 유기 상을 농축시키고, 100ml의 에틸 아세테이트로 다시 그것을 녹인다. </li><li> NH 4 CL (30 ㎖)의 포화 용액으로 유기상을 (a 분리 깔때기를 사용하여) 세척 하였다. </li><li> 유기 상을 복구하고, 무수 나 2 SO 4 (30g)로 섞는다. 현탁액을 15 분 동안 서 보자. </li><li> 현탁액을 여과하고 여액을 복구 할 수 있습니다. </li><li> 회전 증발기로 감압 하에서 (약 20 ㎖까지), 여과 액을 농축시켰다. </li></ol></li><li> 잔류 물 (바닐린)의 정제 <ol><li> 플래시 칼럼 크로마토 그래피 (44)에 의해 잔류 물을 정제. 정지상은 실리카겔하고 이동상을 에틸 아세테이트 - 헥산 (5:95)의 용매 혼합물이다. </li><li> 실리카 겔 크로마토 그래피의 유리 컬럼 (1cm X 30cm)를 포장(1cm X 6cm). 아세테이트 - 헥산 (5:95) 혼합 용매에 열을 포화. </li><li> 조심스럽게 유리 컬럼의 상단에 집중-여과 액을 붓는다. </li><li> 천천히 유리 컬럼에 용매 혼합물을 추가하고 1,200 ml의가 수집 될 때까지 분수를 모두 수집합니다. </li><li> 건조 될 때까지 로타리 증발기로 유기 분획 (1200 ml)에 집중한다. </li><li> 정제 된 바닐린입니다 최종 고체 분말을 복구 할 수 있습니다. </li></ol></li></ol>

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The authors have nothing to disclose.

바닐린 트랜스 -ferulic 산의 촉매 변환을위한 기본적인 공정은 촉매 (HKUST-1)의 활성화이었다. 촉매 (진공하에 100 ℃에서) 반응계에서 활성화되지 않은 경우, 바닐린 트랜스 -ferulic 산의 일부만 변환 (44)이 관찰되었다. 즉, 금속 부위를 열 접근성 촉매 사이클 44 중요하고,이 다공질 코디 폴리머 내의 구리 (II)의 금속 사이트로 조정 된 물을 제거함으로써 달성 될 수...

불균일 촉매 1-4 다공성 배위 고분자 (의 PCP)를 사용하는 비교적 새로운 연구 분야이다. 의 PCP가 보여 매우 흥미로운 특성, 예를 들면, 다공성 규칙, 높은 표면적과 금속 접속으로 인해, 그들은 이종 촉매 5-6에 대한 새로운 대안을 제공 할 수 있습니다. 촉매 활성의 PCP의 생성은 여러 연구 그룹 7-10의 주요 초점이되어왔다. 다공성 배위 중합체 따라서 금속 이온 및 유기 결합제에 의해 구성되며, 이들 재료의 촉매 활성이 부품에 의해 제공된다. 일부의 PCP는 화학 반응 (11)을 촉매 할 수 불포화 (활성) 금속이 포함되어 있습니다. 그러나, 배위 중합체 내에 불포화 금속 자리 (개방 금속 자리)의 발생이 사소한 작업이 아니며은 요약 될 수있는 합성 도전 나타내고 : (I)의 불안정한 리간드 7-11 제거하여 빈 배위 생성하는 단계;(II) 유기 리간드 (이전 합성) 8,12-13를 통합하여 바이메탈의 PCP의 발생; (III) 금속 이온의 PCP의 세공 내에 9,14-15 또는 유기 리간드 (10), 16-17의 합성 후 변형. 방법론 (i)는 이와 같이 단순한이기 때문에 자주 사용이다. 일반적으로, 개방 된 금속 부위의 발생을 H 2 18-19 향해의 PCP의 친 화성을 ​​향상시킬뿐만 아니라, 활성 이종 촉매 20-27 설계에 사용되었다. 양호한 촉매 특성을 달성하기 위해, 추가의 PCP가 열려 금속 사이트, 반응 조건, 촉매의 실험 후에 결정 성의 유지, 상대적으로 높은 열적 안정성 및 화학적 안정성의 접근성에 표시 할 필요가있다. HKUST-1 (구리 3 (BTC) 2 (H 2 O) 3, BTC = 1,3,5- 벤젠 트리 카르 복실 레이트) (7)이카르 복실 리간드와 배위 물 구리 (II) 양이온으로 구성된 잘 조사 다공성 배위 중합체. 흥미롭게도,이 물 분자 (가열)을 제거하고,이 하드 루이스 산의 특성 (11)을 나타내는 구리 이온 주변의 정사각형 평면 조정을 제공 할 수있다. 보르디가와 협력자 (28)이 H 2 O 분자의 제거가 결정 성 (규칙 성 유지율) 및 금속 이온의 산화 상태 (구리 (II))의 영향을받지 한 영향을 미치지 않았 음을 보여 주었다. 촉매로서 HKUST-1의 사용은 광범위하고 특히 29-33 (본 연구에 매우 중요한) 방향족 분자 (34)의 과산화수소 산화 반응을 조사 하였다. 바닐라는 화장품, 의약품 및 식품 산업에서 가장 널리 사용되는 향미 제의 하나이다. 이것은 런 바닐라 planifolia, Vani의 경화 콩으로부터 추출LLA의 tahitiensis와 바닐라 퐁퐁. 이 초콜릿 맛 35-37을 개선하기 때문에 마야와 아즈텍 문명 (콜럼버스 명) 먼저 향미 제로서 바닐라의 엄청난 잠재력을 실현. 바닐라 제 1858 38 단리하며 바닐린의 화학 구조가 마침내 결정되었다 1874 39까지 없었다. (난초 바닐라 planifolia, 바닐라 tahitiensis와 바닐라 퐁퐁에서) 바닐린의 자연 추출은 전 세계 생산량의 1 %를 나타내며,이 과정이 비싸고 (40) 매우 긴이기 때문에, 바닐린의 나머지 (40)를 합성된다. 많은 생물 공학적 접근 그러나, 이러한 방법은 이들 방법은 강한 산화제 독성 용매 41-43를 사용하기 때문에 환경을 해치지 단점이 등 리그닌 페놀 스틸 벤, 이소 유게 놀, 유게 놀, guaicol에서 바닐린의 합성에 사용될 수있다. 여기서, 우리는 r에촉매 HKUST-1을 사용하여 트랜스 -ferulic 산의 산화에 의해 바닐린의 제조 합성 전략 eport.

<table><tbody><tr><td>HKUST-1</td><td>Sigma-Aldrich</td><td>MFCD10567003</td><td></td></tr><tr><td>Ferulic Acid (trans-4-Hydroxy-3-methoxycinnamic acid)</td><td>Sigma-Aldrich</td><td>537-98-4</td><td></td></tr><tr><td>Ethanol</td><td>Sigma-Aldrich</td><td>64-17-5</td><td></td></tr><tr><td>Hydrogen peroxide solution</td><td>Sigma-Aldrich</td><td>7722-84-1</td><td></td></tr><tr><td>Acetonitrile</td><td>Sigma-Aldrich</td><td>75-05-8</td><td></td></tr><tr><td>Ethyl acetate</td><td>Sigma-Aldrich</td><td>141-78-6</td><td></td></tr><tr><td>Ammonium chloride</td><td>Sigma-Aldrich</td><td>12125-02-9</td><td></td></tr><tr><td>Sodium sulfate anhydrous</td><td>Sigma-Aldrich</td><td>7757-82-6</td><td></td></tr><tr><td>Ethyl acetate</td><td>Sigma-Aldrich</td><td>141-78-6</td><td></td></tr><tr><td>n-Hexane</td><td>Sigma-Aldrich</td><td>110-54-3</td><td></td></tr><tr><td>Silica Gel</td><td>Sigma-Aldrich</td><td>112926-00-8</td><td>Size 70/230</td></tr><tr><td>250 ml two-neck round-bottom flask</td><td>Sigma-Aldrich</td><td>Z516872-1EA</td><td>250 ml capacity</td></tr><tr><td>Magnetic stirring bar</td><td>Bel-Art products</td><td>371100002</td><td>Teflon, octagon</td></tr><tr><td>Condenser</td><td>Cole-Parmer</td><td>JZ-34706-00</td><td>200 mm Jacket length</td></tr><tr><td>Vacuum pump (Approx. 10&lt;sup&gt;-2&lt;/sup&gt; bar)</td><td>Cole-Parmer</td><td>JZ-78162-00</td><td>Vacuum/Pressure Diaphragm Pump</td></tr><tr><td>Stopcock</td><td>Cole-Parmer</td><td>EW-30600-00</td><td>with a male Luer slip</td></tr><tr><td>Hose</td><td>Cole-Parmer</td><td>JZ-06602-04</td><td>16.0 mm ID and 23.2&amp;nbsp;mm ED</td></tr><tr><td>Rubber septums</td><td>Cole-Parmer</td><td>JZ-08918-34</td><td>Silicone with PTFE coating</td></tr><tr><td>Hot plate</td><td>Cole-Parmer</td><td>JZ-04660-15</td><td>10.2 cm x 10.2 cm, 5 to 540 &amp;deg;C</td></tr><tr><td>Sand bath</td><td>Cole-Parmer</td><td>GH-01184-00</td><td>Fluidized Sand Bath SBS-4, 50 to 600 &amp;deg;C</td></tr><tr><td>N&lt;sub&gt;2&lt;/sub&gt; gas</td><td>INFRA</td><td>Cod. 103</td><td>Cylinder 9&amp;nbsp;m&lt;sup&gt;3&lt;/sup&gt;</td></tr><tr><td>Ballons (filled with N&lt;sub&gt;2&lt;/sub&gt; gas)</td><td>Sigma-Aldrich</td><td>Z154989-100EA</td><td>Thick-wall, natural latex rubber</td></tr><tr><td>Syringes with removable needles</td><td>Sigma-Aldrich</td><td>Z116912-100EA</td><td>10 ml capacity</td></tr><tr><td>Filter paper</td><td>Cole-Parmer</td><td>JZ-81050-24</td><td>Grade No. 235 qualitative filter paper (90 mm diameter disc)</td></tr><tr><td>Buchner funnel</td><td>Cole-Parmer</td><td>JZ-17815-04</td><td>320 ml capacity which accept standard paper filter sizes</td></tr><tr><td>Buchner flask</td><td>Cole-Parmer</td><td>JZ-34557-02</td><td>250 ml capacity</td></tr><tr><td>Rotary Evaporator</td><td>Cole-Parmer</td><td>JZ-28710-02</td><td></td></tr><tr><td>Beakers</td><td>Cole-Parmer</td><td>JZ-34502-(02,04,05)</td><td>Pyrex Brand 1000 Griffin; 20, 50 and 100 ml</td></tr><tr><td>Separation funnel&amp;nbsp;</td><td>Cole-Parmer</td><td>JZ-34505-44</td><td>Capacity for 125 ml with steam length of 60 mm</td></tr><tr><td>Glass column for chromatography</td><td>Cole-Parmer</td><td>JZ-34695-42</td><td>Column with fritted disk, 10.5 mm ID x 250 mm L</td></tr><tr><td>PXRD diffractometer</td><td>Bruker</td><td></td><td>AXS D8 Advance XRD</td></tr><tr><td>FTIR spectrophotometer</td><td>Thermo scientific</td><td>FT-IR (JZ-83008-02); ATR (JZ-83008-26)</td><td>Nicolet iS5 FT-IR Spectrometer, with KBr Windows and iD5 Diamond ATR</td></tr></tbody></table>

hkust-1 as a heterogeneous catalyst for the synthesis of vanillin

바닐린 (4- 하이드 록시 -3- 메 톡시)는 바닐라 콩 추출물의 주요 성분이다. 천연 바닐라 향기 바닐린 이외에 약 200 취제 다른 화합물의 혼합물이다. (난초 바닐라 planifolia, 바닐라 tahitiensis와 바닐라 퐁퐁에서) 바닐린의 자연 추출은 전 세계 생산량의 1 %를 나타내며,이 과정은 비용이 매우 긴이기 때문에, 바닐린 생산의 나머지 부분은 합성된다. 많은 생물 공학적 방법이 프로세스가 강한 산화제 독성 용매를 사용하기 때문에 환경을 해치지 단점과, 리그닌 등의 페놀 스틸 벤, 이소 유게 놀, 유게 놀, guaicol에서 바닐린의 합성에 사용될 수있다. 따라서, 바닐린 생산에 환경 친화적 인 대안은 현재 조사에서 매우 바람직하므로 있습니다. 다공성 배위 고분자 (의 PCP)는 그 녹화 높은 결정 성 물질의 새로운 클래스입니다고한다면 촉매에 사용되어왔다. HKUST-1 (구리 3 (BTC) 2 (H 2 O) 3, BTC = 1,3,5- 벤젠 트리 카르 복실 레이트)을 광범위 불균일 촉매로서 검토되고있다 매우 잘 알려진 PCP이다. 여기서는 촉매 HKUST-1을 사용하여 트랜스 -ferulic 산의 산화에 의해 바닐린의 제조 합성 전략을보고한다.

오븐에서 1 시간 동안 100 ℃에서 활성화 된 비 - 활성화는 (공기에 노출), 1 100 ℃에서 진공 (10-2 바)하에 활성화 : HKUST-1 세 대표적인 샘플을 적외선 분광법으로 분석 하였다 시간. 따라서, 푸리에 변환 적외선 (FTIR) 스펙트럼은 하나의 반사 다이아몬드 ATR 액세서리 (그림 1)와 분광계를 사용하여 기록 하였다 변환. 모든 스펙트럼의 경우, 4000 ~ 400 cm -1</...

Watch this Scientific Journal Video about HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin at JoVE.com

HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained.

HKUST 바닐린-1의 합성에 대해 불균일 촉매로서

Vanillin (4-hydoxy-3-methoxybenzaldehyde) is the main component of the extract of vanilla bean. The natural vanilla scent is a mixture of approximately ...

hkust-1-as-a-heterogeneous-catalyst-for-the-synthesis-of-vanillin

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JoVE Journal

Chemistry

10.1K 조회수.  Autonomous Metropolitan University-Azcapotzalco. The conversion of trans-ferulic acid to vanillin was achieved by heterogeneous catalysis. HKUST-1 was employed in this synthesis and the essential step in the catalytic process was the generation of unsaturated metal sites. Thus, when the catalyst was activated under vacuum, full vanillin conversion (yield of 95%) was obtained. 

비디오: HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin

Highly Stereoselective Synthesis of 1,6-Ketoesters Mediated by Ionic Liquids: A Three-component Reaction Enabling Rapid Access to a New Class of Low Molecular Weight Gelators

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form catalytically active N-Heterocyclic Carbenes (NHCs). Here we have used ILs as precatalysts in the addition of &#945;,&#946;-unsaturated aldehydes to chalcones to form 1,6-ketoesters, incorporating an anti-diphenyl moiety in a highly stereoselective fashion. The reaction has a broad substrate scope and several functional groups and heteroaromatics can be integrated into the ketoester backbone in generally good yields with maintained stereoselectivity. The reaction protocol is robust and scalable. The starting materials are inexpensive and the products can be obtained after simple filtration, avoiding solvent-demanding chromatography. Furthermore, the IL can be recycled up to 5 times without any loss of reactivity. Moreover, the 1,6-ketoester end product is a potent gelator in several hydrocarbon based solvents. The method enables rapid access to and evaluation of a new class of low molecular weight gelators (LMWGs) from recyclable and inexpensive starting materials.

Ionic liquids (ILs) mediate fast, simple and cheap access to 1,6-ketoesters in high diastereoselectivities and good yields. The reaction protocol is robust and the 1,6-ketoesters can be obtained in gram scale after a simple filtration protocol. Moreover, the 1,6-ketoesters are potent gelators in hydrocarbon solvents.

이온 성 액체에 의해 매개 1,6- Ketoesters의 높은 입체 선택적 합성 : 저 분자량 젤 레이터의 새로운 클래스에 빠른 액세스를 가능하게하는 3 요소 반응

In organic chemistry ionic liquids (ILs) have emerged as safe and recyclable reaction solvents. In the presence of a base ILs can be deprotonated to form ...

연구

화학

Temperature-programmed Deoxygenation of Acetic Acid on Molybdenum Carbide Catalysts

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization, and hydrogenation). The results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 &#176;C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 &#176;C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 &#176;C.

Presented here is a protocol for the operation of a micro-scale temperature-programmed reactor for evaluating the catalytic performance of molybdenum carbide during acetic acid deoxygenation.

몰리브덴 초경 촉매에 초산의 온도 프로그램 탈산 소화

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system ...

Synthesis and Testing of Supported Pt-Cu Solid Solution Nanoparticle Catalysts for Propane Dehydrogenation

A convenient method for the synthesis of bimetallic Pt-Cu catalysts and performance tests for propane dehydrogenation and characterization are demonstrated here. The catalyst forms a substitutional solid solution structure, with a small and uniform particle size around 2 nm. This is realized by careful control over the impregnation, calcination, and reduction steps during catalyst preparation and is identified by advanced in situ synchrotron techniques. The catalyst propane dehydrogenation performance continuously improves with increasing Cu:Pt atomic ratio.

A convenient method for the synthesis of 2 nm supported bimetallic nanoparticle Pt-Cu catalysts for propane dehydrogenation is reported here. In situ synchrotron X-ray techniques allow for the determination of the catalyst structure, which is typically unobtainable using laboratory instruments.

프로판 탈수 소화를위한 Pt-Cu 고용체 나노 입자 촉매 합성 및 시험

A convenient method for the synthesis of bimetallic Pt-Cu catalysts and performance tests for propane dehydrogenation and characterization are ...

Nanosponge Tunability in Size and Crosslinking Density

We describe a protocol for the synthesis of linear polyesters containing pendant epoxide functionality and their incorporation into a nanosponge with controlled dimensions. This approach begins with synthesis of a functionalized lactone which is key to the pendant functionalization of the resulting polymer. Valerolactone (VL) and allyl-valerolactone (AVL) are then copolymerized using ring-opening polymerization. Post-polymerization modification is then used to install an epoxide moiety on some or all of the pendant allyl groups. Epoxy-amine chemistry is employed to form nanoparticles in a dilute solution of both polymer and small molecule diamine crosslinker based on the desired nanosponge size and crosslinking density. Nanosponge sizes can be characterized by transmission electron microscopy (TEM) imaging to determine the dimension and distribution. This method provides a pathway by which highly tunable polyesters can create tunable nanoparticles, which can be used for small molecule drug encapsulation. Due to the nature of the backbone, these particles are hydrolytically and enzymatically degradable for a controlled release of a wide range of hydrophobic small molecules.

This article describes a process for tuning the size and crosslinking density of covalently crosslinked nanoparticles from linear polyesters containing pendant functionality. By tailoring synthesis parameters (polymer molecular weight, pendant functionality incorporation, and crosslinker equivalents), a desired nanoparticle size and crosslinking density can be achieved for drug delivery applications.

Nanosponge Tunability 크기와 가교 밀도

We describe a protocol for the synthesis of linear polyesters containing pendant epoxide functionality and their incorporation into a nanosponge with ...

Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst removal via host-guest interactions. The new NHC ligand possesses an adamantyl (guest) tethered linear ethylene glycol units for hydrophobic inclusion into the cavity of a &#946;-cyclodextrin (&#946;-CD) host compound. The new NHC ligand was applied to a Ru-based olefin metathesis catalyst. The Ru catalyst demonstrated excellent activity in representative ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions in aqueous media as well as organic solvent, CH2Cl2. After the reaction was complete, the lingering Ru residue was removed from the aqueous solution with the efficiency of more than 99% (53 ppm of Ru residue) by simple filtration utilizing a host-guest interaction between insoluble silica-grafted &#946;-CD (host) and the adamantyl moiety (guest) on the catalyst. The new Ru catalyst also demonstrated high removal efficiency via extraction when the reaction is run in organic solvent by partitioning the crude reaction mixture between layers of diethyl ether and water. In this way, the catalyst stays in aqueous layer only. In organic layer, the residual Ru amount was only 0.14 ppm in the RCM reactions of diallyl compounds.

A removable water-soluble N-heterocyclic carbene (NHC) ligand in aqueous media via host-guest interaction has been developed. We demonstrated representative olefin metathesis reactions in water as well as in dichloromethane. Via either host-guest interaction or extraction, the residual ruthenium (Ru) catalyst was as low as 0.14 ppm after the reaction.

호스트-게스트 상호 작용을 통해 수성 매체에서 수용 성 루 테 늄 올레 Metathesis 촉매의 다른 유형의 제거

A highly efficient transition metal catalyst removal method is developed. The water-soluble catalyst contains a newly-designed NHC ligand for the catalyst ...

Tuning the Acidity of Pt/ CNTs Catalysts for Hydrodeoxygenation of Diphenyl Ether

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid nanosheets, a series of Pt/xHMNO6/CNTs with different solid acid compositions (x = 5, 20 wt%; M = Nb, Ta; N = Mo, W) have been prepared by carbon nanotube pretreatment, protonic exchange, solid acid exfoliation, aggregation and finally Pt particles impregnation. The Pt/xHMNO6/CNTs are characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and NH3-temperature programmed desorption. The study revealed that HNbWO6 nanosheets were attached on CNTs, with some edges of the nanosheets being bent in shape. The acid strength of the supported Pt catalysts increases in the following order: Pt/CNTs &#60; Pt/5HNbWO6/CNTs &#60; Pt/20HNbMoO6/CNTs &#60; Pt/20HNbWO6/CNTs &#60; Pt/20HTaWO6/CNTs. In addition, the catalytic hydroconversion of lignin-derived model compound: diphenyl ether using the synthesized Pt/20HNbWO6 catalyst has been investigated.

A protocol for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs is presented.

디페닐 에테르의 수산화를 위한 Pt/CNTs 촉매의 산도 튜닝

We herein present a method for the synthesis of HNbWO6, HNbMoO6, HTaWO6 solid acid nanosheet modified Pt/CNTs. By varying the weight of various solid acid ...

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

CO2 transformations using a one-pot two-step method are presented herein. The purpose of the method is to give access to a variety of value-added products and notably to generate chiral carbon centers. The crucial first step consists in the selective double hydroboration of CO2 catalyzed by an iron hydride complex. The product obtained with this 4 e- reduction is a rare bis(boryl)acetal, compound 1, which is subjected in situ to three different reactions in a second step. The first reaction concerns a condensation reaction with (diisopropyl)phenylamine affording the corresponding imine 2. In the second and third reaction, intermediate 1 reacts with triazol-5-ylidene (Enders&#39; carbene) to afford compounds 3 or 4, depending on the reaction conditions. In both compounds, C-C bonds are formed, and chiral centers are generated from CO2 as the only source of carbon. Compound 4 exhibits two chiral centers obtained in a diastereoselective manner in a formose-type mechanism. We proved that the remaining boryl fragment plays a key role in this unprecedented stereocontrol. The interest of the method stands on the reactive and versatile nature of 1, giving rise to various complex molecules from a single intermediate. The complexity of a two-step method is compensated by the overall short reaction time (2 h for the larger reaction time), and mild reaction conditions (25 &#176;C to 80 &#176;C and 1 to 3 atm of CO2).

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

CO2 transformations are conducted in a one-pot two-step procedure for the synthesis of complex molecules. The selective 4 e- reduction of CO2 with a hydroborane reductant affords a reactive and versatile bis(boryl)acetal intermediate which is subsequently involved in condensation reaction or carbene-mediated C-C coupling generation.

다재다능한CO2를 복합 제품으로 전환: 원포트 2단계 전략

CO2 transformations using a one-pot two-step method are presented herein. The purpose of the method is to give access to a variety of value-added products ...

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 ...

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Ligands like amines are used in the colloidal synthesis approach to protect platinum nanoparticles (Pt NP&#39;s) from agglomeration. Normally, ligands like amines are removed by diverse pre-treatment procedures before use in heterogeneous catalysis as amines are considered as a catalyst poison. However, a possible beneficial influence of these surface modifiers on hydrogenation reactions, which is known from spectator species on metal surfaces, is often neglected.
Therefore, amine-stabilized Pt nanoparticles supported by titania (P25) were used without any pre-treatment in order to elucidate a possible influence of the ligand in liquid phase hydrogenation reactions. The catalytic activity of amine-stabilized Pt nanoparticles of two different sizes was investigated in a double-walled stirring tank reactor at 69 &#176;C to 130 &#176;C and 1 atm hydrogen pressure. The conversion of cyclohexene to cyclohexane was determined by gas chromatography (GC) and was compared to ligand-free Pt particles. All catalysts were checked before and after reaction by transmission electron spectroscopy (TEM) and X-ray photoelectron spectroscopy (XPS) for possible changes in size, shape, and ligand shell. The hydrogenation of cyclohexene in liquid phase revealed a higher conversion for amine-stabilized Pt nanoparticles on titania than the ligand-free particles. The hydrogenation of 5-methylfurfural (5-MF) was chosen for a further test reaction, since the hydrogenation of &#945;, &#946;-unsaturated aldehydes is more complex and exhibits various reaction paths. However, XPS and infrared spectroscopy (IR) proved that 5-MF acts as catalyst poison at the given reaction conditions.

This protocol shows a convenient method for comparing the catalytic properties of supported platinum catalysts, synthesized by deposition of nanosized colloids or by impregnation. The hydrogenation of cyclohexene serves as a model reaction to determine the catalytic activity of the catalysts.

알켄과 알데히드의 수소화 동안 티타니아에 지지된 아민 안정화 및 리간드가 없는 백금 나노입자에서의 촉매 반응

Ligands like amines are used in the colloidal synthesis approach to protect platinum nanoparticles (Pt NP&#39;s) from agglomeration. Normally, ligands ...

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. ...