ACS Catalysis
ACS Catalysis
5 years ago

Structural Transformation of Porous Polyoxometalate Frameworks and Highly Efficient Biomimetic Aerobic Oxidation of Aliphatic Alcohols

Structural Transformation of Porous Polyoxometalate Frameworks and Highly Efficient Biomimetic Aerobic Oxidation of Aliphatic Alcohols
Xian-Wei Zhang, Min Zhao, Chuan-De Wu
Due to their inherent inert nature, it is difficult to oxidize unactivated aliphatic alcohols with molecular oxygen under mild conditions. Inspired by enzymatic catalysis, numerous biomimetic systems have been therefore established. However, low catalytic efficiency and easy auto-oxidative deactivation nature remain the problematic issues. To meet these challenges, we report herein a 2D porous polyoxometalate (POM) framework Gd4(H2O)26[WZn{Cu(H2O)}2(ZnW9O34)2]·24H2O (CZJ-11) and a 3D porous POM framework Gd4(H2O)24[WZn{Cu(H2O)}2(ZnW9O34)2]·11H2O (CZJ-12) transferred from CZJ-11 by partial dehydration, consisting of scaffolded redox-active Cu(II) sites in the sandwich-type POM cluster [WZn{Cu(H2O)}2(ZnW9O34)2]12- (abbreviated as {Zn3Cu2W19}). To mimic the catalytic mechanism of enzymes, N-hydroxyphthalimide (NHPI) and tetramethylammonium bromide (TMAB) were introduced as cocatalysts, which performed as electron donor and electron-transfer mediator, respectively. The coupled catalyst systems demonstrate analogue properties with oxygenase enzymes in the aerobic oxidation of aliphatic alcohols under mild conditions. Compared with molecular POM counterpart and metalloporphyrins, the catalytic efficiency of these POM frameworks is predominant in aerobic oxidation of unactivated aliphatic alcohols by imitating the active sites and the catalytic mechanism of enzymes. Compared with metal–organic coordination complexes, such as metalloporphyrins, the pure inorganic frameworks offer significant superiority of robustness to auto-oxidation and simple recovery for recycling with retained high catalytic efficiency.

Publisher URL: http://dx.doi.org/10.1021/acscatal.7b01985

DOI: 10.1021/acscatal.7b01985

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.