Publisher: American Chemical Society (ACS)

Issue: 9

License: [{"start"=>{"date-parts"=>[[2017, 8, 9]], "date-time"=>"2017-08-09T00:00:00Z", "timestamp"=>1502236800000}, "content-version"=>"vor", "delay-in-days"=>0, "URL"=>"http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html"}]

Publication date(s): 2017/09/01 (print) 2017/08/09 (online)

Pages: 5887-5902

Volume: 7 Issue: 9

Journal: ACS Catalysis

Link: [{"URL"=>"http://pubs.acs.org/doi/pdf/10.1021/acscatal.7b01646", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"}, {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acscatal.7b01646", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

URL: http://dx.doi.org/10.1021/acscatal.7b01646

The ability to generate nanoscale zeolites and direct their assembly into hierarchical structures offers a promising way to maximize their diffusion-dependent catalytic performance. Herein, we report an orientated assembly strategy to construct hierarchical architectures of silicoaluminophosphates (SAPOs) by using prefabricated nanocrystallites as a precursor. Such a synthesis is enabled by interrupting the dry gel conversion process to prepare nanocrystallites, as crystal growth is shown to proceed predominantly by particle attachment. The orientation of assembly can be controlled to form either a three-dimensional, spongelike morphology or a two-dimensional “house-of-cards” structure, by modifying the additives. Structures with a high degree of control over crystal size, shape, architecture, pore network, and acidic properties are achieved. This versatile technique avoids the more tedious and expensive templating routes that have been proposed previously. The catalytic performance for the hydroisomerization of n-heptane was evaluated for a series of Pt-supported catalysts, and a record isomer yield (79%) was attained for a catalyst with spongelike architecture. The hierarchical architecture influences isomer selectivity for two reasons: expanding the intrinsic-reaction-controlled regime to be able to work at higher temperatures or conversion levels, and enhancing mass transport to reduce cracking of dibranched isomers. Such an acidity–diffusivity interplay indicates that strong acidity favors isomerization operating at temperatures away from the diffusion-limited regime, while crystal size and pore connectivity are key factors for enhancing diffusion. The proposed materials offer tremendous opportunities to realize hierarchical catalyst designs that work under optimal operating conditions.