The Catalyst Review December 2019 - 15

EXPERIMENTAL
Combined Alkali-Organoammonium Structure Direction of High-Charge-Density HeteroatomContaining Aluminophosphate Molecular Sieves...
Zeolite molecular sieves are crystalline microporous aluminosilicates of general formula A+[AlSinO2(n+1)], consisting of a charged
tetrahedral framework composed of [AlO4/2]- and [SiO4/2] units.
The structure-directing cations (A+), which are usually alkali and/
or organoammonium cations, reside in the pores, thus balancing
the framework charge. However, framework compositions
have now expanded to include aluminophosphate (AlPO4),
silicoalumino-phosphate (SAPO), metalloaluminophosphate
(MAPO), metallophosphate (A+M2+PO4), germanosilicate, and
silicate families of molecular sieves for the 239 known zeotype
topologies. Herein, the authors report the synthesis of new high
charge density SAPO and MAPO molecular sieves-specifically
SAPO-69 (OFF) and SAPO-79 (ERI) and zincoalumino-phosphate
PST-16 (CGS), PST-17 (BPH), PST-19 (SBS), and ZnAPO-88 (MER).
By enabling alkali-organoammonium structure direction in
these systems, they were able to provide a gateway to an even
larger region of compositional space than that conventionally
encompassed by zeolites (Figure 1).
Table 1 provides the representative reaction
formulations and conditions pursued in this
work along with the resulting products and
compositions. It is evident that a delicate
balance between the reaction charge density
(OH-/H3PO4) and the relative content of alkali
and organoammonium cations is necessary
to achieve a cooperative structure direction
is evident. In addition, the divergence of the
high-charge density (HCD) ZnAPO and SAPO
phases in both structure and incorporation
chemistry under the same reaction conditions
is evident.

Figure 1. a) MAPO phase diagram: AlPO4 black ■, MAPO black □, ACP black ×,
UCSB black ○, ZnAPO-57, -59, and -67 orange □, PST-16 blue □, PST-17 blue ∆,
PST-19 blue +, ZnAPO-88 blue ○, KZnAlP blue ■, ABW blue ●. b) SAPO phase
diagram: AlPO4 black ■, zeolites heavy black line, SAPO black ○, phosphate
zeolites black +, SAPO-59 and -67 orange □, SAPO-69 blue □, SAPO-79 blue ◊.
New species from this work are shown in blue, prior work in black. Cooperative
alkali-quaternary ammonium structure direction in SAPO and MAPO
compositions opens access to larger regions of compositional space than the
corresponding revolutionary advance in zeolite chemistry.

Table 1. Representative heteroatom-substituted aluminophosphate synthesis conditions and chemical
compositions of the resulting products.

The impact of these results is two-fold.
First, many new HCD heteroatom-containing
AlPO4-based molecular sieves can be
developed by applying the charge density
mismatch (CDM) concepts developed in
aluminosilicate chemistry and which have
been shown to be highly effective for achieving the cooperative alkali-organo-ammonium structure direction of such materials.
Second, with respect to the synthesis of even more complex HCD quaternary M2+-Al-P-Si systems, charge density principles can be
used to balance alkali-organoammonium efficacy in structure direction while also balancing the diverging Si and M2+ proclivities for
framework incorporation. Source: Seo S, Ahn NA, Lee JH, et al. (2019). Angew. Chem. Int. Ed., 58: 9032-9037.
From Immobilization to Catalyst Use: A Complete Continuous-Flow Approach Towards the Use of
Immobilized Organocatalysts...
The growing use of organocatalysis has done much to facilitate asymmetric synthesis by promoting high yields and
enantioselectivities for chemical transformations. However, these reactions often present challenging problems related to low
turnover and the impossibility of recovering the catalyst. To overcome these difficulties, efforts have been made to support the
organocatalysts on a range of solid materials, such as polymers or silica, facilitating heterogeneous reactions by allowing for
their usage in continuous-flow reactors. To overcome limitations associated with catalyst deactivation, the authors describe the
advantages of synthesizing and immobilizing an organo-catalyst under continuous-flow conditions and the impact of this method on
catalyst lifetime.
The Catalyst Review 										

December 2019

15



The Catalyst Review December 2019

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