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Engineering frustrated lewis pair active sites in porous organic scaffolds for catalytic CO₂ hydrogenation

Shubhajit Das1, Ruben Laplaza1,2, J. Terence Blaskovits1, Clemence Corminboeuf1,2*

1 Laboratory for Computational Molecular Design (LCMD), Institute of Chemical Sciences and Engineering (ISIC), École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

2 National Center for Competence in Research – Catalysis (NCCR-Catalysis), Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

* Corresponding authors emails: clemence.corminboeuf@epfl.ch
DOI10.24435/materialscloud:31-wz [version v1]

Publication date: Apr 18, 2023

How to cite this record

Shubhajit Das, Ruben Laplaza, J. Terence Blaskovits, Clemence Corminboeuf, Engineering frustrated lewis pair active sites in porous organic scaffolds for catalytic CO₂ hydrogenation, Materials Cloud Archive 2023.66 (2023), https://doi.org/10.24435/materialscloud:31-wz

Description

Frustrated Lewis pairs (FLPs), featuring reactive combinations of Lewis acids and Lewis bases, have been utilized for myriad metal-free homogeneous catalytic processes. Immobilizing the active Lewis sites to a solid support, especially to porous scaffolds, has shown great potential to ameliorate FLP catalysis by circumventing some of its inherent drawbacks, such as product separation and catalyst recyclability. Nevertheless, designing immobilized Lewis pair active sites (LPASs) is challenging due to the requirement of placing the donor and acceptor centers in appropriate geometric arrangements while maintaining the necessary chemical environment to perform catalysis, and clear design rules have not yet been established. In this work, we formulate simple guidelines to build highly active LPASs for direct catalytic hydrogenation of CO₂ through a large-scale screening of a diverse library of 25,000 immobilized FLPs. The library is built by introducing boron-containing acidic sites in the vicinity of the existing basic nitrogen sites of the organic linkers of metal-organic frameworks collected in a "top-down" fashion from an experimental database. The chemical and geometrical appropriateness of these LPASs for CO₂ hydrogenation is determined by evaluating a series of simple descriptors representing the intrinsic strength (acidity and basicity) of the components and their spatial arrangement in the active sites. Analysis of the leading candidates enables the formulation of pragmatic and experimentally-relevant design principles and they constitute the starting point for further exploration of FLP-based catalysts for the reduction of CO₂.

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Files

File name Size Description
README.txt
MD5md5:d68d80db815226438d37f78c103de3ba
1.4 KiB README file detailing the contents of this record.
I2-BPh2-final_chemiscope.json.gz
MD5md5:54514429171569ae3472ea159d184cbb
Visualize on Chemiscope
57.7 KiB Chemiscope file containing the properties and structures of the final BPh2 functionalized linkers.
I2-BMe2-final_chemiscope.json.gz
MD5md5:2051f8702b5c42c3046f3fbe43b3a0f1
Visualize on Chemiscope
4.9 KiB Chemiscope file containing the properties and structures of the final BMe2 functionalized linkers.
I2-BBN-final_chemiscope.json.gz
MD5md5:66ba60e0a3024cad111f39cf3b66d140
Visualize on Chemiscope
25.8 KiB Chemiscope file containing the properties and structures of the final BBN functionalized linkers.
I2-BPh2-final.csv
MD5md5:635f6deebd73b7c4ab6566bf3557f3d9
5.6 KiB CSV file containing the tabulated properties for the final BPh2-functionalized linkers.
I2-BMe2-final.csv
MD5md5:d98097fb743d73b81e6ff018be41cd90
532 Bytes CSV file containing the tabulated properties for the final BMe2-functionalized linkers.
I2-BBN-final.csv
MD5md5:0b2b945e3a53be0b2427f90a949d65e6
2.6 KiB CSV file containing the tabulated properties for the final BBN-functionalized linkers.
I2.tar.gz
MD5md5:22ce2481629f337f5baf28295a55bbcf
14.2 MiB Compressed file with all the XYZ files of the filtered, pre and post screened I2 of the functionalized linkers.
LPAS.tar.gz
MD5md5:b4df3718fe70c9456697cc53415a175c
16.4 MiB Compressed file with all the XYZ files of the filtered functionalized linkers.
DL-database.tar.gz
MD5md5:dbf1118341b6add829acf456ce5cb44e
29.8 MiB Compressed file with all the XYZ files of the functionalized linkers.
seed-database.tar.gz
MD5md5:64128ee5d2b44ed2854639b9522715ef
756.1 KiB Compressed file with all the XYZ files of the initial N-containing linkers.
chemiscopify.ipynb
MD5md5:3f1f769af8f50f9efacffa2791359107
6.5 KiB Notebook exemplifying how the provided XYZ structures and csv files can be combined to generate the Chemiscope json files.

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

Keywords

catalysis volcano plot frustrated lewis pairs molecular catalysts metal-organic frameworks EPFL

Version history:

2024.15 (version v2) Jan 29, 2024 DOI10.24435/materialscloud:dq-z3
2023.66 (version v1) [This version] Apr 18, 2023 DOI10.24435/materialscloud:31-wz