Shubhajit Das¹, Ruben Laplaza^1,2, J. Terence Blaskovits¹, Clemence Corminboeuf^1,2*

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:90-b6 [version v3]

Publication date: Apr 17, 2024

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 2024.58 (2024), https://doi.org/10.24435/materialscloud:90-b6

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.

Materials Cloud sections using this data

Files

File name	Size	Description
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.
README.txt MD5md5:fdfd9ffc5c21583d92d1742369ca83b8	1.8 KiB	README file detailing the contents of this record.
I2-BPh2-final_chemiscope.json.gz MD5md5:1d188c541180d5d0e89c03e96ff6e9df Visualize on Chemiscope	54.4 KiB	Chemiscope file containing the properties and structures of the final BPh2 functionalized linkers.
I2-BMe2-final_chemiscope.json.gz MD5md5:975889de3f7feeedf325722ffc0363c6 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 MD5md5:50a1086a5ecb8a7dbbc1a2cc86e766ef Visualize on Chemiscope	25.8 KiB	Chemiscope file containing the properties and structures of the final BBN functionalized linkers.
I2-BPh2-final.csv MD5md5:08dc52e7b974a8588295c0da43c4456d	5.2 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 MD5md5:17b18d4463a4968259ecd92e7741650d	15.0 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.
predicted_PLD.csv MD5md5:447288a70359334b9f9be3a0ab1db142	1.0 MiB	Predicted PLD for the functionalized linkers.
mofs.tar.gz MD5md5:ba8dd59211da763d9e9c80b9d5dcd87e	254.8 KiB	Compressed file with all the CIF files of the MOFs containing functionalized linkers.
mofs_data.csv MD5md5:97bf45727f379cb95189a200d515bef1	2.0 KiB	CSV file containing the tabulated properties for the MOFs containing functionalized linkers.

License

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Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

External references

Keywords

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