Published April 17, 2024 | Version v3
Dataset Open

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

  • 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

* Contact person

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.

Files

File preview

files_description.md

All files

Files (61.1 MiB)

Name Apps Size
md5:e245f5a55a5dba2ce4a4ae47fb0844ac
1.8 KiB Preview Download
md5:3f1f769af8f50f9efacffa2791359107
6.5 KiB Preview Download
md5:dbf1118341b6add829acf456ce5cb44e
29.8 MiB Download
md5:0b2b945e3a53be0b2427f90a949d65e6
2.6 KiB Preview Download
md5:50a1086a5ecb8a7dbbc1a2cc86e766ef
25.8 KiB Download
md5:d98097fb743d73b81e6ff018be41cd90
532 Bytes Preview Download
md5:975889de3f7feeedf325722ffc0363c6
4.9 KiB Download
md5:08dc52e7b974a8588295c0da43c4456d
5.2 KiB Preview Download
md5:1d188c541180d5d0e89c03e96ff6e9df
54.4 KiB Download
md5:22ce2481629f337f5baf28295a55bbcf
14.2 MiB Download
md5:17b18d4463a4968259ecd92e7741650d
15.0 MiB Download
md5:ba8dd59211da763d9e9c80b9d5dcd87e
254.8 KiB Download
md5:97bf45727f379cb95189a200d515bef1
2.0 KiB Preview Download
md5:447288a70359334b9f9be3a0ab1db142
1.0 MiB Preview Download
md5:fdfd9ffc5c21583d92d1742369ca83b8
1.8 KiB Preview Download
md5:64128ee5d2b44ed2854639b9522715ef
756.1 KiB Download

References

Preprint (Preprint where the data is discussed.)
S. Das, R. Laplaza, J.T. Blaskovits, C. Corminboeuf, ChemRxiv (2023), doi: 10.26434/chemrxiv-2023-09mdd