Selectivity

Physics

Control engineering

Electron

Nanotechnology

Organic chemistry

Decoupling (probability)

Mathematics

Engineering

Catalysis

Mathematical analysis

Valence (chemistry)

Computational chemistry

Nanoparticle

Atomic orbital

Chemical physics

Inorganic chemistry

Chemistry

Materials science

Fermi level

Electronic effect

Quantum mechanics

Separable space

Redox

Electronic structure

Antibonding molecular orbital

Nature Communications

Decoupling the electronic and geometric effects has been a long cherished goal for heterogeneous catalysis due to their tangled relationship. Here, a novel orthogonal decomposition method is firstly proposed to settle this issue in p -chloronitrobenzene hydrogenation reaction on size- and shape-controlled Pt nanoparticles (NPs) carried on various supports. Results suggest Fermi levels of catalysts can be modulated by supports with varied work function ( W f ). And the selectivity on Pt NPs of similar size and shape is linearly related with the W f of support. Optimized Fermi levels of the catalysts with large W f weaken the ability of Pt NPs to fill valence electrons into the antibonding orbital of C–Cl bond, finally suppressing the hydrodehalogenation side reaction. Foremost, the geometric effect is firstly spun off through orthogonal relation based on series of linear relationships over various sizes of Pt NPs reflecting the electronic effect. Moreover, separable nested double coordinate system is established to quantitatively evaluate the two effects.

Decoupling the electronic and geometric effects of Pt catalysts in selective hydrogenation reaction