Abstract

As the extremely-sized nanocrystals and nanopores, an adatom (M) and atomic vacancy (V₀) exhibit extraordinary capability of catalysis with however little knowledge about the catalyst-reactant interfacial bonding dynamics. With the aid of density functional theory calculations, we examined the dehydrogenization of a single CH₄ molecule catalyzed using the Rh(111,100), W(110), Ru(0001) surfaces, and monolayer graphene, with and without M or V0. It is uncovered in the following three components: (i) catalyst polarization due to atomic under- or hetero-coordination raises the valence band of the catalyst by bond contraction and atomistic dipolar (MP) and vacancy dipolar (V₀) formation; (ii) reactant bond elongation by the interplay of the (MP/V₀):H attraction and (MP/V₀):⇔C repulsion with the ":" denoting the negative pole of the MP/V0; and (iii) reactant conversion, i.e., the scale of H-C elongation, the catalyst valence-band shift, the adsorption energy, and the catalytic activity are proportional to the charge quantity of the MP/V₀ whose local electric field matters.

Abstract

As the extremely-sized nanocrystals and nanopores, an adatom (M) and atomic vacancy (V₀) exhibit extraordinary capability of catalysis with however little knowledge about the catalyst-reactant interfacial bonding dynamics. With the aid of density functional theory calculations, we examined the dehydrogenization of a single CH₄ molecule catalyzed using the Rh(111,100), W(110), Ru(0001) surfaces, and monolayer graphene, with and without M or V0. It is uncovered in the following three components: (i) catalyst polarization due to atomic under- or hetero-coordination raises the valence band of the catalyst by bond contraction and atomistic dipolar (MP) and vacancy dipolar (V₀) formation; (ii) reactant bond elongation by the interplay of the (MP/V₀):H attraction and (MP/V₀):⇔C repulsion with the ":" denoting the negative pole of the MP/V0; and (iii) reactant conversion, i.e., the scale of H-C elongation, the catalyst valence-band shift, the adsorption energy, and the catalytic activity are proportional to the charge quantity of the MP/V₀ whose local electric field matters.

Abstract

As the extremely-sized nanocrystals and nanopores, an adatom (M) and atomic vacancy (V₀) exhibit extraordinary capability of catalysis with however little knowledge about the catalyst-reactant interfacial bonding dynamics. With the aid of density functional theory calculations, we examined the dehydrogenization of a single CH₄ molecule catalyzed using the Rh(111,100), W(110), Ru(0001) surfaces, and monolayer graphene, with and without M or V0. It is uncovered in the following three components: (i) catalyst polarization due to atomic under- or hetero-coordination raises the valence band of the catalyst by bond contraction and atomistic dipolar (MP) and vacancy dipolar (V₀) formation; (ii) reactant bond elongation by the interplay of the (MP/V₀):H attraction and (MP/V₀):⇔C repulsion with the ":" denoting the negative pole of the MP/V0; and (iii) reactant conversion, i.e., the scale of H-C elongation, the catalyst valence-band shift, the adsorption energy, and the catalytic activity are proportional to the charge quantity of the MP/V₀ whose local electric field matters.

Abstract

As the extremely-sized nanocrystals and nanopores, an adatom (M) and atomic vacancy (V₀) exhibit extraordinary capability of catalysis with however little knowledge about the catalyst-reactant interfacial bonding dynamics. With the aid of density functional theory calculations, we examined the dehydrogenization of a single CH₄ molecule catalyzed using the Rh(111,100), W(110), Ru(0001) surfaces, and monolayer graphene, with and without M or V0. It is uncovered in the following three components: (i) catalyst polarization due to atomic under- or hetero-coordination raises the valence band of the catalyst by bond contraction and atomistic dipolar (MP) and vacancy dipolar (V₀) formation; (ii) reactant bond elongation by the interplay of the (MP/V₀):H attraction and (MP/V₀):⇔C repulsion with the ":" denoting the negative pole of the MP/V0; and (iii) reactant conversion, i.e., the scale of H-C elongation, the catalyst valence-band shift, the adsorption energy, and the catalytic activity are proportional to the charge quantity of the MP/V₀ whose local electric field matters.