Low-dimensional non-metal catalysts: principles for regulating p-orbital-dominated reactivity

Abstract

Activation of p-block elements to replace the rare and precious transition metals for renewable energy applications is highly desirable. In this review, we go over recent experimental and theoretical progress on the low-dimensional non-metal materials for clean energy production, including carbon, silicon, oxide, boron, and phosphorus-based nanostructures, with the p-block elements serving as active sites. We aim to elucidate the mechanism for triggering activity in different kinds of non-metal systems, and extract general principles for controlling the p-orbital-mediated reactivity from a theoretical point of view. The perspectives and challenges for developing high-efficiency non-metal catalysts are provided in the end.

P-block tin single atom catalyst for improved electrochemistry in a lithium–sulfur battery: a theoretical and experimental study

“…1b, the projected density of states (PDOS) of N and C have changed upon single Sn atom incorporation. The p band centers ( ε p ) of the p-block elements were calculated by the following formula 46 where D ( E ) is the density of states from the p orbitals of the p-block atoms at a given energy E ; the integral is taken for all occupied states.…”

“…45 Compared with the d-block transition metal elements, the p-block elements show outstanding stability due to the poor electronic flexibility. 46 Surface engineering, like the N-doped carbon supported single p-block metal atom materials, offers a wealth of pathways for activating p-block materials. 46 It should be noted that main group p-block metal-based SACs have never been considered for catalyzing the Li–S electrochemistry.…”

“…46 Surface engineering, like the N-doped carbon supported single p-block metal atom materials, offers a wealth of pathways for activating p-block materials. 46 It should be noted that main group p-block metal-based SACs have never been considered for catalyzing the Li–S electrochemistry. In fact, due to the fully occupied d bands, the p-block metals routinely display limited surface catalytic reactivity, leading to much fewer studies for electrocatalysis applications.…”

A theoretical roadmap for the best oxygen reduction activity in two-dimensional transition metal tellurides

“…50,[65][66][67][68][69][70] As we already know that the partially filled pz orbital is responsible for the Te-O interactions upon O2 adsorption, we introduced a descriptor εpz defined as a centroid of the projected density of states of the pz orbital relative to the Fermi level analog to d-band center. [71][72][73][74][75] As presented in Figure 4c-d, εpz of the active Te atoms shows reasonable linear relationship to the adsorption energies of O2 and intermediate oxygen-containing adsorbates. The linear relationships between ΔGO2 and other possible descriptors, such as the p-band center εp, are also calculated as shown in Figure S18, all of which are inferior to that of εpz.…”

Single‐Atom Catalysts for Hydrogen Generation: Rational Design, Recent Advances, and Perspectives

“…In fact, the p‐block elements lacking electronic flexibility and tend to certain oxidation states may endow the prepared catalysts with attractive stability and adjustability. [ 77 ] The light p‐block with natural abundance and low toxicity, such as carbon, oxygen, nitrogen, sulfur, or phosphorus, are ideal candidates for the fabrication of heteroatom‐doped catalysts. Introducing heteroatoms (such as N, S, P) into the supports has been proved an efficient strategy for regulating the coordination environment.…”