Strong Metal‐Support Interactions through Sulfur‐Anchoring of Metal Catalysts on Carbon Supports

Abstract

In supported metal catalysts, the supports would strongly interact with the metal components instead of just acting as a carrier, which greatly affects both of their synthesis and catalytic activity, selectivity, and stability. Carbon is considered as very important but inert support and thus hard to induce strong metal-support interaction (SMSI). This mini-review highlights that sulfur-a documented poison reagent for metal catalysts-when doped in a carbon supports can induce diverse SMSI phenomenon, including electronic metal-support interaction (EMSI), classic SMSI, and reactive metal-support interaction (RMSI). These SMSI between metal and sulfur-doped carbon (SÀ C) supports enables the catalysts with extraordinary resistance to sintering at high temperatures of up to 1100 °C, which allows the general synthesis of single-atom, alloy cluster, and intermetallic compound catalysts with high dispersion and metal loading for a variety of applications.

Tailoring the Nonmetal Elements in Carbon-Based Single-Atom Catalysts toward Hydrogen Energy Catalysis

“…For M–S x –C structures, direct pyrolysis of sulfur-containing precursors and further anchoring of metal centers are undoubtedly the most convenient methods, especially for some sulfur-containing polymers with high thermal stability that can be directly pyrolyzed and carbonized into S–C carriers at high temperatures . The most critical point among them is the sulfur content of the S–C carrier, which directly determines the single-atom loading of the metal.…”

“…Different from N-doped carbon materials, this strong metal support interaction (SMSI) enables S–C materials to better disperse loaded precious metals . SMSI phenomena include electron metal–support interaction (EMSI), classical SMSI, and reactive metal–support interaction (RMSI).…”

Intermetallic Nanocrystals for Fuel-Cells-Based Electrocatalysis

“…Generally, the weak interaction between metal nanocrystals and supports tends to be caused by the intrinsically chemical inert carbon surface constituted of sp 2 or sp 3 hybridized carbon atoms. Doping heteroatoms into the crystal lattice of carbon matrix or inarching functional groups onto carbon surface can adjust the function of carbon supports, thus beneficial for regulating the interaction with supported nanocrystals. − The enhanced metal–support interaction can provide powerful adhesion strength between metal and optimized supports, thus generating outstanding unique antisintering properties, making intermetallics be more stable even at higher loading or higher annealing temperature. Using high-loading PtCo intermetallic nanoparticles as an example, the sintering resistance of a series of small molecule additives containing coordinating heteroatoms (O, N, and S) was investigated .…”

Controllable Porous Nanogrids of Chromium Nitride with Strong Metal–Support Interactions for Achieving Stable Oxygen Reduction Reaction

“…The reactant starvation brought on by the water flooding process, high potential brought on by repeated startup and shutdown cycles, and a cumulative temporal impact of long-term operation were determined to be the three primary causes of carbon corrosion in PEMFC. − This corrosion compromises the catalyst’s activity, resulting in negative impacts on the fuel cell’s performance. Moreover, the weak connection between the carbon support and Pt leads to the agglomeration of Pt nanoparticles (NPs), which results in decreased Pt utilization. , Although strategies such as heteroatom (e.g., S, N) doping have been explored to ameliorate this problem, the fundamental issue of carbon corrosion remains unresolved. − Therefore, there is plenty of interest in exploring substitute supports for ORR catalysts that exhibit an SMSI effect and excellent corrosion resistance.…”