Strong Metal Phosphide–Phosphate Support Interaction for Enhanced Non‐Noble Metal Catalysis

Abstract

Strong metal‐support interaction (SMSI) is crucial for supported catalysts in heterogeneous catalysis. Here is the first report on strong metal phosphide‐phosphate support interaction (SMPSI). The key to SMPSI is the activation of P species on the support, which leads to simultaneous generation of metal phosphide nanoparticles (NPs) and core–shell nanostructures formed by support migration onto the NPs. The encapsulation state of metal phosphide and charge transfer are identical to those of classical SMSIs and can be optimally regulated. Furthermore, the strong interactions of Co2PL/MnP‐3 not only significantly enhance the anti‐oxidation and anti‐acid capability of non‐noble metal but also exhibit excellent catalytic activity and stability toward hydrogenating a wide range of compounds into value‐added fine chemicals with 100% selectivity, which is even better than Pd/C and Pt/C. The SMPSI construction can be generally extended to other systems such as Ni2PL/Mn3(PO4)2, Co2PL/LaPO4, and CoPL/CePO4. This study provides a new approach for the rational design of advanced non‐noble metal catalysts and introduce a novel paradigm for the strong interaction between NPs and support.

Surface Engineering of Cr-Doped Cobalt Molybdate toward High-Performance Hydrogen Evolution

“…From the O 1s spectra of XPS in Figures e and S7, compared with Cr-CoMoO 4 and P-Cr-CoMoO 4 , the Mo–O bond strength (530.3 eV) of E-Cr-CoMoO 4 decreases significantly and the strength of the Co–O/OH bond (531.2 eV) increases due to the leaching of Mo cations and exposure of more cobalt sites. , As for Figure S8, the doublets at 129.0 and 130.1 eV can be assigned to the phosphide, and a peak of PO 4 3– at 134.5/134.1 eV is attributed to surface oxidation in P-Cr-CoMoO 4 and PE-Cr-CoMoO 4 . , The content of phosphide in PE-Cr-CoMoO 4 is higher, proving that the phosphide in PE-Cr-CoMoO 4 is more sufficient, which is decided by its special surface structure. Finally, we further analyze the influence of alkaline etching and phosphating process at the surface properties of materials by comparing the content change of elements in different samples by XPS (Table S1).…”

“…3− at 134.5/134.1 eV is attributed to surface oxidation in P-Cr-CoMoO 4 and PE-Cr-CoMoO 4 . 27,28 The content of phosphide in PE-Cr-CoMoO 4 is higher, proving that the phosphide in PE-Cr-CoMoO 4 is more sufficient, which is decided by its special surface structure. Finally, we further analyze the influence of alkaline etching and phosphating process at the surface properties of materials by comparing the content change of elements in different samples by XPS (Table S1).…”

Facet-Induced Strong Metal Chloride−Support Interaction over CuCl2/γ-Al2O3 Catalyst to Enhance Ethylene Oxychlorination Performance

“…4,5 The classical SMSI has been mainly focusing on the reducible metal oxide supports with noble metals. 6 In addition, the oxide supported metal cluster or metal salt clusters have greatly magnified MSI in nano-catalysts and has plenty of potential in building the model of interfacial effects associated with MSI at the atomic level. 7 One interesting phenomenon that makes the oxide supports (TiO 2 , γ-Al 2 O 3 , etc.)…”

“…Most of the supports are not only acting as the carriers but also interacting with the active species. The significance of the interaction between the metal species and the support can be reflected from that strong metal–support interaction (SMSI) has been regarded as the most important concept in heterogeneous catalysis. − The parallel influence of the oxide support upon the supported metal oxides or metal salts, like chlorides, sulfides, and carbides (represented as MX n ) through the MX n –support interaction is also striking and follows a similar pattern with SMSI. , The classical SMSI has been mainly focusing on the reducible metal oxide supports with noble metals . In addition, the oxide supported metal cluster or metal salt clusters have greatly magnified MSI in nano-catalysts and has plenty of potential in building the model of interfacial effects associated with MSI at the atomic level …”

Enhanced Hydrogenation Properties of Pd Single Atom Catalysts with Atomically Dispersed Ba Sites as Electronic Promoters

“…Single atom catalysts (SACs), as a rising star in heterogeneous catalysis, exhibit a unique geometric/electronic structure and superior catalytic performance, which have attracted continuous interest. − However, in hydrogenation reactions, the activity is strongly affected by electronic structure of the catalysts. − The electron-deficient single atoms (SAs) should be less active for H 2 dissociation, resulting in low activity, which is generally rate limiting. , Thus, it is challenging to fabricate highly efficient catalysts with electron-rich active sites at the atomic scale . Nowadays, various protocols including introducing other components, − forming vacancies, , constructing heterojunctions, and creating strong metal–support interactions, , have been developed to finely tune and control the electronic structure of catalysts. − …”