From metal–organic frameworks to single/dual-atom and cluster metal catalysts for energy applications

Hou, Chun‐Chao; Wang, Haofan; Li, Caixia; Xu, Qiang

doi:10.1039/c9ee04040d

Cited by 394 publications

(257 citation statements)

References 213 publications

Supporting

Mentioning

257

Contrasting

Order By: Relevance

“…In the past five years, several DACs have been reported for ORR, and most of the experimentally realized DACs were supported on carbon materials, especially N–C, [ 26a,28a,d,62,75 ] ( Table 2 ) because of their outstanding electrical conductivity, highly exposed active sites, and ultrahigh porosity. [ 76 ] Homonuclear DACs including Co [ 75b ] and Fe pairs [ 28d ] anchored on N–C, which were synthesized through the precise tuning of metal loading, have been demonstrated as highly efficient ORR electrocatalysts. By controlling the atomic‐scale structure of the bimetal–organic framework before pyrolysis through a self‐adjusted strategy, Xiao et al.…”

Section: Practical Applications Of Dacs In Heterogeneous Catalysismentioning

confidence: 99%

“More is Different:” Synergistic Effect and Structural Engineering in Double‐Atom Catalysts

Ying

Luo

Qiao

et al. 2020

Adv Funct Materials

226

158

View full text Add to dashboard Cite

Double-atom catalysts (DACs) have emerged as a novel frontier in heterogeneous catalysis because the synergistic effect between adjacent active sites can promote their catalytic activity while maintaining high atomic utilization efficiency, good selectivity, and high stability originating from the atomically dispersed nature. In this review, the recent progress in both experimental and theoretical research on DACs for various catalytic reactions is focused. Specifically, the central tasks in the design of DACs-manipulating the synergistic effect and engineering atomic and electronic structures of catalysts-are systematically reviewed, along with the prevailing experimental, characterization, and computational modeling approaches. Furthermore, the practical applications of DACs in water splitting, oxygen reduction reaction, nitrogen reduction reaction, and carbon dioxide reduction reaction are addressed. Finally, the future challenges for DACs are summarized and an outlook on the further investigations of DACs toward heterogeneous catalysis in high-performance energy and environmental applications is provided.

show abstract

Section: Practical Applications Of Dacs In Heterogeneous Catalysismentioning

confidence: 99%

“More is Different:” Synergistic Effect and Structural Engineering in Double‐Atom Catalysts

Ying

Luo

Qiao

et al. 2020

Adv Funct Materials

226

158

View full text Add to dashboard Cite

show abstract

“…In this context, atomically isolated metal atoms embedded in suitable supports generate a new kind of catalysts, which patches up the gap between homogeneous and heterogeneous catalysis. The dispersion of metal on an atomic scale generates maximum utilization efficiency (nearly 100%), remarkable quantum size effect, unsaturated coordination environment, and strong metal-support interaction, as shown in Figure 1 [ 4 ], which enables metal atoms dramatically boosted activity, selectivity, and stability. Furthermore, recent progress in advanced characterization techniques makes it possible to confirm the exact geometric structure of the active centers due to their simplicity and homogeneity, which provides an ideal platform for establishing theoretical calculation models and deeply understanding catalytic mechanisms at the atomic-scale level to elucidate the fundamental synthesis-structure-performance correlations for rational design of catalysts for targeted reactions.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Single-Atom Electrocatalysts for Oxygen Reduction Reaction

2020

View full text Add to dashboard Cite

Oxygen reduction reaction (ORR) plays significant roles in electrochemical energy storage and conversion systems as well as clean synthesis of fine chemicals. However, the ORR process shows sluggish kinetics and requires platinum-group noble metal catalysts to accelerate the reaction. The high cost, rare reservation, and unsatisfied durability significantly impede large-scale commercialization of platinum-based catalysts. Single-atom electrocatalysts (SAECs) featuring with well-defined structure, high intrinsic activity, and maximum atom efficiency have emerged as a novel field in electrocatalytic science since it is promising to substitute expensive platinum-group noble metal catalysts. However, finely fabricating SAECs with uniform and highly dense active sites, fully maximizing the utilization efficiency of active sites, and maintaining the atomically isolated sites as single-atom centers under harsh electrocatalytic conditions remain urgent challenges. In this review, we summarized recent advances of SAECs in synthesis, characterization, oxygen reduction reaction (ORR) performance, and applications in ORR-related H2O2 production, metal-air batteries, and low-temperature fuel cells. Relevant progress on tailoring the coordination structure of isolated metal centers by doping other metals or ligands, enriching the concentration of single-atom sites by increasing metal loadings, and engineering the porosity and electronic structure of the support by optimizing the mass and electron transport are also reviewed. Moreover, general strategies to synthesize SAECs with high metal loadings on practical scale are highlighted, the deep learning algorithm for rational design of SAECs is introduced, and theoretical understanding of active-site structures of SAECs is discussed as well. Perspectives on future directions and remaining challenges of SAECs are presented.

show abstract

“…Note that this work falls within the emerging area of research of supported Dual-Atom Catalysts (DACs), [33,34] although the mild SOMC catalyst preparation approach is drastically different from classically used high temperature (750-1200°C) pyrolytic treatment of metal-organic precursors leading to carbon-derived materials containing dual M-M' sites. [35][36][37][38][39] Scheme 1. Methodologies to access heterobimetallic surface species through a SOMC approach.…”

Section: Introductionmentioning

confidence: 99%

Stepwise construction of silica-supported tantalum/iridium heteropolymetallic catalysts using surface organometallic chemistry

Lassalle

Jabbour

Rosal

et al. 2020

Journal of Catalysis

View full text Add to dashboard Cite

A stepwise surface organometallic chemistry (SOMC) methodology consisting in using a silica-supported tantalum species, [(≡SiO)Ta(CH t Bu)(CH2 t Bu)2], as a reactive center to coordinate an iridium site, was developed to construct tantalum/iridium heterobimetallic edifices. The resulting material, MAT-2, exhibits enhanced catalytic performances-both in H/D isotopic exchange and alkane metathesis reactions-in comparison to MAT-1, which was prepared from the direct grafting on silica of a well-defined heterobimetallic Ta/Ir complex. We projected that the difference in catalytic activity was due to the presence of distinct active sites and we used a combination of advanced spectroscopic methods (IR, solid-state NMR and XAS spectroscopies) as well as modeling (computational studies and molecular models) to identify the structure of these surface species. These investigations point towards the presence of three types of active sites at the surface of MAT-2: the heterobimetallic surface species, [≡SiOTa(CH2 t Bu)2{IrH2(Cp*)}] 2-s, which is also found in MAT-1, as well as an unanticipated heterotrimetallic species, [≡SiOTa(CH2 t Bu)2{IrH2(Cp*)}], 3-s along with some unreacted monometallic Ta sites [(≡SiO)Ta(CH t Bu)(CH2 t Bu)2], 1-s. The well-defined trimetallic surface species 3-s was independently prepared and characterized to support this hypothesis. This study highlights the importance of the synthetic methodology used for the preparation of heterobimetallic species through SOMC, and the difficulty to obtain true single-sites surface species.

show abstract

From metal–organic frameworks to single/dual-atom and cluster metal catalysts for energy applications

Abstract: Single/dual-atom and cluster metal catalysts have emerged as a new frontier in catalysis. This review highlights recent advances and provides a state-of-the-art understanding of MOF-based synthesis strategies and their prospective applications.

Cited by 394 publications

References 213 publications

“More is Different:” Synergistic Effect and Structural Engineering in Double‐Atom Catalysts

“More is Different:” Synergistic Effect and Structural Engineering in Double‐Atom Catalysts

Recent Advances in Single-Atom Electrocatalysts for Oxygen Reduction Reaction

Stepwise construction of silica-supported tantalum/iridium heteropolymetallic catalysts using surface organometallic chemistry

Contact Info

Product

Resources

About