Single Atoms Anchored in Hexagonal Boron Nitride for Propane Dehydrogenation from First Principles

Xiong, Chuanye; Dai, Sheng; Wu, Zili; Jiang, De‐en

doi:10.1002/cctc.202200133

Cited by 6 publications

(9 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The calculated binding energy (E b ) of the Au atom on the B-vacancy of h -BN (AuBN, Figure 1 a) in a triplet ground state is −3.54 eV and is comparable to calculated (−2.90 eV), previous theoretical (−3.03 eV) [ 68 ] and experimental results of bulk Au (−3.81 eV) [ 69 ], suggesting AuBN would be plausible over other potential Au deposition structures [ 52 , 53 ]. Considering the poor E b of the Au atom (−0.11 and −0.10 eV, respectively, on top of N and B atoms on pristine h -BN), the outward diffusion of Au from AuBN would be highly endothermic (>3 eV), so it is hard to expect that the Au atom would diffuse away.…”

Section: Resultssupporting

confidence: 82%

“…The metal/defective h -BN interaction stabilizes the metal species and tailors their reactivity [ 43 , 44 , 45 , 46 , 47 , 48 , 49 ]. Several h -BN-supported SACs have been proposed effective for reactions of practical interest, such as the electroreduction of N 2 and CO 2 [ 47 , 48 , 49 , 50 ], hydrogenation of Cinnamaldehyde [ 51 ], dehydrogenation of light alkanes [ 52 ] and CO oxidation [ 53 , 54 ] etc. However, the active site and active species in reaction conditions for these processes have not been addressed.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Coadsorption Interfered CO Oxidation over Atomically Dispersed Au on h-BN

2022

View full text Add to dashboard Cite

Similar to the metal centers in biocatalysis and homogeneous catalysis, the metal species in single atom catalysts (SACs) are charged, atomically dispersed and stabilized by support and substrate. The reaction condition dependent catalytic performance of SACs has long been realized, but seldom investigated before. We investigated CO oxidation pathways over SACs in reaction conditions using atomically dispersed Au on h-BN (AuBN) as a model with extensive first-principles-based calculations. We demonstrated that the adsorption of reactants, namely CO, O2 and CO2, and their coadsorption with reaction species on AuBN would be condition dependent, leading to various reaction species with different reactivity and impact the CO conversion. Specifically, the revised Langmuir–Hinshelwood pathway with the CO-mediated activation of O2 and dissociation of cyclic peroxide intermediate followed by the Eley–Rideal type reduction is dominant at high temperatures, while the coadsorbed CO-mediated dissociation of peroxide intermediate becomes plausible at low temperatures and high CO partial pressures. Carbonate species would also form in existence of CO2, react with coadsorbed CO and benefit the conversion. The findings highlight the origin of the condition-dependent CO oxidation performance of SACs in detailed conditions and may help to rationalize the current understanding of the superior catalytic performance of SACs.

show abstract

Section: Resultssupporting

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Coadsorption Interfered CO Oxidation over Atomically Dispersed Au on h-BN

2022

View full text Add to dashboard Cite

show abstract

“…The achievements made in this work provide a way to construct stable and active supported metal NP catalysts by leveraging the defects in h-BN scaffolds. DFT calculations showed that the defects in h-BN can stabilize the Pt single atom for propane dehydrogenation …”

Section: Modulating the Electronic Properties Of Metal Nanoparticlesmentioning

confidence: 99%

“…DFT calculations showed that the defects in h-BN can stabilize the Pt single atom for propane dehydrogenation. 48 Regarding the ubiquitous application of supported metal NPs in heterogeneous catalysis, extensive studies have been focused on the stability enhancement during the long-term procedures to avoid deactivation caused by metal sintering or impurity adsorption. 49 Besides the as-stated supports' premodification, the confinement effect within the channels or pores (e.g., in zeolites or silica) could to some extent protect the metal NPs from sintering but could not suppress the Ostwald ripening and Brownian-like motion behavior of metal NPs.…”

Section: Modulating the Electronic Properties Of Metal Nanoparticlesmentioning

confidence: 99%

Engineering Nanostructured Interfaces of Hexagonal Boron Nitride-Based Materials for Enhanced Catalysis

et al. 2022

Self Cite

View full text Add to dashboard Cite

Hexagonal boron nitrides (h-BNs) are attractive two-dimensional (2D) nanomaterials that consist of alternating B and N atoms and layered honeycomblike structures similar to graphene. They have exhibited unique properties and promising application potentials in the field of energy storage and transformation. Recent advances in utilizing h-BN as a metal-free catalyst in the oxidative dehydrogenation of propane have triggered broad interests in exploring h-BN in catalysis. However, h-BN-based materials as robust nanocatalysts in heterogeneous catalysis are still underexplored because of the limited methodologies capable of affording h-BN with controllable crystallinity, abundant porosity, high purity, and defect engineering, which played important roles in tuning their catalytic performance. In this Account, our recent progress in addressing the above issues will be highlighted, including the synthesis of high-quality h-BN-based nanomaterials via both bottom-up and top-down pathways and their catalytic utilization as metal-free catalysts or as supports to tune the interfacial electronic properties on the metal nanoparticles (NPs). First, we will focus on the large-scale fabrication of h-BN nanosheets (h-BNNSs) with high crystallinity, improved surface area, satisfactory purity, and tunable defects. h-BN derived from the traditional approaches using boron trioxide and urea as the starting materials generally contains carbon/oxygen impurities and has low crystallinity. Several new strategies were developed to address the issues. Using bulk h-BN as the precursor via gas exfoliation in liquid nitrogen, single-or few-layered h-BNNS with abundant defects could be generated. Amorphous h-BN precursors could be converted to h-BN nanosheets with high crystallinity assisted by a magnesium metallic flux via a successive dissolution/precipitation/crystallization procedure. The as-fabricated h-BNNS featured high crystallinity and purity as well as abundant porosity. An ionothermal metathesis procedure was developed using inorganic molten salts (NaNH 2 and NaBH 4 ) as the precursors. The h-BN scaffolds could be produced on a large scale with high yield, and the asafforded materials possessed high purity and crystallinity. Second, utilization of the as-prepared h-BN library as metal-free catalysts in dehydrogenation and hydrogenation reactions will be summarized, in which they exhibited enhanced catalytic activity over the counterparts from the previous synthesis method. Third, the interface modulation between metal NPs with the as-prepared defects' abundant h-BN support will be highlighted. The h-BN-based strong metal−support interaction (SMSI) nanocatalysts were constructed without involving reducible metal oxides via the ionothermal procedure we developed by deploying specific inorganic metal salts, acting as robust nanocatalysts in CO oxidation. Under conditions simulated for practical exhaust systems, promising catalytic efficiency together with high thermal stability and sintering resistance was achieved. Across all of these ...

show abstract

“…25,35,37 Additionally, with density functional theory (DFT) calculations, SACs supported on defective h-BN have been rationally designed and predicted to possess prominent catalytic reactivity toward various reactions, such as propane dehydrogenation, CO oxidation, NO electrochemical reduction, N 2 electrocatalytic reduction, hydrogen evolution reaction, etc. 19,36,[44][45][46][47][48][49][50][51] For ODS applications, h-BN as the support has been reported to anchor metal nanoparticles, polyoxometalates, and ionic liquids. 1,3,10,13 However, atomically dispersed metal on h-BN for ODS catalysts has not yet been reported.…”

Section: Introductionmentioning

confidence: 99%