Hexagonal Boron Nitride Meeting Metal: A New Opportunity and Territory in Heterogeneous Catalysis

Dong, Jinhu; Gao, Lijun; Fu, Qiang

doi:10.1021/acs.jpclett.1c02626

Cited by 31 publications

(19 citation statements)

References 100 publications

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“…However, the dense phase texture of the as-formed overlayers and their reversible nature under redox opposite reaction conditions have limitations in practical catalysis application. The metal-free nature, high thermal/chemical stability, nanoporous structure, and capability of modulating the interfacial electronic property of metal NPs being possessed by h-BN scaffolds envisaged us to explore the possibility to construct h-BN-derived SMSI in a supported metal NP catalyst …”

Section: Modulating the Electronic Properties Of Metal Nanoparticlesmentioning

confidence: 99%

“…The metal-free nature, high thermal/chemical stability, nanoporous structure, and capability of modulating the interfacial electronic property of metal NPs being possessed by h-BN scaffolds envisaged us to explore the possibility to construct h-BN-derived SMSI in a supported metal NP catalyst. 14 By leveraging the facile ionothermal procedure in h-BN construction using inorganic salt mixtures, 32 an in situ SMSI construction approach was developed with NaNH 2 , NaBH 4 , and PdCl 2 as the starting materials via a facile thermal treatment procedure, which enabled the formation of h-BN skeletons, the reduction of Pd 2+ to its metallic form, and h-BN overlayer introduction (Figure 8A). 2 HR-TEM and high-angle annular dark field scanning transmission electron microscope (HAADF-STEM) images verified that in the as-formed Pd/h-BN-SMSI skeletons, Pd NPs (particle size of 5.8 ± 0.7 nm) were uniformly distributed within the h-BN scaffolds, which consisted of encapsulation by h-BN layers with a thickness of about 2.5 nm (Figure 8B).…”

Section: Modulating the Electronic Properties Of Metal Nanoparticlesmentioning

confidence: 99%

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

et al. 2022

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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 ...

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Section: Modulating the Electronic Properties Of Metal Nanoparticlesmentioning

confidence: 99%

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

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“…30,31 Therefore, the essentiality of constructing defects on the h-BN surface has been recognized. 32 In particular, Lin et al 33 clarifies that Pt ions can be stabilized at the terminal oxygen species at the edge of h-BN. Meanwhile, as proposed by Grant et al, 21 the terminal oxygen at the boundary of h-BN can be used as the catalytic active site in the selective oxidative dehydrogenation of propane.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, hexagonal boron nitride (h-BN) has attracted much attention due to its excellent thermal conductivity and chemical stability. , The unique surface chemical and electronic properties of h-BN make it widely applicable in catalysis, such as photocatalysis, oxidative dehydrogenation, and CO oxidation, − and MDR, where the h-BN displays excellent coke resistance. − However, the surface inertia of pristine h-BN restrains the dispersion of the supported active metal, leading to weak metal–support interaction. , Therefore, the essentiality of constructing defects on the h-BN surface has been recognized . In particular, Lin et al clarifies that Pt ions can be stabilized at the terminal oxygen species at the edge of h-BN.…”

Section: Introductionmentioning

confidence: 99%

Coking- and Sintering-Resistant Ni Nanocatalysts Confined by Active BN Edges for Methane Dry Reforming

Zhang

Deng

Lan

et al. 2022

ACS Appl. Mater. Interfaces

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Methane dry reforming (MDR) has attracted significant attention for effectively consuming greenhouse gases and producing valuable syngas. The development of coking-and sintering-resistant catalysts is still a challenge. Herein, highly active Ni nanocatalysts confined by the active edges of boron nitride have been originally developed, and the coking-and sinteringresistant MDR mechanism has also been unraveled. The active edges of boron nitride consisted of boundary BO x species interact with Ni nanoparticles (NPs), which can contribute to the activation of both CH 4 and CO 2 . The etching of BN is restrained under the buffer of boundary BO x species. Operando spectra reveal that the formation and conversion of active bicarbonate species is accelerated by the boundary BO x species. The complete decomposition of CH 4 is suppressed, and thus the coke formation is restricted. The functional groups of active BN edges are confirmed to stabilize the Ni NPs and facilitate the MDR reaction. This work provides a novel approach for the development of coking-and sintering-resistant catalysts for MDR.

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“…Defects, such as vacancies, etc., that are capable of modulating electronic properties of h -BN, can be created by electron beam irradiation, solvent and gas exfoliation, ball milling [ 41 , 42 ], etc. 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.…”

Section: Introductionmentioning

confidence: 99%

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

2022

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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.

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Hexagonal Boron Nitride Meeting Metal: A New Opportunity and Territory in Heterogeneous Catalysis

Cited by 31 publications

References 100 publications

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

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

Coking- and Sintering-Resistant Ni Nanocatalysts Confined by Active BN Edges for Methane Dry Reforming

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

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