Rational screening of single-atom-doped ZnO catalysts for propane dehydrogenation from microkinetic analysis

Ma, Fei; Chang, Qing‐Yu; Yin, Qiang; Sui, Zhi‐Jun; Zhou, Xinggui; Chen, De; Zhu, Yi‐An

doi:10.1039/d0cy00609b

Cited by 22 publications

(29 citation statements)

References 61 publications

(71 reference statements)

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“…Catalytic conversion of light alkanes to more valuable chemicals, commodities, and fuels has attracted much attention in recent years [1][2][3]. Giving the scarcity of fossil fuels and suddenly increased low-cost light alkanes supplement from the shale gas revolution, propane conversion is becoming popular, and is regarded as an attractive way to meet the increasing demand for propylene and aromatics [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Relationship between Acidity and Activity on Propane Conversion over Metal-Modified HZSM-5 Catalysts

Zhou

Zhang

et al. 2021

Catalysts

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A systematic study of the comparative performances of different metal-impregnated HZSM-5 catalysts (Zn, Ga, Mo, Co, and Zr) for propane conversion is presented. The physicochemical properties of catalysts were characterized by means of XRD, BET, SEM, TEM, FTIR, XPS, 27Al MAS NMR, NH3-TPD and Py-FTIR. It was found that the acidities of the catalysts were significantly influenced by loading metal. More specifically, Mo-, Co- or Zr-modified catalysts showed a large metal size and low acidic density, resulting high olefin selectivity, while Zn- or Ga-modified catalysts maintained their small metal size and acidic density, and mainly reduced B/L due to the Lewis acid sites created by Zn or Ga species, resulting in high aromatics selectivity. Experimental results also showed that there is a balance between metals size and medium and strong acidity on propane conversion. Moreover, based on the different acidity of metal-modified HZSM-5 catalysts, the mechanism of propane conversion was also discussed.

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Section: Introductionmentioning

confidence: 99%

Relationship between Acidity and Activity on Propane Conversion over Metal-Modified HZSM-5 Catalysts

Zhou

Zhang

et al. 2021

Catalysts

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“…The using of 0.5H 2 (g), half energy of the gas phase H 2 , in Figure 5 to balance the initial state of 2 nd dehydrogenation step is exactly in accordance with the recent PDH works. [ 10,15‐16,36 ]…”

Section: Resultsmentioning

confidence: 99%

“…[ 4,13 ] It has been categorically demonstrated in previous studies that the catalytic properties of transition‐metal oxides can be enhanced by creating the oxygen vacancies and doping the structure with stable transition metals such as Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. [ 8,14‐16 ] The reactivity of Cr 2 O 3 and ZnO was changed by creating the oxygen vacancy, while it also serves as the active site. [ 8 ] Moreover, the oxygen vacancy, by changing significant properties in the catalyst structure, can enable the metal atoms to actively break the C—H bond and lead the surface to a more efficient catalytic action towards the C—H bond activation.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Effects of Oxygen Vacancy and Pt Doping on the Catalytic Performance of CeO₂ in Propane Dehydrogenation: A First‐Principles Study

et al. 2021

Self Cite

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Main observation and conclusion The catalytic properties of the CeO2 catalyst for propane dehydrogenation (PDH) are examined by employing the density functional theory calculations. Surface modifications and their effects on the surface reactivity are explored by creating the oxygen vacancy and single Pt atom doping. A comparative study between the binding energies of the different PDH reaction species reveals a considerable Lewis acid‐base interaction over the pristine and defective surfaces, which dominantly strengthens the bond formation between the adsorbates and the catalyst surface, resulting in the enhancement of surface reactivity. The creation of oxygen vacancy and doping the CeO2(111) surface with single Pt atoms changes the charge distribution over the surface on account of excess 4f electrons. This electronic change increases the bond formation abilities of the inactive Ce atom and hence increases the adsorption strength. Oxygen vacancy in the defective CeO2(111) surface migrates over the surface with the addition of an appropriate adsorbate. Moreover, it is revealed that the propylene is more strongly adsorbed on the single‐Pt‐atom‐doped CeO2(111) surface than the pristine and defective surfaces, which decreases the deep dehydrogenation energy barrier and ultimately results in the lowering of the selectivity.

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“…For Cr-based catalysts, without doubt, the hexavalent Cr(VI) is very harmful to the environment. Therefore, more catalyst systems have been developed to achieve activity or/and selectivity comparable with them, including (i) a metal alloy such as RhCu, (ii) first-row 3d and group IIIA (13) metal oxide based catalysts such as VO x , , ZnO, , BO x , , GaO x , − and InO x , , and (iii) catalysts with oxygen vacancies. − …”

Section: Introductionmentioning

confidence: 99%

“…18 For Cr-based catalysts, without doubt, the hexavalent Cr(VI) is very harmful to the environment. Therefore, more catalyst systems have been developed to achieve activity or/ and selectivity comparable with them, including (i) a metal alloy such as RhCu, 19 (ii) first-row 3d and group IIIA (13) metal oxide based catalysts such as VO x , 20,21 ZnO, 22,23 BO x , 24,25 GaO x , 26−28 and InO x , 29,30 and (iii) catalysts with oxygen vacancies. 31−33 Different from the metal-alloy-based catalysts with zerovalent metal, the active sites of the metal in the other catalyst systems are all ionic states with an −M δ+ −O δ− − structure either contained in the metal oxides or formed by interaction with the supporter.…”

Section: Introductionmentioning

confidence: 99%

Suppressing C–C Bond Dissociation for Efficient Ethane Dehydrogenation over the Isolated Co(II) Sites in SAPO-34

Zhang

et al. 2021

ACS Catal.

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Various Co-based SAPO-34 catalysts were prepared using different methods, including ion exchange (IE), incipientwetness impregnation (IWI), and solid-phase grinding (SPG), to correlate the chemical states of Co species with the C−H and C−C bond scissions in ethane dehydrogenation. The IE-prepared Co/ SAPO-34 led to stable, unreducible, and isolated exchanged Co sites anchored on the zeolite framework with a structure of −Al F − O−Co−O− and showed the highest selectivity to ethylene of close to 98% at 600 °C, which suggests that these Co sites favors suppressing the C−C bond scission in ethane. In comparison, the IWI-and SPG-prepared Co/SAPO-34 catalysts, especially for those with a high Co loading, inevitably give Co oxide clusters that are easily reduced into metallic Co. Together with catalytic results, characterizations, and DFT calculations, it is confirmed that the reduced Co clusters, especially for those outside SAPO-34 channels without the confinement effect, favor both C−H and C−C bond scission, boosting the conversion of ethane into CH 4 or/and coke; however, the ionic-state −Co−O− species can smoothly terminate the ethane dehydrogenation for the ethylene product due to relatively high energy barriers for both C−H and C−C bond scission, avoiding a deep dehydrogenation and C−C cracking. As expected, the unreducible −Co−O− sites are very stable in the title reaction without deanchoring from the zeolite framework in a 100 h cyclic test. This study not only demonstrates the stable −M δ+ −O δ− structure favorable for suppressing C−C bond scission but also highlights a catalyst-constructing strategy for Co-based and similar metal-based catalysts for dehydrogenation of other light alkanes.

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Rational screening of single-atom-doped ZnO catalysts for propane dehydrogenation from microkinetic analysis

Abstract: Descriptor-based microkinetic analysis is performed to screen single-atom-doped ZnO for PDH, and Mn1- and Cu1–ZnO prove to be good candidates.

Cited by 22 publications

References 61 publications

Relationship between Acidity and Activity on Propane Conversion over Metal-Modified HZSM-5 Catalysts

Relationship between Acidity and Activity on Propane Conversion over Metal-Modified HZSM-5 Catalysts

Effects of Oxygen Vacancy and Pt Doping on the Catalytic Performance of CeO₂ in Propane Dehydrogenation: A First‐Principles Study

Suppressing C–C Bond Dissociation for Efficient Ethane Dehydrogenation over the Isolated Co(II) Sites in SAPO-34

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Rational screening of single-atom-doped ZnO catalysts for propane dehydrogenation from microkinetic analysis

Abstract: Descriptor-based microkinetic analysis is performed to screen single-atom-doped ZnO for PDH, and Mn1- and Cu1–ZnO prove to be good candidates.

Cited by 22 publications

References 61 publications

Relationship between Acidity and Activity on Propane Conversion over Metal-Modified HZSM-5 Catalysts

Relationship between Acidity and Activity on Propane Conversion over Metal-Modified HZSM-5 Catalysts

Effects of Oxygen Vacancy and Pt Doping on the Catalytic Performance of CeO2 in Propane Dehydrogenation: A First‐Principles Study

Suppressing C–C Bond Dissociation for Efficient Ethane Dehydrogenation over the Isolated Co(II) Sites in SAPO-34

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Effects of Oxygen Vacancy and Pt Doping on the Catalytic Performance of CeO₂ in Propane Dehydrogenation: A First‐Principles Study