Non-mercury catalytic acetylene hydrochlorination over Ru catalysts enhanced by carbon nanotubes

Li, Guangbi; Li, Wei; Zhang, Haiyang; Pu, Yanfeng; Sun, Mengxia; Zhang, Jinli

doi:10.1039/c4ra12017e

Cited by 44 publications

(29 citation statements)

References 38 publications

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“…20,21,40 For instance, the amount of Ru 0 was increased, while the amount of Ru 3+ was reduced when the cobalt component was added into RuCl 3 catalyst, which resulted in the better catalytic activity of 1%Ru1Co3/SAC than that of 1%Ru/SAC. 21 Our present DFT results further confirmed that both Ru 0 and Ru 3+ were active species for the reaction of acetylene hydrochlorination.…”

Section: The Effect Of Chloride Coordination Number On the Catalytic mentioning

confidence: 94%

Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study

Han

Sun

et al. 2015

Phys. Chem. Chem. Phys.

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The catalytic mechanism of Ru-based catalysts in the acetylene hydrochlorination reaction has been investigated via the density functional theory (DFT) method. To study the effect of the chlorine coordination number on the catalytic mechanism, Ru3Cl9, Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 clusters were chosen as the catalytic models. Our results show that the energy barrier for acetylene hydrochlorination on Ru3Cl9 was as high as 1.51 eV at 458 K. When the chlorine coordination number decreased, the energy barriers on Ru3Cl7, Ru5Cl7, Ru3Cl3 and Ru3 were 1.29, 0.89, 1.01 and 1.42 eV, respectively. On Ru3Cl9, the H and Cl atoms of HCl were simultaneously added to C2H2 to form C2H3Cl, while the reaction was divided into two steps on Ru3Cl7, Ru3Cl3 and Ru3 clusters. The first step was the addition of H atom of HCl to C2H2 to form C2H3˙, and the second step was the addition of Cl atom to C2H3˙ to form C2H3Cl. The step involving the addition of Cl was the rate-controlling step during the whole reaction. On Ru5Cl7 cluster, there was an additional step before the steps involving the addition of H and Cl: the transfer of H atom from HCl to Ru atom. This step was the rate-controlling step during the reaction of acetylene hydrochlorination on Ru5Cl7 and its energy barrier was the lowest among all the above-mentioned catalytic models. Therefore, the Ru5Cl7 cluster played the most predominant role in acetylene hydrochlorination with the largest reaction rate constant kTST of 10(3).

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Section: The Effect Of Chloride Coordination Number On the Catalytic mentioning

confidence: 94%

Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study

Han

Sun

et al. 2015

Phys. Chem. Chem. Phys.

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“…[19,20] Due to the relatively lower activity and shorter lifetime of non-metallic catalysts, some distance remains from industrialization. As for metal catalysts, a series of metal chlorides, including Pt 4 + , [8,[21][22][23] Pd 2 + , [21,[24][25][26][27] Ru 2 + , [12,[28][29][30][31][32] Cu 2 + , [33,34] Sn 2 + , [35] have been explored as potential Hg-free catalysts, but Au-based catalysts possessing a higher standard reduction potential are considered as the most promising replacement. [4,[36][37][38][39] The coking deposition and the agglomeration or the reduction of active species are the main reasons for the deactivation of Au-based catalyst, which have been briefly introduced in the previous literatures.…”

Section: Introductionmentioning

confidence: 99%

Hydrochlorination of Acetylene Over the Activated‐Carbon‐Supported Au Catalysts Modified by N−P−O‐Containing Ligand

Zhang

et al. 2019

ChemCatChem

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Etidronic acid (HEDP) and Nitrilotri(methylphosphonic acid) (ATMP) were selected as heteroatoms-containing ligands to modify Au catalysts for acetylene hydrochlorination. Results from several analytical methods reveal an optimal mole ratio of Au/ligand (L) of 1 : 1, with obvious increments over the Au 1 -L 1 / AC catalyst. The coordination between the Au and the heteroatoms, especially the collocative presence of N, P, and O promoted electron transfer from the heteroatoms to the Au n + and increased the density of the electron cloud around active centers. This stabilized the Au n + and increased the difficulty in the reduction of Au species, and re-oxidized the Au 0 to active Au n + species. Moreover, the coordination inhibited the migration of active components. The increased density of the electron cloud around active centers also weakens the adsorption capacity for C 2 H 2 and strengthens the adsorption ability for HCl of the catalysts, which is conductive for constructing the micro-environment favorable to the reaction. DFT calculations proved the stabilization effect of the heteroatoms-containing ligands, and the energy sequence of the transition states supported the experimental results.

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“…Moreover, the group also proposed that an Ru-based catalyst may be another promising candidate [20]. Theoretical and experimental studies on the hydrochlorination of acetylene using Ru-based catalysts have also been carried out previously [21][22][23][24][25][26]. Furthermore, Pd-based catalysts have been extensively studied in the past.…”

Section: Introductionmentioning

confidence: 99%

Single-Atom X/g-C3N4(X = Au1, Pd1, and Ru1) Catalysts for Acetylene Hydrochlorination: A Density Functional Theory Study

Zhou

Kang

2019

Catalysts

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The mechanisms of the single-atom X/g-C3N4(X = Au1, Pd1, and Ru1) catalysts for the acetylene hydrochlorination reaction were systematically investigated using the density functional theory (DFT) B3LYP method. The density functional dispersion correction obtained by the DFT-D3 method was taken into account. During the reaction, C2H2 and HCl were well activated and the analysis of the adsorption energy demonstrated the adsorption performance of C2H2 is better than that of HCl. The catalytic mechanisms of the three catalysts consist of one intermediate and two transition states. Moreover, our results showed that the three single-atom catalysts improve the catalytic activity of the reaction to different degrees. The calculated energy barrier declines in the order of Pd1/g-C3N4 > Ru1/g-C3N4 > Au1/g-C3N4, and the energy barrier for the Au1/g-C3N4 catalyst was only 13.66 kcal/mol, proving that single-atom Au1/g-C3N4 may be a potential catalyst for hydrochlorination of acetylene to vinyl chloride.

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Non-mercury catalytic acetylene hydrochlorination over Ru catalysts enhanced by carbon nanotubes

Cited by 44 publications

References 38 publications

Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study

Influence of chlorine coordination number on the catalytic mechanism of ruthenium chloride catalysts in the acetylene hydrochlorination reaction: a DFT study

Hydrochlorination of Acetylene Over the Activated‐Carbon‐Supported Au Catalysts Modified by N−P−O‐Containing Ligand

Single-Atom X/g-C3N4(X = Au1, Pd1, and Ru1) Catalysts for Acetylene Hydrochlorination: A Density Functional Theory Study

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