PdZn alloy nanoparticles encapsulated within a few layers of graphene for efficient semi-hydrogenation of acetylene

Yang, Lini; Guo, Yushu; Long, Jun; Xia, Lixin; Li, Dan; Xiao, Jianping; Li, Hongyang

doi:10.1039/c9cc06442g

Cited by 31 publications

(24 citation statements)

References 24 publications

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“…The applications of reaction phase diagram have shown a great success understanding experimental results, where the predicted activity variations have been verified by several experiments. 22,[49][50][51][53][54][55]63 The volcano plot at the thermodynamic level indicates it is usually a reasonable prediction for electrocatalysis. 26 However, some thermochemical processes do occur in electrocatalysis, for instance, C-N bond synthesis and C-C coupling.…”

Section: Discussionmentioning

confidence: 98%

“…Alkynes hydrogenation is widely needed in petrochemical industries, where the activity of catalytic reactions and, more importantly, selectivity between olefin and alkanes products were focused. [52][53][54] DFT calculations with reaction phase diagram were used in the investigation of phenylacetylene hydrogenation over Pt nanoparticles, confined by N-doped graphene (CN@Pt). 54 The elementary steps were listed in the following: Again, a single reaction pathway was considered.…”

Section: Alkynes Hydrogenationmentioning

confidence: 99%

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Toward computational design of chemical reactions with reaction phase diagram

Guo

Long

et al. 2021

WIREs Comput Mol Sci

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Density functional theory (DFT) was rapidly developed and achieved a great success in the last decades. As the advancement of general concepts in heterogeneous catalysis, theoretical study of chemical reactions based on DFT calculations has become more and more feasible, which provides a guideline for the rational design of novel catalysts toward higher reaction activity and specific selectivity. Here, we review an innovate scheme, namely reaction phase diagram (RPD), which can offer not only an in-depth understanding of reaction mechanisms, but also the prediction of catalytic activity and selectivity trend over a collection of catalysts. The RPD analysis was successfully applied to understand the activity variation of CO 2 electroreduction to CO and formic acid, as well as thermochemical hydrogenation and dehydrogenation. Meanwhile, the RPD analysis also exhibits a success of studying the product selectivity in syngas conversion to methane, ethanol, and methanol with complicated reaction pathways. At the end, we review a successful case of catalyst rational design with a target of NO selective electroreduction to ammonia. The foundation of RPD analysis is based on the scaling relation of adsorption energies and the correlation between kinetic barriers and reaction energies at elementary steps. Therefore, microkinetic modeling is complementary to the RPD analysis. A few of limitations and the prospect of the development regarding the RPD analysis are addressed in this review. This article is categorized under:Structure and Mechanism > Reaction Mechanisms and Catalysisdensity functional theory, full pathway construction, global energy optimization, heterogeneous catalysis, reaction phase diagram | INTRODUCTIONHeterogeneous catalysis possesses a momentous value in many chemical processes, which has been widely focused in industry. Besides, it has been widely studied in academia, for example Fischer-Tropsch (FT) and ammonia synthesis, 1-3 selective catalytic reduction (SCR), CO oxidation, 4-5 CO 2 reduction reaction (CO 2 RR), and oxygen reduction reaction Chenxi Guo and Xiaoyan Fu contributed equally in this work.

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Section: Discussionmentioning

confidence: 98%

Section: Alkynes Hydrogenationmentioning

confidence: 99%

Toward computational design of chemical reactions with reaction phase diagram

Guo

Long

et al. 2021

WIREs Comput Mol Sci

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“…The density functional theory (DFT) calculation shows that the key reason for low selectivity is that styrene adsorption on Pd nanoparticles is difficult to desorb in time, thus causing excessive hydrogenation [15] . Therefore, a large number of researchers began to introduce other metal elements into Pd nanoparticles for solving this problem [16–22] . Wang and his colleagues introduced Au to form Pd−Au bimetallic catalyst, which was loaded on carbon nanotubes in the semi‐hydrogenation of phenylacetylene [23] .…”

Section: Introductionmentioning

confidence: 99%

Pd−Zn Alloy Nanoparticles Encapsulated into Mesoporous Silica with Confinement Effect for Highly Selective Semi‐Hydrogenation of Phenylacetylene

Liu

et al. 2020

ChemCatChem

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In the process of hydrogenation of phenylacetylene to styrene, it is a crucial step to improve the reaction selectivity of the target product styrene. Herein, we have designed the Pd−Zn alloy nanoparticles encapsulated into mesoporous silica with confinement effect (Pd−Zn@MS) for highly selective semi‐hydrogenation of phenylacetylene via annealing the Pd NPs@ZIF‐8 in reducing atmosphere. The as‐obtained Pd−Zn@MS achieved up to the 95 % of conversion rate and 92 % of selectivity, because the mesoporous silica exhibits a steric hindrance effect for the reactant molecular size, and the Pd−Zn alloy nanoparticles shows the high selectivity for the target product styrene. DFT calculations demonstrates that the PdZn alloy nanoparticles can reduce significantly the desorption energy barrier of styrene from 1.72 eV to 0.95 eV, compared with the Pd nanoparticles. Meanwhile the mesoporous silica in the outer layer greatly guarantees the stability of the catalytic performance of the catalyst, and the catalytic performance did not drop after the five‐cycle test. This work provides a new idea for the selective hydrogenation of phenylacetylene and the process of limited‐area catalysis.

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“…The most commonly used catalyst is the low‐surface‐area alumina‐supported Pd catalyst modified by Ag [7,8] . In addition, Ga, [9–11] Zn, [12–14] Au, [15–17] Cu, [18–21] and In [22,23] are also used as the promoters. Recently, Liu et al [24,25] .…”

Section: Introductionmentioning

confidence: 99%

High‐Performance Catalysts Derived from Cupric Subcarbonate for Selective Hydrogenation of Acetylene in an Ethylene Stream

Zeng

Wang

et al. 2021

Eur J Inorg Chem

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A high‐performance base metal catalyst for acetylene selective hydrogenation was prepared from cupric subcarbonate (Cu2(OH)2CO3) by thermal treatment with an acetylene‐containing gas followed by hydrogen reduction. The characterization results revealed that the copper catalyst was composed of interstitial copper carbide (CuxC) and metal Cu, which were embedded in porous carbon matrix. The CuxC crystallites, which showed outstanding hydrogenation activity, were derived from the hydrogen reduction of copper (II) acetylide (CuC2) which was generated from the reaction between acetylene and Cu2(OH)2CO3. The Cu particles and porous carbon were generated from the unavoidable thermal decomposition of CuC2. The prepared Cu‐derived catalyst completely removed the acetylene impurity in an ethylene stream with a very low over‐hydrogenation selectivity at 110 °C and atmospheric pressure. No obvious deactivation was observed in a 180‐h test run. In the Cu‐derived catalyst, CuxC served as the catalytic site for H2 dissociation, Cu mainly functioned as the site for selective hydrogenation of acetylene, whereas the porous carbon matrix posed a steric hindrance effect on the chain growth of linear hydrocarbons so as to suppress the undesired oligomerization.

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PdZn alloy nanoparticles encapsulated within a few layers of graphene for efficient semi-hydrogenation of acetylene

Abstract: PdZn alloy NPs encapsulated within a few layers of graphene exhibit enhanced acetylene selectivity and robust long-term stability in selective hydrogenation of acetylene, compared with that of traditional supported Pd and PdZn alloy catalysts.

Cited by 31 publications

References 24 publications

Toward computational design of chemical reactions with reaction phase diagram

Toward computational design of chemical reactions with reaction phase diagram

Pd−Zn Alloy Nanoparticles Encapsulated into Mesoporous Silica with Confinement Effect for Highly Selective Semi‐Hydrogenation of Phenylacetylene

High‐Performance Catalysts Derived from Cupric Subcarbonate for Selective Hydrogenation of Acetylene in an Ethylene Stream

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