Hydroxyl improving the activity, selectivity and stability of supported Ni single atoms for selective semi-hydrogenation

Abstract Heterogeneous single-atom catalyst (SAC) opens a unique entry to establishing structure–performance relationship at the molecular level similar to that in homogeneous catalysis. The challenge lies in manipulating the coordination chemistry of single atoms without changing single-atom dispersion. Here, we develop an efficient synthetic method for SACs by using ethanediamine to chelate Pt cations and then removing the ethanediamine by a rapid thermal treatment (RTT) in inert atmosphere. The coordination chemistry of Pt single atoms on a Fe2O3 support is finely tuned by merely adjusting the RTT temperature. With the decrease in Pt-O coordination number, the oxidation state of Pt decreases, and consequently the hydrogenation activity increases to a record level without loss of chemoselectivity. The tunability of the local coordination chemistry, oxidation states of the metal, and the catalytic performance of single atoms reveals the unique role of SACs as a bridge between heterogeneous and homogeneous catalysis.

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Porous Materials Confining Single Atoms for Catalysis

Frontiers in Chemistry ◽

10.3389/fchem.2021.717201 ◽

2021 ◽

Vol 9 ◽

Author(s):

Tao Zhu ◽

Yiwei Han ◽

Shuai Liu ◽

Bo Yuan ◽

Yatao Liu ◽

...

Keyword(s):

Porous Material ◽

Porous Materials ◽

Shape Selectivity ◽

Catalytic Performance ◽

High Specific Surface Area ◽

Single Atom ◽

Research Progress ◽

Porous Support ◽

Support Materials ◽

Single Atoms

In recent years, single-atom catalysts (SACs) have received extensive attention due to their unique structure and excellent performance. Currently, a variety of porous materials are used as confined single-atom catalysts, such as zeolites, metal-organic frameworks (MOFs), or carbon nitride (CN). The support plays a key role in determining the coordination structure of the catalytic metal center and its catalytic performance. For example, the strong interaction between the metal and the carrier induces the charge transfer between the metal and the carrier, and ultimately affects the catalytic behavior of the single-atom catalyst. Porous materials have unique chemical and physical properties including high specific surface area, adjustable acidity and shape selectivity (such as zeolites), and are rational support materials for confined single atoms, which arouse research interest in this field. This review surveys the latest research progress of confined single-atom catalysts for porous materials, which mainly include zeolites, CN and MOFs. The preparation methods, characterizations, application fields, and the interaction between metal atoms and porous support materials of porous material confined single-atom catalysts are discussed. And we prospect for the application prospects and challenges of porous material confined single-atom catalysts.

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Spatially Resolved and Quantitatively Revealed Charge Transfer between Single Atoms and Catalyst Supports

Journal of Materials Chemistry A ◽

10.1039/d1ta08353h ◽

2021 ◽

Author(s):

Bin Di ◽

Zhantao Peng ◽

Zhongyi Wu ◽

Xiong Zhou ◽

Kai Wu

Keyword(s):

Charge Transfer ◽

Charge State ◽

Catalytic Performance ◽

Single Atom ◽

Catalyst Supports ◽

Single Atoms ◽

Spatially Resolved

The charge state of supported single atoms is one of the most significant aspects determining the catalytic performance of single atom catalysts (SACs) which have drawn tremendous attention in recent...

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Theoretical study of the electrochemical reduction of CO2 on cerium dioxide supported palladium single atoms and nanoparticles

Physical Chemistry Chemical Physics ◽

10.1039/d1cp03835d ◽

2021 ◽

Author(s):

Yan nv Guo ◽

haiyan zhu ◽

He Zhao ◽

Qinfu Zhao ◽

Caihua Zhou ◽

...

Keyword(s):

Electrochemical Reduction ◽

Cerium Dioxide ◽

Theoretical Study ◽

Catalytic Performance ◽

Single Atom ◽

Pd Nanoparticle ◽

Single Atoms ◽

Nanoparticle Clusters ◽

Supported Palladium ◽

Reduction Of Co2

Pd/CeO2 catalysts show superior catalytic performance owing to their optimal cycling activity and stability. In this study, single-atom Pd and eight-atoms Pd nanoparticle clusters were supported on the surface of...

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Tunable Carbon Surface from Mono- to Multi-Metallic Single Atoms

10.26434/chemrxiv.12264083 ◽

2020 ◽

Author(s):

Weihong Lai ◽

Heng Wang ◽

Quan jiang ◽

Zichao Yan ◽

Hanwen Liu ◽

...

Keyword(s):

Synergistic Effects ◽

Structural Evolution ◽

Charge Compensation ◽

Catalytic Reactions ◽

Single Atom ◽

Carbon Surface ◽

Hydrogen Electrode ◽

Single Atoms ◽

Mass Activity ◽

Co Doped

Herein, we develop a non-selective charge compensation strategy to prepare multi-single-atom doped carbon (MSAC) in which a sodium p-toluenesulfonate (PTS-Na) doped polypyrrole (S-PPy) polymer is designed to anchor discretionary mixtures of multiple metal cations, including iron (Fe3+), cobalt (Co3+), ruthenium (Ru3+), palladium (Pd2+), indium (In3+), iridium (Ir2+), and platinum (Pt2+) . As illustrated in Figure 1, the carbon surface can be tuned with different level of compositional complexities, including unary Pt1@NC, binary (MSAC-2, (PtFe)1@NC), ternary (MSAC-3, (PtFeIr)1@NC), quaternary (MSAC-4, (PtFeIrRu)1@NC), quinary (MSAC-5, (PtFeIrRuCo)1@NC), senary (MSAC-6, (PtFeIrRuCoPd)1@NC), and septenary (MSAC-7, (PtFeIrRuCoPdIn)1@NC) samples. The structural evolution of carbon surface dictates the activities of both ORR and HER. The senary MSAC-6 achieves the ORR mass activity of 18.1 A·mgmetal-1 at 0.9 V (Vs reversible hydrogen electrode (RHE)) over 30K cycles, which is 164 times higher than that of commercial Pt/C. The quaternary MSAC-4 presented a comparable HER catalytic capability with that of Pt/C. These results indicate that the highly complexed carbon surface can enhance its ability over general electrochemical catalytic reactions. The mechanisms regarding of the ORR and HER activities of the alternated carbon surface are also theoretically and experimentally investigated in this work, showing that the synergistic effects amongst the co-doped atoms can activate or inactivate certain single-atom sites.

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Improving peroxymonosulfate activation by copper ion-saturated adsorbent-based single atom catalysts for the degradation of organic contaminants: electron-transfer mechanism and the key role of Cu single atoms

Journal of Materials Chemistry A ◽

10.1039/d1ta02237g ◽

2021 ◽

Author(s):

Jingwen Pan ◽

Baoyu Gao ◽

Pijun Duan ◽

Kangying Guo ◽

Muhammad Akram ◽

...

Keyword(s):

Electron Transfer ◽

Organic Contaminants ◽

High Salinity ◽

Copper Ion ◽

Single Atom ◽

Electron Transfer Mechanism ◽

Persulfate Oxidation ◽

Single Atoms ◽

Oxidation Technology

Nonradical pathway-based persulfate oxidation technology is considered to be a promising method for high-salinity organic wastewater treatment.

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Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction

Nature Communications ◽

10.1038/s41467-021-22948-w ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Xiaowen Chen ◽

Mi Peng ◽

Xiangbin Cai ◽

Yunlei Chen ◽

Zhimin Jia ◽

...

Keyword(s):

Coordination Number ◽

Density Functional ◽

Activation Barrier ◽

Density Functional Theory Calculation ◽

Catalytic Performance ◽

Atomic Level ◽

Metal Nanoparticle ◽

Single Atom ◽

Nano Structure ◽

Theory Calculation

AbstractMetal nanoparticle (NP), cluster and isolated metal atom (or single atom, SA) exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures. To maximize atom efficiency and boost activity for catalysis, the construction of structure–performance relationship provides an effective way at the atomic level. Here, we successfully fabricate fully exposed Pt3 clusters on the defective nanodiamond@graphene (ND@G) by the assistance of atomically dispersed Sn promoters, and correlated the n-butane direct dehydrogenation (DDH) activity with the average coordination number (CN) of Pt-Pt bond in Pt NP, Pt3 cluster and Pt SA for fundamentally understanding structure (especially the sub-nano structure) effects on n-butane DDH reaction at the atomic level. The as-prepared fully exposed Pt3 cluster catalyst shows higher conversion (35.4%) and remarkable alkene selectivity (99.0%) for n-butane direct DDH reaction at 450 °C, compared to typical Pt NP and Pt SA catalysts supported on ND@G. Density functional theory calculation (DFT) reveal that the fully exposed Pt3 clusters possess favorable dehydrogenation activation barrier of n-butane and reasonable desorption barrier of butene in the DDH reaction.

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Highly dispersed Pt atoms and clusters on hydroxylated indium tin oxide: A view from first-principles calculations

Journal of Materials Chemistry A ◽

10.1039/d1ta03177e ◽

2021 ◽

Author(s):

Simran Kumari ◽

Philippe Sautet

Keyword(s):

Heterogeneous Catalysis ◽

Metal Atom ◽

Tin Oxide ◽

Indium Tin Oxide ◽

First Principles ◽

Catalytic Performance ◽

Small Cluster ◽

Single Atom ◽

First Principles Calculations ◽

Highly Dispersed

Supported single-atom and small cluster catalysts have become highly popular in heterogeneous catalysis. These catalysts can maximize the metal atom utilization while still showcasing superior catalytic performance. One of the...

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