A vicinal effect for promoting catalysis of Pd1/TiO2: supports of atomically dispersed catalysts play more roles than simply serving as ligands

Liu, Pengxin; Zhao, Yun; Qin, Ruixuan; Gu, Lin; Zhang, Peng; Fu, Gang; Zheng, Nanfeng

doi:10.1016/j.scib.2018.03.002

Cited by 84 publications

(73 citation statements)

References 49 publications

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“…Zheng and co‐workers employed a photodeposition method and successfully synthesized the atomically dispersed Pd on ultrathin TiO 2 nanosheets . As shown in Figure c, during the synthesis process, the two‐atom‐thick TiO 2 nanosheets were first prepared by reacting TiCl 4 with ethylene glycolate, and then mixed with H 2 PdCl 4 to allow the adsorption of Pd species thereon.…”

Section: Challenges In Sac Fabricationmentioning

confidence: 99%

Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married”

Zang

Kou

Pennycook

et al. 2020

Advanced Energy Materials

124

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There is an intensive search for heterogeneous single atom catalysts (SACs) of high activity, efficiency, durability, and selectivity for a wide variety of electrocatalytic conversion and chemical reactions, such as the hydrogen evolution reaction (HER), oxygen evolution/reduction reaction (OER and ORR), CO2 reduction reaction (CO2 RR), and nitrogen reduction reaction (NRR). With the downsizing from nanoparticles and clusters to single atoms, there are steady changes in the bond and coordination environment for each and every atom involved. Indeed, the single atoms in these electrocatalysts are not “singles”; they are “married” to the supporting surfaces, and their performance is controlled by the bonding and coordination with the substrate surfaces. Herein, an overview is presented on the brief history leading to the rapid development of SACs and their current status, by focusing on their synthesis, control of composition, strategies to realize single atoms with the desired bonds and coordination, and targeted performance in selected reactions. Their applications in the selected spectrum of energy conversion and chemical reactions are discussed, in relation to their structures at varying length scales down to the atomic level. A particular emphasis is placed on on‐going research activities, together with the future perspectives and particular challenges for SACs.

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Section: Challenges In Sac Fabricationmentioning

confidence: 99%

Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married”

Zang

Kou

Pennycook

et al. 2020

Advanced Energy Materials

124

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“…The catalyst was used to solve the intractable regioselectivity problems of Heck reactions.Pd@POP-9 can efficiently activate the ends of olefins,therebyleading to high selectivity for substitution at the external position. [13] For metal-catalyzed organic reactions,l igands generally play as ignificant role.I ns ome organic reactions,t he costs of ligands are more expensive than those of the corresponding metal catalysts. This Heckr eaction is the first to be catalyzedb yarecyclable mononuclear metal catalyst with unprecedented catalytic activity and regioselectivity.…”

mentioning

confidence: 99%

“…[8][9][10][11] Fora tomically dispersed catalysts,t he support is very important. [13] For metal-catalyzed organic reactions,l igands generally play as ignificant role.I ns ome organic reactions,t he costs of ligands are more expensive than those of the corresponding metal catalysts. [13] For metal-catalyzed organic reactions,l igands generally play as ignificant role.I ns ome organic reactions,t he costs of ligands are more expensive than those of the corresponding metal catalysts.…”

mentioning

confidence: 99%

Constructing Mononuclear Palladium Catalysts by Precoordination/Solvothermal Polymerization: Recyclable Catalyst for Regioselective Oxidative Heck Reactions

Xiong

et al. 2019

Angew Chem Int Ed

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Heterogeneous,m etal, single-site catalysts often exhibit higher catalytic performance than other catalysts because of their maximized atom efficiency of 100 %. Reported herein is aprecoordination/solvothermal polymerization strategy to fabricate as table mononuclear Pd-metalized porous organic polymer catalyst (Pd@POP). Pd@POP was easy to use in regioselective organic reactions because the internal structure of this Pd@POP can be easily modified. The catalyst was used to solve the intractable regioselectivity problems of Heck reactions.Pd@POP-9 can efficiently activate the ends of olefins,therebyleading to high selectivity for substitution at the external position. To understand the reason underlying the high selectivity and activity of the catalyst, the systemic characterization of Pd@POP-9 and density-functional theory calculations were conducted. This Heckr eaction is the first to be catalyzedb yarecyclable mononuclear metal catalyst with unprecedented catalytic activity and regioselectivity.Compared with the homogeneous metal/ligand catalytic mode,t he heterogenization of corresponding homogeneous catalysts is an attractive tool for achieving recyclable catalysts and highly selective organic synthesis. [1][2][3][4] Forh eterogeneous catalysts,decreasing the size of catalytic metals can maximize the utilization of precious metals.B ecause only as mall number of metal particles,with appropriate size distribution, can be used as catalytic active sites,and particles of other sizes are either inert or cause side reactions. [5][6][7] Dispersing metal active sites into isolated metal atoms (ions) is an effective strategy for solving these problems.T herefore,m any atomically dispersed catalysts with either single atoms or mononuclear metal complexes (single metal ions) have been prepared for this purpose. [8][9][10][11] Fora tomically dispersed catalysts,t he support is very important. [12] Unfortunately,i n the existing literature,m ost supports do not play the role of the ligand, thereby preventing its large-scale application in ligand-controlled regioselective organic reactions. [13] For metal-catalyzed organic reactions,l igands generally play as ignificant role.I ns ome organic reactions,t he costs of ligands are more expensive than those of the corresponding metal catalysts. [14,15] Therefore,t he development of ah ighly efficient ligand that can be recycled and applied as asupport to am ononuclear metal catalyst will result in the development of modern organic synthesis methods.Porous organic polymers (POPs) have remained aperennial focus as an intriguing platform for incorporating homogeneous metal/ligand catalytic systems into heterogeneous supports. [16][17][18][19] In our previous work, [20][21][22][23] we demonstrated the advantages of phosphorus-doped (P-doped) POPs in catalytic regioselective and chemoselective reactions,a nd as an effective metal support for as ingle-site catalyst. When Pdoped POPs are used as supports,m ononuclear metal catalysts with 100 %m etal dispersion can be efficiently synthe...

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“…[7][8][9][10][11] However,the preparation of single-atom-distributed catalysts is still quite challenging,a nd their characterization is highly dependent on advanced microscopy and synchrotron radiation techniques. [14][15][16][17] Accordingly,t he associated and highly desirable structureperformance relationships are still not well understood. [14][15][16][17] Accordingly,t he associated and highly desirable structureperformance relationships are still not well understood.…”

mentioning

confidence: 99%

“…[12,13] Moreover,d ue to the lack of atomic structures,i ti sr ather difficult to study the metal-support interaction and the functional role of the support which is crucial for the performance of such catalyst systems. [14][15][16][17] Accordingly,t he associated and highly desirable structureperformance relationships are still not well understood.…”

mentioning

confidence: 99%

Ag₁₀Ti₂₈‐Oxo Cluster Containing Single‐Atom Silver Sites: Atomic Structure and Synergistic Electronic Properties

Chen

Fang

et al. 2019

Angewandte Chemie

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Supported single-atom catalysts have been emerging as promising materials in av ariety of energy catalysis applications.H owever,s tudying the role of metal-support interactions at the molecular level remains am ajor challenge, primarily due to the lacko fp recise atomic structures.I nt his work, by replacing the frequently used TiO 2 support with its molecular analogue,t itanium-oxo cluster (TOC), we successfully produced anew kind of Ti-O material doped with single silver sites.T he as-obtained Ag 10 Ti 28 cluster,c ontaining four exposed and six embedded Ag sites,isthe largest noble-metaldoped Ti-O cluster reported to date.Density functional theory (DFT) calculations show that the Ag 10 Ti 28 core exhibits properties distinct from those of metallic Ag-based materials. This Ti-O material doped with single Ag sites presents ahigh e d and moderate CO binding capacity comparable to that of metallic Cu-based catalysts,s uggesting that it might display different catalytic performance from the common Ag-based catalysts,f or example,f or CO 2 reduction. These results prove that the synergism of active surface metal atoms and the Ti-O cluster support result in unique physical properties,w hich might open anew direction for single-atom-included catalysts.Inthe field of catalysis,i th as been well established that the catalytic performance of materials is highly dependent on size,m orphology,a nd structure. [1][2][3][4][5][6] Especially,t he recently developed single-atom catalysts are attracting tremendous interest due to their excellent activity and selectivity. [7][8][9][10][11] However,the preparation of single-atom-distributed catalysts is still quite challenging,a nd their characterization is highly dependent on advanced microscopy and synchrotron radiation techniques. [12,13] Moreover,d ue to the lack of atomic structures,i ti sr ather difficult to study the metal-support interaction and the functional role of the support which is crucial for the performance of such catalyst systems. [14][15][16][17] Accordingly,t he associated and highly desirable structureperformance relationships are still not well understood.Nanoparticles or nanoclusters of noble metals have been applied as promising catalysts in avariety of fields, [18][19][20][21][22][23] while titanium dioxide (TiO 2 )h as been extensively investigated as as upport for heterogeneous catalysts and also single atoms. [24][25][26][27][28][29] Recent developments in the molecular analogues of TiO 2 ,crystalline polyoxotitanium clusters (PTCs), provides us with wonderful opportunities to investigate the structures and reactivities of titanium oxides at the molecular level. [30][31][32][33][34][35][36][37][38][39] Therefore,itishighly desirable to design and synthesize anew type of cluster-stabilized single-atom material by decorating single atoms of catalytically active noble metals on titaniumoxo clusters.I nt his way,t he synergism between the Ti-oxo cluster support and noble-metal active site could lead to unique physical properties (Scheme 1). More important...

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A vicinal effect for promoting catalysis of Pd1/TiO2: supports of atomically dispersed catalysts play more roles than simply serving as ligands

Cited by 84 publications

References 49 publications

Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married”

Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married”

Constructing Mononuclear Palladium Catalysts by Precoordination/Solvothermal Polymerization: Recyclable Catalyst for Regioselective Oxidative Heck Reactions

Ag₁₀Ti₂₈‐Oxo Cluster Containing Single‐Atom Silver Sites: Atomic Structure and Synergistic Electronic Properties

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A vicinal effect for promoting catalysis of Pd1/TiO2: supports of atomically dispersed catalysts play more roles than simply serving as ligands

Cited by 84 publications

References 49 publications

Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married”

Heterogeneous Single Atom Electrocatalysis, Where “Singles” Are “Married”

Constructing Mononuclear Palladium Catalysts by Precoordination/Solvothermal Polymerization: Recyclable Catalyst for Regioselective Oxidative Heck Reactions

Ag10Ti28‐Oxo Cluster Containing Single‐Atom Silver Sites: Atomic Structure and Synergistic Electronic Properties

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Ag₁₀Ti₂₈‐Oxo Cluster Containing Single‐Atom Silver Sites: Atomic Structure and Synergistic Electronic Properties