Zero‐Valent Palladium Single‐Atoms Catalysts Confined in Black Phosphorus for Efficient Semi‐Hydrogenation

2021 ◽  
pp. 2008471
Author(s):  
Cheng Chen ◽  
Wei Ou ◽  
Kah‐Meng Yam ◽  
Shibo Xi ◽  
Xiaoxu Zhao ◽  
...  
Keyword(s):  
Black Phosphorus ◽  
Single Atoms

scholarly journals Zero-valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-hydrogenation

2020 ◽  
Author(s):  
cheng chen ◽  
Ou Wei ◽  
Yam Kahmeng ◽  
Xi Shibo ◽  
Zhao Xiaoxu ◽  
...  
Keyword(s):  
Atomic Layer ◽  
Pd Nanoparticles ◽  
Black Phosphorus ◽  
Single Atom ◽  
Chemical Transformations ◽  
Confined Space ◽  
Organic Transformations ◽  
Single Atoms ◽  
Wide Range ◽  
High Valence State

<p></p><p>Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. Here, we demonstrated that two-dimensional (2D) black phosphorus (BP) act as giant phosphorus (P) ligand to confine a high density of single atoms (eg, Pd1, Pt1) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd1/P SAC shows a highly selective semi-hydrogenation of phenylacetylene towards styrene, outperforming high-valence Pt1/P SAC, and also distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Our DFT calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb over electron-rich region for the subsequent hydrogenation. Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially-hydrogenated product over the fully-hydrogenated one. Our work provides a new route towards the synthesis of zero-valent SACs on BP for a wide range of organic transformations. <br></p><p></p>

scholarly journals Zero-valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-hydrogenation

2020 ◽  
Author(s):  
cheng chen ◽  
Ou Wei ◽  
Yam Kahmeng ◽  
Xi Shibo ◽  
Zhao Xiaoxu ◽  
...  
Keyword(s):  
Atomic Layer ◽  
Pd Nanoparticles ◽  
Black Phosphorus ◽  
Single Atom ◽  
Chemical Transformations ◽  
Confined Space ◽  
Organic Transformations ◽  
Single Atoms ◽  
Wide Range ◽  
High Valence State

<p></p><p>Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. Here, we demonstrated that two-dimensional (2D) black phosphorus (BP) act as giant phosphorus (P) ligand to confine a high density of single atoms (eg, Pd1, Pt1) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd1/P SAC shows a highly selective semi-hydrogenation of phenylacetylene towards styrene, outperforming high-valence Pt1/P SAC, and also distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Our DFT calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb over electron-rich region for the subsequent hydrogenation. Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially-hydrogenated product over the fully-hydrogenated one. Our work provides a new route towards the synthesis of zero-valent SACs on BP for a wide range of organic transformations. <br></p><p></p>

Single atoms spied on graphene sliver

Nature ◽  
2008 ◽  
Author(s):  
Katharine Sanderson
Keyword(s):  
Single Atoms

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

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

<p>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 (Fe<sup>3+</sup>), cobalt (Co<sup>3+</sup>), ruthenium (Ru<sup>3+</sup>), palladium (Pd<sup>2+</sup>), indium (In<sup>3+</sup>), iridium (Ir<sup>2+</sup>), and platinum (Pt<sup>2+</sup>) . As illustrated in Figure 1, the carbon surface can be tuned with different level of compositional complexities, including unary Pt<sub>1</sub>@NC, binary (MSAC-2, (PtFe)<sub>1</sub>@NC), ternary (MSAC-3, (PtFeIr)<sub>1</sub>@NC), quaternary (MSAC-4, (PtFeIrRu)<sub>1</sub>@NC), quinary (MSAC-5, (PtFeIrRuCo)<sub>1</sub>@NC), senary (MSAC-6, (PtFeIrRuCoPd)<sub>1</sub>@NC), and septenary (MSAC-7, (PtFeIrRuCoPdIn)<sub>1</sub>@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·mg<sub>metal</sub><sup>-1</sup> 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.</p>

Biomimetic Extracellular Vesicles Embedded with Black Phosphorus for Molecular Recognition-Guided Biomineralization

2018 ◽  
Author(s):  
Yingqian Wang ◽  
Xiaoxia Hu ◽  
Lingling Zhang ◽  
Chunli Zhu ◽  
Jie Wang ◽  
...  
Keyword(s):  
Molecular Recognition ◽  
Extracellular Vesicles ◽  
Inorganic Phosphate ◽  
Physiological Activity ◽  
Medical Engineering ◽  
Matrix Vesicles ◽  
Black Phosphorus ◽  
Photothermal Effect ◽  
Biological Processes ◽  
Extracellular Environment

Extracellular vesicles (EVs) are involved in the regulation of cell physiological activity and the reconstruction of extracellular environment. Matrix vesicles (MVs) are a type of EVs, and they participate in the regulation of cell mineralization. Herein, bioinspired MVs embedded with black phosphorus are functionalized with cell-specific aptamer (denoted as Apt-bioinspired MVs) for stimulating biomineralization. The aptamer can direct bioinspired MVs to targeted cells, and the increasing concentration of inorganic phosphate originated from the black phosphorus can facilitate cell biomineralization. The photothermal effect of the Apt-bioinspired MVs also positively affects mineralization. In addition, the Apt-bioinspired MVs display outstanding bone regeneration performance. Considering the excellent behavior of the Apt-bioinspired MVs for promoting biomineralization, our strategy provides a way of designing bionic tools for studying the mechanisms of biological processes and advancing the development of medical engineering.<br>

Sequentially Triggered Delivery System of Black Phosphorus Quantum Dots with Surface Charge-Switching Ability for Precise Tumor Radiosensitization

ACS Nano ◽  
2018 ◽  
Vol 12 (12) ◽  
pp. 12401-12415 ◽  
Author(s):  
Leung Chan ◽  
Pan Gao ◽  
Wenhua Zhou ◽  
Chaoming Mei ◽  
Yanyu Huang ◽  
...  
Keyword(s):  
Quantum Dots ◽  
Surface Charge ◽  
Delivery System ◽  
Black Phosphorus ◽  
Black Phosphorus Quantum Dots

Super-Slippery Degraded Black Phosphorus/Silicon Dioxide Interface

2020 ◽  
Vol 12 (6) ◽  
pp. 7717-7726 ◽  
Author(s):  
Shuai Wu ◽  
Feng He ◽  
Guoxin Xie ◽  
Zhengliang Bian ◽  
Yilong Ren ◽  
...  
Keyword(s):  
Silicon Dioxide ◽  
Black Phosphorus

scholarly journals Robust Carbon-Stabilization of Few-Layer Black Phosphorus for Superior Oxygen Evolution Reaction

Coatings ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 695 ◽  
Author(s):  
Mengjie Zhang ◽  
Wenchang Zhu ◽  
Xingzhe Yang ◽  
Meng Feng ◽  
Hongbin Feng
Keyword(s):  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Black Phosphorus ◽  
Carbon Stabilization ◽  
High Durability ◽  
Carbon Coated ◽  
Alkaline Conditions ◽  
Doped Graphene ◽  
A Current

Few-layer exfoliated black phosphorus (Ex-BP) has attracted tremendous attention owing to its promising applications, including in electrocatalysis. However, it remains a challenge to directly use few-layer Ex-BP as oxygen-involved electrocatalyst because it is quite difficult to restrain structural degradation caused by spontaneous oxidation and keep it stable. Here, a robust carbon-stabilization strategy has been implemented to prepare carbon-coated Ex-BP/N-doped graphene nanosheet (Ex-BP/NGS@C) nanostructures at room temperature, which exhibit superior oxygen evolution reaction (OER) activity under alkaline conditions. Specifically, the as-synthesized Ex-BP/NGS@C hybrid presents a low overpotential of 257 mV at a current density of 10 mA cm−2 with a small Tafel slope of 52 mV dec−1 and shows high durability after long-term testing.

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