scholarly journals Hydrogen spillover and its relation to catalysis: observations on structurally defined single-atom sites

2021 ◽  
Author(s):  
Max Hülsey ◽  
Victor Fung ◽  
Ning Yan
Keyword(s):  
Catalyst Support ◽  
Structural Evolution ◽  
Hydrogen Spillover ◽  
Atomic Level ◽  
Chemical Processes ◽  
Single Atom ◽  
Hydrogenation Kinetics ◽  
Level Information ◽  
Kinetics Of ◽  
Characterisation Techniques

Abstract Hydrogen spillover, involving the transfer of H atoms from metal sites onto the catalyst support, is ubiquitous in chemical processes such as catalytic hydrogenation and hydrogen storage and is therefore of tremendous fundamental and technological interest. However, atomic level information concerning the kinetics of this process, the structural evolution of the catalysts during hydrogen spillover, as well as the nature of participation of the spilled over H in catalysis, remain vastly lacking. Here, we provide insights to those questions with the development of a solubilised polyoxometalate-supported single-atom catalyst which allows for the use of characterisation techniques generally inaccessible to study heterogeneous catalysis. Hydrogenation kinetics together with poisoning studies further reveal that hydrogen spillover can be either detrimental or beneficial for catalysis – the direction and magnitude of which depends predominantly on the nature of the reducible bond in the substrate. Similar trends were observed on one of the most prototypical hydrogen spillover catalysts, Pt/WO3, supporting the generalisability of the observations.

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>

Single atom catalysts supported on N-doped graphene toward fast kinetic Li−S batteries: a theoretical study

2021 ◽  
Author(s):  
Xu Han ◽  
Zeyun Zhang ◽  
Xuefei Xu
Keyword(s):  
Theoretical Study ◽  
Single Atom ◽  
Discharge Process ◽  
Fast Kinetics ◽  
Shuttle Effect ◽  
Sufficient Stability ◽  
Doped Graphene ◽  
Fast Kinetic ◽  
Kinetics Of ◽  
Charge Discharge

To suppress the shuttle effect of lithium polysulfides and promote fast kinetics of charge−discharge process in Li−S batteries, it is essential to search promising catalysts with sufficient stability and high...

scholarly journals Electronic metal–support interaction modulates single-atom platinum catalysis for hydrogen evolution reaction

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yi Shi ◽  
Zhi-Rui Ma ◽  
Yi-Ying Xiao ◽  
Yun-Chao Yin ◽  
Wen-Mao Huang ◽  
...  
Keyword(s):  
Hydrogen Evolution ◽  
Hydrogen Evolution Reaction ◽  
Structure Activity Relationship ◽  
Atomic Level ◽  
Single Atom ◽  
Activity Relationship ◽  
Support Interaction ◽  
Structure Activity ◽  
Metal Support Interaction ◽  
Metal Support

AbstractTuning metal–support interaction has been considered as an effective approach to modulate the electronic structure and catalytic activity of supported metal catalysts. At the atomic level, the understanding of the structure–activity relationship still remains obscure in heterogeneous catalysis, such as the conversion of water (alkaline) or hydronium ions (acid) to hydrogen (hydrogen evolution reaction, HER). Here, we reveal that the fine control over the oxidation states of single-atom Pt catalysts through electronic metal–support interaction significantly modulates the catalytic activities in either acidic or alkaline HER. Combined with detailed spectroscopic and electrochemical characterizations, the structure–activity relationship is established by correlating the acidic/alkaline HER activity with the average oxidation state of single-atom Pt and the Pt–H/Pt–OH interaction. This study sheds light on the atomic-level mechanistic understanding of acidic and alkaline HER, and further provides guidelines for the rational design of high-performance single-atom catalysts.

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

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.

Atomic-level insight into reasonable design of metal-based catalysts for hydrogen oxidation in alkaline electrolytes

2021 ◽  
Author(s):  
Lulu An ◽  
Xu Zhao ◽  
Tonghui Zhao ◽  
Deli Wang
Keyword(s):  
Fuel Cell ◽  
Anion Exchange ◽  
Hydrogen Oxidation ◽  
Anion Exchange Membrane ◽  
Atomic Level ◽  
Alkaline Electrolytes ◽  
Exchange Membrane ◽  
Kinetics Of ◽  
Insight Into ◽  
Hydrogen Utilization

Anion exchange membrane fuel cell (AEMFC) is becoming highly attractive for hydrogen utilization owing to the advantages of employing economic catalysts in alkaline electrolytes. Nevertheless, the kinetics of anodic hydrogen...

Elastic Properties of Steps at Interphase Boundaries

1991 ◽  
Vol 238 ◽  
Author(s):  
G. J. Shiflet
Keyword(s):  
Energy Density ◽  
Elastic Properties ◽  
Mathematical Analysis ◽  
Strain Energy ◽  
Chemical Processes ◽  
Diffusion Kinetics ◽  
Interphase Boundaries ◽  
Kinetics Of ◽  
Maximum Stresses

ABSTRACTStresses are introduced in crystals at interphase boundaries where steps improve the registry of atoms. A model and mathematical analysis based on an approach previously taken by van der Merwe and Shiflet1–4 of the problem incorporating a coherent step are presented. Computed distributions of stresses, strains, dilatation and energy density in the form of contours and nets are given for a coherent monatomic step. It is concluded that the maximum stresses are quite large and the fields decay fairly rapidly with distance from the steps, the gradient of dilatation around steps will significantly affect diffusion kinetics of impurities and the strain energy seems too low to significantly enhance chemical processes.

Hydrogenation kinetics of toluene on Pt/ZSM-22

2002 ◽  
Vol 90 (1-2) ◽  
pp. 117-129 ◽  
Author(s):  
Joris W. Thybaut ◽  
Mark Saeys ◽  
Guy B. Marin
Keyword(s):  
Hydrogenation Kinetics ◽  
Kinetics Of

scholarly journals Study of Hydrogen Generation of Aluminum-Containing Compositions with Boric Acid

2018 ◽  
Vol 3 (3) ◽  
pp. 230
Author(s):  
Salakhova A.A. ◽  
Suvorov V.A. ◽  
Firsova A. I. ◽  
Belozerov V.I. ◽  
Milinchuk V.K.
Keyword(s):  
Boric Acid ◽  
Hydrogen Generation ◽  
Sodium Metasilicate ◽  
Chemical Processes ◽  
System Management ◽  
Control Rod ◽  
Radiation Fields ◽  
Fuel Elements ◽  
And Control ◽  
Kinetics Of

The results of investigations of the kinetics of hydrogen generation compositions with aluminum, chemical activators (hydrated sodium metasilicate, oxide and calcium hydroxide) boric acid. Aluminium and its alloys used for the manufacture of protective sheaths of fuel elements and control rod protection system management, pipelines, tanks, and various support structures in the active zone of atomic reactors RBMK, research water-cooled reactors. The aluminum is protected from direct contact with water and steam surface layer of metal oxide having a high corrosion resistance at high temperatures in powerful radiation fields. However, after removal or when the discontinuity of the oxide layer of activated metal efficiently decompose water to hydrogen. It is established that the hydrogen aluminum-containing compositions is dependent on the concentration of boric acid. The discovery of the involvement of boric acid in these reactions expands the ideas about regularities of chemical processes of formation of hydrogen flowing in the water coolant of VVER reactors with the participation of the corrective additives and impurities.

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