scholarly journals Morphological Attributes Govern CO2 Reduction on Mesoporous Carbon Nanosphere with Embedded Axial Co-N5 Sites

2021 ◽  
Author(s):  
Youzhi Li ◽  
Bo Wei ◽  
Zhongjian Li ◽  
Lei Fan ◽  
Qike Jiang ◽  
...  
Keyword(s):  
Mesoporous Carbon ◽  
High Performance ◽  
Density Functional ◽  
Rational Design ◽  
Co2 Reduction ◽  
Catalytic Performance ◽  
Reduction Reaction ◽  
Single Atom ◽  
High Turnover ◽  
Morphological Attributes

Abstract Although single-atom catalysts (SACs) have been widely employed in the CO2 reduction reaction (CO2RR), the understanding regarding the effect of morphological attributes on catalytic performance are still lacking, which prevents the rational design of high-performance catalysts for electrochemical CO2RR. Here, we developed a novel catalyst with axial Co-N5 sites embedded on controllable mesoporous carbon nanosphere with different graded pore structures. Benefiting from the precise control of porosity, the influence of morphological attributes on catalytic performance was well revealed. In situ characterization combined with density functional theory (DFT) calculations revealed that axial N-coordination induced local d-p orbitals coupling enhancement of Co with oxides and the optimal pore size of 27 nm promoted the interfacial bonding characteristics, which facilitate both the COOH* generation and CO desorption. Consequently, A superior selectivity of nearly 100% at -0.8 V vs. RHE and commercially relevant current densities of >150 mA cm−2 could be achieved, and a strikingly high turnover frequency of 1.136*104 h−1 at -1.0 V has been obtained, superior to the most of Co-based catalysts.

Rational design of three-dimensional nitrogen-doped carbon nanoleaf networks for high-performance oxygen reduction

2015 ◽  
Vol 3 (10) ◽  
pp. 5617-5627 ◽  
Author(s):  
Liang Chen ◽  
Chenyu Xu ◽  
Ran Du ◽  
Yueyuan Mao ◽  
Cheng Xue ◽  
...  
Keyword(s):  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
High Performance ◽  
Rational Design ◽  
Three Dimensional ◽  
Catalytic Performance ◽  
Reduction Reaction ◽  
Nitrogen Doped ◽  
Nitrogen Doped Carbon ◽  
Excellent Catalytic Performance

“Carbon nanoleaf” aerogels were developed, constructed with nitrogen-doped CNTs/GNRs, which show excellent catalytic performance in oxygen reduction reaction.

scholarly journals A general strategy for preparing pyrrolic-N4 type single-atom catalysts via pre-located isolated atoms

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Junjie Li ◽  
Ya-fei Jiang ◽  
Qi Wang ◽  
Cong-Qiao Xu ◽  
Duojie Wu ◽  
...  
Keyword(s):  
Active Sites ◽  
Density Functional ◽  
Rational Design ◽  
Catalytic Performance ◽  
Single Atom ◽  
General Strategy ◽  
New Findings ◽  
Synthesis Strategy ◽  
Structure Density ◽  
Application Fields

AbstractSingle-atom catalysts (SACs) have been applied in many fields due to their superior catalytic performance. Because of the unique properties of the single-atom-site, using the single atoms as catalysts to synthesize SACs is promising. In this work, we have successfully achieved Co1 SAC using Pt1 atoms as catalysts. More importantly, this synthesis strategy can be extended to achieve Fe and Ni SACs as well. X-ray absorption spectroscopy (XAS) results demonstrate that the achieved Fe, Co, and Ni SACs are in a M1-pyrrolic N4 (M= Fe, Co, and Ni) structure. Density functional theory (DFT) studies show that the Co(Cp)2 dissociation is enhanced by Pt1 atoms, thus leading to the formation of Co1 atoms instead of nanoparticles. These SACs are also evaluated under hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), and the nature of active sites under HER are unveiled by the operando XAS studies. These new findings extend the application fields of SACs to catalytic fabrication methodology, which is promising for the rational design of advanced SACs.

scholarly journals Recent Advances in Isolated Single-Atom Catalysts for Zinc Air Batteries: A Focus Review

Nanomaterials ◽  
2019 ◽  
Vol 9 (10) ◽  
pp. 1402 ◽  
Author(s):  
Weimin Zhang ◽  
Yuqing Liu ◽  
Lipeng Zhang ◽  
Jun Chen
Keyword(s):  
Electrocatalytic Activity ◽  
High Performance ◽  
Rational Design ◽  
High Energy ◽  
Reduction Reaction ◽  
High Energy Density ◽  
Single Atom ◽  
Design And Synthesis ◽  
Dual Metal ◽  
Zinc Air Batteries

Recently, zinc–air batteries (ZABs) have been receiving attention due to their theoretically high energy density, excellent safety, and the abundance of zinc resources. Typically, the performance of the zinc air batteries is determined by two catalytic reactions on the cathode—the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Therefore, intensive effort has been devoted to explore high performance electrocatalysts with desired morphology, size, and composition. Among them, single-atom catalysts (SACs) have emerged as attractive and unique systems because of their high electrocatalytic activity, good durability, and 100% active atom utilization. In this review, we mainly focus on the advance application of SACs in zinc air batteries in recent years. Firstly, SACs are briefly compared with catalysts in other scales (i.e., micro- and nano-materials). A main emphasis is then focused on synthesis and electrocatalytic activity as well as the underlying mechanisms for mono- and dual-metal-based SACs in zinc air batteries catalysis. Finally, a prospect is provided that is expected to guide the rational design and synthesis of SACs for zinc air batteries.

Double-atom catalysts for energy-related electrocatalysis applications: a theoretical perspective

2022 ◽  
Author(s):  
Donghai Wu ◽  
Bingling He ◽  
Yuanyuan Wang ◽  
Peng Lv ◽  
Dongwei Ma ◽  
...  
Keyword(s):  
Rational Design ◽  
Synergetic Effect ◽  
Catalytic Performance ◽  
Reduction Reaction ◽  
Atomic Scale ◽  
Theoretical Research ◽  
Single Atom ◽  
Research Attention ◽  
Wide Range ◽  
Electrocatalytic Reactions

Abstract Due to the excellent activity, selectivity, and stability, atomically dispersed metal catalysts with well-defined structures have attracted intensive research attention. As the extension of single-atom catalyst (SAC), double-atom catalyst (DAC) has recently emerged as a research focus. Compared with SAC, the higher metal loading, more complicated and flexible active site, easily tunable electronic structure, and the synergetic effect between two metal atoms could provide DACs with better catalytic performance for a wide range of catalytic reactions. This review aims to summarize the recent advance in theoretical research on DACs for diverse energy-related electrocatalytic reactions. It starts with a brief introduction to DACs. Then an overview of the main experimental synthesis strategies of DACs is provided. Emphatically, the catalytic performance together with the underlying mechanism of the different electrocatalytic reactions, including nitrogen reduction reaction, carbon dioxide reduction reaction, oxygen reduction reaction, and oxygen and hydrogen evolution reactions, are highlighted by discussing how the outstanding attributes mentioned above affect the reaction pathway, catalytic activity, and product selectivity. Finally, the opportunities and challenges for the development of DACs are prospected to shed fresh light on the rational design of more efficient catalysts at the atomic scale in the future.

Robust wrinkled MoS2/N-C bifunctional electrocatalysts interfaced with single Fe atoms for wearable zinc-air batteries

2021 ◽  
Vol 118 (40) ◽  
pp. e2110036118
Author(s):  
Yan Yan ◽  
Shuang Liang ◽  
Xiang Wang ◽  
Mingyue Zhang ◽  
Shu-Meng Hao ◽  
...  
Keyword(s):  
High Performance ◽  
Density Functional ◽  
High Capacity ◽  
Density Functional Theory Calculations ◽  
Catalytic Performance ◽  
Cycling Stability ◽  
Single Atom ◽  
Core Shell ◽  
Bifunctional Electrocatalysts ◽  
Zinc Air Batteries

The ability to create highly efficient and stable bifunctional electrocatalysts, capable of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in the same electrolyte, represents an important endeavor toward high-performance zinc-air batteries (ZABs). Herein, we report a facile strategy for crafting wrinkled MoS2/N-doped carbon core/shell nanospheres interfaced with single Fe atoms (denoted MoS2@Fe-N-C) as superior ORR/OER bifunctional electrocatalysts for robust wearable ZABs with a high capacity and outstanding cycling stability. Specifically, the highly crumpled MoS2 nanosphere core is wrapped with a layer of single-Fe-atom-impregnated, N-doped carbon shell (i.e., Fe-N-C shell with well-dispersed FeN4 sites). Intriguingly, MoS2@Fe-N-C nanospheres manifest an ORR half-wave potential of 0.84 V and an OER overpotential of 360 mV at 10 mA⋅cm−2. More importantly, density functional theory calculations reveal the lowered energy barriers for both ORR and OER, accounting for marked enhanced catalytic performance of MoS2@Fe-N-C nanospheres. Remarkably, wearable ZABs assembled by capitalizing on MoS2@Fe-N-C nanospheres as an air electrode with an ultralow area loading (i.e., 0.25 mg⋅cm−2) display excellent stability against deformation, high special capacity (i.e., 442 mAh⋅g−1Zn), excellent power density (i.e., 78 mW⋅cm−2) and attractive cycling stability (e.g., 50 cycles at current density of 5 mA⋅cm−2). This study provides a platform to rationally design single-atom-interfaced core/shell bifunctional electrocatalysts for efficient metal-air batteries.

scholarly journals Boron-Doped MXenes as Electrocatalysts for Nitrogen Reduction Reaction: A Theoretical Study

2021 ◽  
Vol 3 ◽  
Author(s):  
Yuan Wang ◽  
Xu Qian ◽  
Guokui Zheng ◽  
Ziqi Tian ◽  
Qiuju Zhang
Keyword(s):  
Triple Bond ◽  
Density Functional ◽  
Rational Design ◽  
Surface Composition ◽  
Lone Pair ◽  
Catalytic Performance ◽  
Reduction Reaction ◽  
Nitrogen Reduction ◽  
Boron Doped ◽  
Reduction Catalysts

Electrocatalytic nitrogen reduction reaction (NRR) is a promising and sustainable approach for ammonia production. Since boron as an active center possesses electronic structure similar to that of transition metals with d-orbitals (J. Am. Chem. Soc., 2019, 141 (7), 2884), it is supposed to be able to effectively activate the triple bond in N2. MXenes can be applied as substrates due to the large specific surface area, high conductivity, and tunable surface composition. In this work, the catalytic performance of a series of MXenes-supported single boron atom systems (labeled as B@MXenes) has been systematically studied by using density functional theory (DFT). B@Nb4C3O2, B@Ti4N3O2, and B@Ti3N2O2 were screened out owing to outstanding catalytic activity with limiting potentials of −0.26, −0.15, and −0.10 V, respectively. Further analysis shows that the unique property of boron that can intensely accept lone pair and back-donate the anti-bond of nitrogen contributes to the activation of inert triple bond. This work provides a new idea for the rational design of NRR catalyst and is of great significance for the future development of nitrogen reduction catalysts.

scholarly journals Theoretical Inspection of TM-P4C Single-Atom Electrocatalyst: Ultra-High Performance for bifunctional Oxygen Reduction and Evolution Reactions

2021 ◽  
Author(s):  
Hong Zhu ◽  
Chaohong Guan
Keyword(s):  
Catalytic Activity ◽  
Oxygen Reduction ◽  
High Performance ◽  
Density Functional ◽  
Density Functional Theory Method ◽  
Cost Effective ◽  
Reduction Reaction ◽  
Single Atom ◽  
Single Transition ◽  
The Cost

Developing the cost-effective or even bifunctional electrocatalysts for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) with industrially relevant activity is highly desired for metal-air batteries at the current stage. Herein, in this work, the catalytic performances of the single transition metal (TM) atom embeds graphene sheet with the tetra-coordinates Phosphorus (TMP4) for ORR and OER were investigated based on the density functional theory method. The results demonstrate that the most promising ORR and OER catalytic activity can achieved on the CoP4 with the smallest potential gap ∆E and the lowest overpotentials of 0.37 and 0.32 eV among all TMP4 systems, respectively, and the catalytic activity is even better than that of the traditional Pt and IrO2 catalysts. Furthermore, the AIMD calculation was conducted to confirm the thermodynamics stability of CoP4. This work screens out promising candidates for novel graphene-based bifunctional ORR and OER catalysts and provides the theoretical guidance for the development of single-atom catalysts.

scholarly journals Mo-doped boron nitride monolayer as a promising single-atom electrocatalyst for CO2 conversion

2019 ◽  
Vol 10 ◽  
pp. 540-548 ◽  
Author(s):  
Qianyi Cui ◽  
Gangqiang Qin ◽  
Weihua Wang ◽  
Lixiang Sun ◽  
Aijun Du ◽  
...  
Keyword(s):  
Boron Nitride ◽  
Density Functional ◽  
Experimental Studies ◽  
Catalytic Performance ◽  
Reduction Reaction ◽  
Single Atom ◽  
Ambient Conditions ◽  
Functional Theory ◽  
Earth Abundant ◽  
Insight Into

The design of new, efficient catalysts for the conversion of CO2 to useful fuels under mild conditions is urgent in order to reduce greenhouse gas emissions and alleviate the energy crisis. In this work, a series of transition metals (TMs), including Sc to Zn, Mo, Ru, Rh, Pd and Ag, supported on a boron nitride (BN) monolayer with boron vacancies, were investigated as electrocatalysts for the CO2 reduction reaction (CRR) using comprehensive density functional theory (DFT) calculations. The results demonstrate that a single-Mo-atom-doped boron nitride (Mo-doped BN) monolayer possesses excellent performance for converting CO2 to CH4 with a relatively low limiting potential of −0.45 V, which is lower than most catalysts for the selective production of CH4 as found in both theoretical and experimental studies. In addition, the formation of OCHO on the Mo-doped BN monolayer in the early hydrogenation steps is found to be spontaneous, which is distinct from the conventional catalysts. Mo, as a non-noble element, presents excellent catalytic performance with coordination to the BN monolayer, and is thus a promising transition metal for catalyzing CRR. This work not only provides insight into the mechanism of CRR on the single-atom catalyst (Mo-doped BN monolayer) at the atomic level, but also offers guidance in the search for appropriate earth-abundant TMs as electrochemical catalysts for the efficient conversion of CO2 to useful fuels under ambient conditions.

High-Entropy Alloys as Catalysts for the CO2 and CO Reduction Reactions

2019 ◽  
Author(s):  
Jack Pedersen ◽  
Thomas Batchelor ◽  
Alexander Bagger ◽  
Jan Rossmeisl
Keyword(s):  
Density Functional ◽  
Rational Design ◽  
Hydrogen Adsorption ◽  
Co Adsorption ◽  
Reduction Reaction ◽  
Supervised Machine Learning ◽  
High Entropy Alloys ◽  
High Entropy ◽  
Co Reduction ◽  
Disordered Alloy

Using the high-entropy alloys (HEAs) CoCuGaNiZn and AgAuCuPdPt as starting points we provide a framework for tuning the composition of disordered multi-metallic alloys to control the selectivity and activity of the reduction of carbon dioxide (CO2) to highly reduced compounds. By combining density functional theory (DFT) with supervised machine learning we predicted the CO and hydrogen (H) adsorption energies of all surface sites on the (111) surface of the two HEAs. This allowed an optimization for the HEA compositions with increased likelihood for sites with weak hydrogen adsorption{to suppress the formation of molecular hydrogen (H2) and with strong CO adsorption to favor the reduction of CO. This led to the discovery of several disordered alloy catalyst candidates for which selectivity towards highly reduced carbon compounds is expected, as well as insights into the rational design of disordered alloy catalysts for the CO2 and CO reduction reaction.

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