General approach for atomically dispersed precious metal catalysts toward hydrogen reaction

As a carbon-free energy carrier,hydrogen has become the pivot for future clean energy,while efficient hydrogen production and combustion still require precious metal-based catalysts.Single-atom catalysts(SACs)with high atomic utilization open up a desirable perspective for the scale applications of precious metals,but the general and facile preparation of various precious metal-based SACs remains challenging.Herein,a general movable printing method has been developed to synthesize various precious metal-based SACs,such as Pd,Pt,Rh,Ir,and Ru,and the features of highly dispersed single atoms with nitrogen coordination have been identified by comprehensive characterizations.More importantly,the synthesized Pt-and Ru-based SACs exhibit much higher activities than their corresponding nanoparticle counterparts for hydrogen oxidation reaction and hydrogen evolution reaction(HER).In addition,the Pd-based SAC delivers an excellent activity for photocatalytic hydrogen evolution.Especially for the superior mass activity of Ru-based SACs toward HER,density functional theory calculations confirmed that the adsorption of the hydrogen atom has a significant effect on the spin state and electronic structure of the catalysts.

Isolated Co Atoms Anchored on Defective Nitrogen-doped Carbon Graphene as Efficient Oxygen Reduction Reaction Electrocatalysts

Oxygen reduction reaction(ORR)is the heart of many new energy conversions and storage devices,such as metal-air batteries and fuel cells.However,ORR is currently facing the dilemma of sluggish intrinsic kinetics and the noble electrocatalysts of high price and low reserves.In this work,isolated Co atoms anchored on defective nitrogen-doped carbon graphene single-atom catalyst(Co-SAC/NC)are synthesized via the proposed movable type printing method.The prepared Co-SAC/NC catalyst demonstrates admirable ORR performance,with a high half-wave potential of 0.884 V in alkaline electrolytes and outstanding durability.In addition,an assembled zinc–air battery with prepared Co-SAC/NC as air-cathode catalyst displays a high-peak power density of 179 mW cm^(-2)and a high-specific capacity(757 mAh g^(-1)).Density functional theory calculations confirm that the true active sites of the prepared catalyst are Co-N_(4)moieties,and further reveal a significantly electronic structure evolution of Co sites in the ORR process,in which the project density of states and local magnetic moment of Co atom varies during its whole reaction process.This work not only paves a new avenue for synthesizing SACs as robust electrocatalysts,but also provides an electronic-level insight into the evolution of the electronic structure of single-atom catalysts.

Rational design ternary platinum based electrocatalysts for effective methanol oxidation reaction

Exploring effective, durable, and affordable electrocatalysts of methanol oxidation reaction(MOR) is of vital significance for the industrial application of direct methanol fuel cells. Herein, an efficient, general,and expandable method is developed to synthesis two-dimensional(2D) ternary Pt Bi M nanoplates(NPLs), in which various M(Co, Ni, Cu, Zn, Sn) is severed as the third component to the binary Pt Bi system. The MOR performance of Pt Bi M NPLs is entirely investigated, demonstrating that both the MOR activity and durability is enhanced with the introduction of the additional composition. Pt3Bi3Zn NPLs shows much higher MOR activity and stability than that of the Pt Bi counterparts, not to mention the current advanced Pt Ru/C and Pt/C catalysts. The prominent performances are attributed to the modulated electronic structure of the surface Pt in Pt Bi NPLs by the addition of Zn, resulting in a weakened affination between Pt and the adsorbed poisoning species(mainly CO) compared with Pt Bi NPLs, verified by density functional theory(DFT) calculations. In addition, the absorbed OH can be generated on the surface of Zn atom due to its favorable water activation properties, thus the CO removal on the adjacent Pt atoms is accelerated, further leading to a high activity and anti-poisoning performance of the resulting Pt_(3)Bi_(3)Zn catalyst. This work provides new insights and robust strategy for highly efficient MOR electrocatalyst with extraordinary anti-poisoning performance and stability.

Single atomic cobalt electrocatalyst for efficient oxygen reduction reaction

Robust oxygen reduction reaction(ORR)catalysts are essential for energy storage and conversion devices,but their development remains challenging.Herein,we design a single-atom catalyst featuring isolated Co anchored on nitrogen-doped carbon(Co-SAC/NC)via a highly efficient“plasma-bombing”strategy.With a high loading(up to 2.5​wt%),the well-dispersed single Co atoms in Co-SAC/NC give it robust ORR performance in an alkaline medium.It also demonstrates excellent battery performance when implemented as the air-cathode catalyst in a zinc-air battery(ZAB).Theoretical calculations reveal that the Co-N_(4)moiety experiences an“extraction/recovery”structural evolution during the ORR process,and the reaction's rate-determining step is the formation of OOH∗(reaction intermediate).This work provides a new strategy for designing robust ORR catalysts for high-performance ZABs and other energy-conversion devices.