Pt Single Atoms Supported on Defect Ceria as an Active and Stable Dual-Site Catalyst for Alkaline Hydrogen Evolution.

This work evaluates the feasibility of alkaline hydrogen evolution reaction (HER) using Pt single-atoms (1.0 wt %) on defect-rich ceria (Pt1/CeOx) as an active and stable dual-site catalyst. The catalyst displayed a low overpotential and a small Tafel slope in an alkaline medium. Moreover, Pt1/CeOx presented a high mass activity and excellent durability, competing with those of the commercial Pt/C (20 wt %). In this picture, the defective CeOx is active for water adsorption and dissociation to create H* intermediates, providing the first site where the reaction occurs. The H* intermediate species then migrate to adsorb and react on the Pt2+ isolated atoms, the site where H2 is formed and released. DFT calculations were also performed to obtain mechanistic insight on the Pt1/CeOx catalyst for the HER. The results indicate a new possibility to improve the state-of-the-art alkaline HER catalysts via a combined effect of the O vacancies on the ceria support and Pt2+ single atoms.

Switch Volmer-Heyrovsky to Volmer-Tafel Pathway for Efficient Acidic Electrocatalytic Hydrogen Evolution by Correlating Pt Single Atoms with Clusters.

As cost-effective catalysts, platinum (Pt) single-atom catalysts (SACs) have attracted substantial attention. However, most studies indicate that Pt SACs in acidic hydrogen evolution reaction (HER) follow the slow Volmer-Heyrovsky (VH) mechanism instead of the fast kinetic Volmer-Tafel (VT) pathway. Here, this work propose that the VH mechanism in Pt SACs can be switched to the faster VT pathway for efficient HER by correlating Pt single atoms (SAs) with Pt clusters (Cs). Our calculations reveal that the correlation between Pt SAs and Cs significantly impacts the electronic structure of exposed Pt atoms, lowering the adsorption barrier for atomic hydrogen and enabling a faster VT mechanism. To validate these findings, this work purposely synthesize three catalysts: l-Pt@MoS2, m-Pt@MoS2 and h-Pt@MoS2 with low, moderate, and high Pt-loading, having different distributions of Pt SAs and Cs. The m-Pt@MoS2 catalyst with properly correlating Pt SAs and Cs exhibits outstanding performance with an overpotential of 47 mV and Tafel slope of 32 mV dec-1. Further analysis of the Tafel values confirms that the m-Pt@MoS2 sample indeed follows the VT reaction mechanism, aligning with the theoretical findings. This study offers a deep understanding of the synergistic mechanism, paving a way for designing novel-advanced catalysts.

Facilely Fabricated Single-Site Ptδ+-O(OH)x- Species Associated with Alkali on Zirconia Exhibiting Superior Catalytic Oxidation Reactivity.

Fabrication of robust isolated atom catalysts has been a research hotspot in the environment catalysis field for the removal of various contaminants, but there are still challenges in improving the reactivity and stability. Herein, through facile doping alkali metals in Pt catalyst on zirconia (Pt-Na/ZrO2), the atomically dispersed Ptδ+-O(OH)x- associated with alkali metal via oxygen bridge was successfully fabricated. This novel catalyst presented remarkably higher CO and hydrocarbon (HCs: C3H8, C7H8, C3H6, and CH4) oxidation activity than its counterpart (Pt/ZrO2). Systematically direct and solid evidence from experiments and density functional theory calculations demonstrated that the fabricated electron-rich Ptδ+-O(OH)x- related to Na species rather than the original Ptδ+-O(OH)x-, serving as the catalytically active species, can readily react with CO adsorbed on Ptδ+ to produce CO2 with significantly decreasing energy barrier in the rate-determining step from 1.97 to 0.93 eV. Additionally, owing to the strongly adsorbed and activated water by Na species, those fabricated single-site Ptδ+-O(OH)x- linked by Na species could be easily regenerated during the oxidation reaction, thus considerably boosting its oxidation reactivity and durability. Such facile construction of the alkali ion-linked active hydroxyl group was also realized by Li and K modification which could guide to the design of efficient catalysts for the removal of CO and HCs from industrial exhaust.

Platinum single atom on CsPbBr3 nanocrystals as electrocatalyst boosts electrochemical sensing of ascorbic acid.

Monitoring ascorbic acid (AA) levels in human body can provide valuable clues for disease diagnosis. Anchoring noble metal single atoms on perovskite substrate is a promising strategy to design electrocatalysts with outstanding electrocatalytic performance. Herein, we design an electrochemical method for detecting AA by utilizing Pt single atoms-doped CsPbBr3 nanocrystals (Pt SA/CsPbBr3 NCs) fixed on a glassy carbon electrode as an electrochemical catalyst. The uncharged 3,5,3',5'-tetramethylbenzidine (TMB) undergoes oxidation to form the positively charged oxidized TMB (oxTMB) owing to the exceptional electrochemical catalytic performance of Pt SA/CsPbBr3 NCs. Subsequently, the target AA reduces oxTMB to TMB, which is then electrocatalytically oxidized to oxTMB, producing significant oxidation current. In this way, such characteristic provides a sensitive electrochemical strategy for AA detection, achieving a concentration range of 50-fold with the detection limit of 0.0369 µM. The developed electrochemical method also successfully generates accurate detection response of AA in complex sample media (urine). Overall, this approach is expected to offer a novel way for early disease diagnosis.

Achieving Negatively Charged Pt Single Atoms on Amorphous Ni(OH)2 Nanosheets with Promoted Hydrogen Absorption in Hydrogen Evolution.

Single-atom (SA) catalysts with nearly 100% atom utilization have been widely employed in electrolysis for decades, due to the outperforming catalytic activity and selectivity. However, most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates, which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts. In this work, Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)2 nanosheet arrays. Based on the X-ray absorption fine structure analysis and first-principles calculations, Pt SA was bonded with Ni sites of amorphous Ni(OH)2, rather than conventional O sites, resulting in negatively charged Ptδ-. In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms, which were the essential intermediate for alkaline hydrogen evolution reaction. The hydrogen spillover process was revealed from amorphous Ni(OH)2 that effectively cleave the H-O-H bond of H2O and produce H atom to the Pt SA sites, leading to a low overpotential of 48 mV in alkaline electrolyte at -1000 mA cm-2 mg-1Pt, evidently better than commercial Pt/C catalysts. This work provided new strategy for the controllable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.

Realizing the Tailored Catalytic Performances on Atomic Pt-Promoted Transition Metal Moieties Implanted Layered Double Hydroxides for Water Electrolysis.

High-performance production of green hydrogen gas is necessary to develop renewable energy generation technology and to safeguard the living environment. This study reports a controllable engineering approach to tailor the structure of nickel-layered double hydroxides via doped and absorbed platinum single atoms (PtSA) promoted by low electronegative transition metal (Mn, Fe) moieties (PtSA-Mn,Fe-Ni LDHs). We explore that the electron donation from neighboring transition metal moieties results in the well-adjusted d-band center with the low valence states of PtSA(doped) and PtSA(ads.), thus optimizing adsorption energy to effectively accelerate the H2 release. Meanwhile, a tailored local chemical environment on transition metal centers with unique charge redistribution and high valence states functions as the main center for H2O catalytic dissociation into oxygen. Therefore, the PtSA-Mn,Fe-Ni LDH material possesses a small overpotential of 42 and 288 mV to reach 10 mA·cm-2 for hydrogen and oxygen evolution, respectively, superior to most reported LDH-based catalysts. Additionally, the mass activity of PtSA-Mn,Fe-Ni LDHs proves to be 15.45 times higher than that of commercial Pt-C. The anion exchange membrane electrolyzer stack of PtSA-Mn,Fe-Ni LDHs(+,-) delivers a cell voltage of 1.79 V at 0.5 A·cm-2 and excellent durability over 600 h. This study presents a promising electrocatalyst for a practical water splitting process.

Anchoring Pt single atoms on specific nitrogen vacancies of carbon nitride to accelerate photogenerated carrier transfer.

The anchoring sites of metal single atoms are closely related to photogenerated carrier dynamics and surface reactions. Achieving smooth photogenerated charge transfer through precise design of single-atom anchoring sites is an effective strategy to enhance the activity of photocatalytic hydrogen evolution. In this study, Pt single atoms were loaded onto ultra-thin carbon nitride with two-coordination nitrogen vacancies (VN2c-UCN-Pt) and ultra-thin carbon nitride with three-coordination nitrogen vacancies (VN3c-UCN-Pt). This paper investigated the photocatalytic hydrogen evolution performance and photogenerated carrier behavior of Pt single atoms at different anchoring sites. Surface photovoltage measurements indicated that VN2c-UCN-Pt exhibits a superior carrier separation efficiency compared to VN3c-UCN-Pt. More importantly, the surface photovoltage signal under the presence of H2O molecules revealed a significant decrease. Theoretical calculations suggest that VN2c-UCN-Pt exhibits superior capabilities in adsorbing and activating H2O molecules. Consequently, the photocatalytic hydrogen evolution efficiency of VN2c-UCN-Pt reaches 1774 µmol g-1h-1, which is 1.8 times that of VN3c-UCN-Pt with the same Pt loading. This work emphasized the structure-activity relationship between single-atom anchoring sites and photocatalytic activity, providing a new perspective for designing precisely dispersed single-atom sites to achieve efficient photocatalytic hydrogen evolution.