Electrochemical Knocking-Down of Zn Metal Clusters into Single Atoms.

Single Atoms Catalysts (SACs) have emerged as a class of highly promising heterogeneous catalysts, where the traditional bottom-up synthesis approaches often encounter considerable challenges in relation to aggregation issues and poor stability. Consequently, achieving densely dispersed atomic species in a reliable and efficient manner remains a key focus in the field. Herein, we report a new facile electrochemical knock-down strategy for the formation of SACs, whereby the metal Zn clusters are transformed into single atoms. While a defect-rich substrate plays a pivotal role in capturing and stabilizing isolated Zn atoms, the feasibility of this novel strategy is demonstrated through a comprehensive investigation, combining experimental and theoretical studies. Furthermore, when studied in exploring for potential applications, the material prepared shows a remarkable improvement of 58.21% for the Li+ storage and delivers a capacity over 300 Wh kg-1 after 500 cycles upon the transformation of Zn clusters into 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.

Distribution of Pt single atom coordination environments on anatase TiO2 supports controls reactivity.

Single-atom catalysts (SACs) offer efficient metal utilization and distinct reactivity compared to supported metal nanoparticles. Structure-function relationships for SACs often assume that active sites have uniform coordination environments at particular binding sites on support surfaces. Here, we investigate the distribution of coordination environments of Pt SAs dispersed on shape-controlled anatase TiO2 supports specifically exposing (001) and (101) surfaces. Pt SAs on (101) are found on the surface, consistent with existing structural models, whereas those on (001) are beneath the surface after calcination. Pt SAs under (001) surfaces exhibit lower reactivity for CO oxidation than those on (101) surfaces due to their limited accessibility to gas phase species. Pt SAs deposited on commercial-TiO2 are found both at the surface and in the bulk, posing challenges to structure-function relationship development. This study highlights heterogeneity in SA coordination environments on oxide supports, emphasizing a previously overlooked consideration in the design of SACs.

Mechanistic Insights into the Synthesis of Nickel-Graphene Nanostructures for Gas Sensors.

Toxic gases are used in different types of industries and thus, present a potential health hazard. Therefore, highly sensitive gas sensing materials are essential for the safety of those operating in their environments. A process involving electrospinning polymer solutions impregnated with transition metal ions are developed to yield nanofibers that are annealed to form graphitic carbon / nickel nanoparticle-based fibers for gas sensing applications. The performance of these gas sensors is strongly related to the ability to control the material parameters of the active material. As the formation of these nanostructures, which nucleate within solid carbon scaffolds, have not been investigated, the growth mechanisms are look to understand in order to exert control over the resulting material. Evaluation of these growth mechanisms are conducted through a combination of thermogravimetric analysis with mass spectrometry (TGA-MS), x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS) and reveal nucleation of nickel at the onset of the polymer scaffold decomposition with subsequent growth processes, including surface diffusion, aggregation, coalescence and evaporation condensation, that are activated at different temperatures. Gas sensing experiments conducted on analyte gases demonstrate good sensitivity and response times, and significant potential for use in other energy and environmental applications.

Correction to How Pt Influences H2 Reactions on High Surface-Area Pt/CeO2 Powder Catalyst Surfaces.

[This corrects the article DOI: 10.1021/jacsau.3c00330.].

Alkali cation-induced cathodic corrosion in Cu electrocatalysts.

The reconstruction of Cu catalysts during electrochemical reduction of CO2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value (e.g., -0.4 VRHE when using 0.1 M KHCO3). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.

Synergizing Fe2O3 Nanoparticles on Single Atom Fe-N-C for Nitrate Reduction to Ammonia at Industrial Current Densities.

The electrochemical reduction of nitrates (NO3 -) enables a pathway for the carbon neutral synthesis of ammonia (NH3), via the nitrate reduction reaction (NO3RR), which has been demonstrated at high selectivity. However, to make NH3 synthesis cost-competitive with current technologies, high NH3 partial current densities (jNH3) must be achieved to reduce the levelized cost of NH3. Here, the high NO3RR activity of Fe-based materials is leveraged to synthesize a novel active particle-active support system with Fe2O3 nanoparticles supported on atomically dispersed Fe-N-C. The optimized 3×Fe2O3/Fe-N-C catalyst demonstrates an ultrahigh NO3RR activity, reaching a maximum jNH3 of 1.95 A cm-2 at a Faradaic efficiency (FE) for NH3 of 100% and an NH3 yield rate over 9 mmol hr-1 cm-2. Operando XANES and post-mortem XPS reveal the importance of a pre-reduction activation step, reducing the surface Fe2O3 (Fe3+) to highly active Fe0 sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe2O3 particles and Fe-Nx sites at highly cathodic potentials, maintaining a current of -1.3 A cm-2 over 24 hours. This work exhibits an effective and durable active particle-active support system enhancing the performance of the NO3RR, enabling industrially relevant current densities and near 100% selectivity.