Single Atom Research Articles

Direct generation of time-energy-entangled W triphotons in atomic vapor.

Entangled multiphoton sources are essential for both fundamental tests of quantum foundations and building blocks of contemporary optical quantum technologies. While efforts over the past three decades have focused on creating multiphoton entanglement through multiplexing existing biphoton sources with linear optics and postselections, our work presents a groundbreaking approach. We observe genuine continuous-mode time-energy-entangled W-class triphotons with an unprecedented production rate directly generated through spontaneous six-wave mixing (SSWM) in a four-level triple-Λ atomic vapor cell. Using electromagnetically induced transparency and coherence control, our SSWM scheme allows versatile narrowband triphoton generation with advantageous properties, including long temporal coherence and controllable waveforms. This advancement is ideal for applications like long-distance quantum communications and information processing, bridging single photons and neutral atoms. Most importantly, our work establishes a reliable and efficient genuine triphoton source, facilitating accessible research on multiphoton entanglement.

Synergistic effect of Fe-Ru alloy and Fe-N-C sites on oxygen reduction reaction

In the pursuit of optimizing Fe-N-C catalysts for the oxygen reduction reaction (ORR), the incorporation of alloy nanoparticles has emerged as a prominent strategy. In this work, we effectively synthesized the FeRu-NC catalyst by anchoring Fe-Ru alloy nanoparticles and FeN4 single atom sites onto carbon nanotubes. The FeRu-NC catalyst exhibits significantly enhanced ORR activity and long-term stability, with a high half-wave potential of 0.89 V (vs. RHE) in alkaline conditions, and the half-wave potential remains nearly unchanged after 5000 cycles. The zinc-air battery (ZAB) assembled with FeRu-NC demonstrates a power density of 169.1 mW cm−2, surpassing that of commercial Pt/C. Density functional theory (DFT) calculations reveal that the synergistic interaction between the Fe–Ru alloy and FeN4 single atoms alters the electronic structure and facilitates charge transfer at the FeN4 sites, thereby modulating the adsorption and desorption of ORR intermediates. This enhancement in catalytic activity for the ORR process underscores the potential of this approach for refining M-N-C catalysts, providing novel insights into their optimization strategies.

Ru Single Atom Dispersed Cu Nanoparticle with Dual Sites Enables Outstanding Photocatalytic CO2 Reduction.

Cu-based catalysts are promising candidates for CO2 reduction owing to the favorable energetics of Cu sites for CO2 adsorption and transformation. However, CO2 reduction involving insurmountable activation barriers and various byproducts remains a significant challenge to achieve high activity and selectivity. Herein, a photocatalyst constructed with single-Ru-site-on-Cu-nanoparticle on Bi4Ti3O12 exhibits exceptional activity and selectivity for CO2 conversion to CO. The experimental and theoretical results consistently reveal that the Ru-Cu dual sites allow the rapid transfer of photogenerated carriers for closely interacting with CO2 molecules. Importantly, the Ru-Cu dual sites exhibit extremely strong CO2 adsorption ability, and the Gibbs free energy of the rate-determining step (*CO2 to *COOH) has been significantly reduced, synergistically enhancing the entire CO2 conversion process. The optimal BTOCu2Ru0.5 photocatalyst manifests a high performance for selective reduction of CO2 to CO, yielding 10.84 μmol over 15 mg of photocatalyst in 4 h (180.67 μmol·g-1·h-1) under a 300 W Xe lamp without any photosensitizer and sacrificial reagent, outperforming all bismuth-based materials and being one of the best photocatalysts ever reported under similar reaction conditions. This work presents a strategy for the rational design of multiple metal sites toward efficient photocatalytic reduction of CO2.

Strong Electronic Metal-Support Interactions Enable the Increased Spin State of Co-N4 Active Sites and Performance for Acidic Oxygen Reduction Reaction.

Nonprecious metal catalysts, particularly M-N-C catalysts, are widely recognized as promising contenders for the oxygen reduction reaction (ORR). However, a notable performance gap persists between M-N-C catalysts and Pt-based catalysts under acidic conditions. In this study, hybrid catalysts comprising single Co atoms and ultralow concentrations of Pt3Co intermetallic nanoparticles (NPs) are introduced to enhance ORR performance. Under acidic conditions, these hybrid catalysts demonstrate ORR efficiency with a half-wave potential of 0.895 V, negligible decay even after 80 000 cycles, and a high maximum power density of 1.34 W cm-2 in fuel cells. This performance surpasses those of Co-N-C and Pt/Co-N-C catalysts. Both experimental findings and theoretical computations suggest that the heightened ORR activity stems from an increase in the spin density of Co sites induced by noble metal NPs, facilitating the activation of O-O bonds via side-on overlapping and enabling a transition in the reaction pathway from associative to dissociative processes. This research offers a promising avenue for the systematic design of M-N-C cathodes with an enhanced performance for acidic fuel cells.

Shear‐Strained Pd Single‐Atom Electrocatalysts for Nitrate Reduction to Ammonia

AbstractElectrochemical nitrate reduction method (NitRR) is a low‐carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper‐based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO3. However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by‐product NO2−. In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd−CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol. gcat−1. h−1, and a Faraday efficiency of 90 % for ammonia production at −0.5 V vs. RHE. Electrochemical in situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress obviously promote the production of active hydrogen, reduce the reaction energy barrier of the decision‐making step for nitrate conversion to ammonia, further promote ammonia generation.

Shear-Strained Pd Single-Atom Electrocatalysts for Nitrate Reduction to Ammonia.

Electrochemical nitrate reduction method (NitRR) is a low-carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper-based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO3. However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by-product NO2 -. In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd-CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol. gcat -1. h-1, and a Faraday efficiency of 90 % for ammonia production at -0.5 V vs. RHE. Electrochemical in situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress obviously promote the production of active hydrogen, reduce the reaction energy barrier of the decision-making step for nitrate conversion to ammonia, further promote ammonia generation.

Recent Advances on Two-Dimensional Nanomaterials Supported Single-Atom for Hydrogen Evolution Electrocatalysts.

Water electrolysis has been recognized as a promising technology that can convert renewable energy into hydrogen for storage and utilization. The superior activity and low cost of catalysis are key factors in promoting the industrialization of water electrolysis. Single-atom catalysts (SACs) have attracted attention due to their ultra-high atomic utilization, clear structure, and highest hydrogen evolution reaction (HER) performance. In addition, the performance and stability of single-atom (SA) substrates are crucial, and various two-dimensional (2D) nanomaterial supports have become promising foundations for SA due to their unique exposed surfaces, diverse elemental compositions, and flexible electronic structures, to drive single atoms to reach performance limits. The SA supported by 2D nanomaterials exhibits various electronic interactions and synergistic effects, all of which need to be comprehensively summarized. This article aims to organize and discuss the progress of 2D nanomaterial single-atom supports in enhancing HER, including common and widely used synthesis methods, advanced characterization techniques, different types of 2D supports, and the correlation between structural hydrogen evolution performance. Finally, the latest understanding of 2D nanomaterial supports was proposed.

Coherent spin dynamics between electron and nucleus within a single atom

The nuclear spin, being much more isolated from the environment than its electronic counterpart, presents opportunities for quantum experiments with prolonged coherence times. Electron spin resonance (ESR) combined with scanning tunnelling microscopy (STM) provides a bottom-up platform to study the fundamental properties of nuclear spins of single atoms on a surface. However, access to the time evolution of nuclear spins remained a challenge. Here, we present an experiment resolving the nanosecond coherent dynamics of a hyperfine-driven flip-flop interaction between the spin of an individual nucleus and that of an orbiting electron. We use the unique local controllability of the magnetic field emanating from the STM probe tip to bring the electron and nuclear spins in tune, as evidenced by a set of avoided level crossings in ESR-STM. Subsequently, we polarize both spins through scattering of tunnelling electrons and measure the resulting free evolution of the coupled spin system using a DC pump-probe scheme. The latter reveals a complex pattern of multiple interfering coherent oscillations, providing unique insight into hyperfine physics on a single atom level.

Expanding the Landscape of Phosphorous-Based Open Shell Species: Stable Mono-, Di-, and Trianionic Radicals Based on a Contorted Triphosphaalkene.

The stepwise reduction of the highly contorted truxene-based triphosphaalkene 1 using KC8 led to the isolation of mono-, di-and tri-anionic species. The solid-state molecular structures of mono- and diradical anionic species were elucidated by single crystal X-ray diffractions, revealing elongated P-C bonds and a pronounced "indene" aromatization compared to the parent system. All three radical species displayed distinct Electron Paramagnetic Resonance (EPR) spectra, providing compelling evidence for the open-shell electronic configuration of both the diradical and triradical species-an observation unprecedented in any previously reported phosphorous-based anionic polyradicals. Mulliken spin density calculations revealed a dominant localization of radical spin on a single phosphorous atom in the monoanion. In the dianion, spin localization is observed on two phosphorous atoms (~34% each), with a minor contribution from the third phosphorous (0.13%), while the trianion demonstrates a uniform distribution of spin density (~30%) across each phosphorous atom.

Facile synthesis of graphitized carbon nanosheets from Chlorella with multiple Fe active sites to modify separator for efficient Li-S batteries

Li-S battery as an alternative to next-generation battery systems suffers from electrical insulating properties of sulfur, “shuttle effects” and slow kinetics of lithium polysulfides (LiPSs). Separator modification via catalysts with multiple scales of active sites are great potential; however, the preparation of such a kind of catalysts is still complex and tedious. Here, we developed a facile pyrolysis strategy to fabricate multiple Fe active sites on N-doped porous graphitized carbon nanosheets (Fe-NG) from Chlorella, including atomically dispersed Fe single atoms, Fe nanoclusters and carbon-coated Fe nanoparticles, which enhanced the affinity to LiPSs and accelerated their conversion kinetics. As Fe-NG was utilized to modify the separators, the resulting Li-S battery demonstrated an initial discharge capacity of 1062.1 mAh g−1 at 1 C and maintained at 678 mAh g−1 after 500 cycles with the average capacity decay rate of 0.072 % per cycle. This work provides a rational design and large-scale preparation routes for separator modifying catalysts with heterogeneous active species on biomass-derived carbons.

Mutual self-regulation of d electrons of single atoms and adjacent nanoparticles for acetaldehyde manufacture

Mutual self-regulation of d electrons of single atoms and adjacent nanoparticles for acetaldehyde manufacture

Synergy of nitrogen dopants and cobalt single atoms in calcium niobate nanosheets for photocatalytic oxygen evolution

Abstract Successful separation of photoexcited charge carriers and their effective utilization are crucial for overcoming the slow kinetics of the four-electron process for photocatalytic oxygen evolution. Herein, a novel strategy utilizing urea as a source of N-doping on Ca2Nb3O10 nanosheets is adopted followed by the successful deposition of Co single atoms (Co-SAs) to achieve a synergistic effect. The presence of N-dopants and Co-SAs is validated via various experimental techniques. Besides, it is observed that the presence of N-doping contributed towards deposition of higher content of Co-SAs (0.21 wt%) in Ca2Nb3O10-xNx¬-CoSA nanosheets compared to 0.15 wt% for non-doped Ca2Nb3O10-CoSA. The optimized Ca2Nb3O10-xNx-CoSA nanosheets exhibited an impressive photocatalytic O2 evolution of ~727.22 µmol g-1 h-1 via the synergy of N-dopants and Co-SAs. As a result, O2 evolution response of Ca2Nb3O10-xNx-CoSA is 3.6 times higher than pristine Ca2Nb3O10 nanosheets (201.26 µmol g-1 h-1), 2.24 times better than Ca2Nb3O10-xNx nanosheets (323.42 µmol g-1 h-1), and 1.77 times higher compared to Ca2Nb3O10-CoSA, (409.33 µmol g-1 h-1), clearly demonstrated the synergistic effect of N-dopants and Co-SAs in Ca2Nb3O10-xNx-CoSA nanosheets. Base on the finding of various characterization techniques, the co-presence of N-dopants and Co-SAs is observed to contribute towards better charge carriers separation, and utilization to achieve superior photocatalytic response. Thus, this work presents a novel approach for incorporating N-dopants and Co-SAs on Ca2Nb3O10 nanosheets which can be extended to wide range of nanosheets produced by the soft chemical exfoliation method.

Unraveling the Microstructure‐Property Relationship of Fe Single‐Atoms via Introducing Asymmetric P‐Coordination for Photocatalytic Hydrogen Evolution

AbstractThe local atomic environments of single‐atom photocatalysts play a decisive role in determining the solar‐to‐hydrogen energy conversion efficiency. However, controllably modulating the microstructure of single‐atom sites to enhance catalytic activity and deeply understanding the structure‐property relationship remain great challenges. Herein, electron‐rich P atoms are introduced to accurately regulate the local coordination environment and electronic configuration of Fe single atoms and construct a unique asymmetrical FeN3P2 motif into carbon nitride (FeN3P2‐CN) for significantly improving the photocatalytic H2 evolution activity and stability. Specifically, in the absence of noble metal cocatalyst and photosensitizer, the FeN3P2‐CN achieves a remarkable H2 evolution rate of 2668.5 µmol g−1 h−1 under visible light irradiation (λ > 420 nm), more than 105 times higher than that of unregulated FeN4 sample. Systematic characterizations and theoretical calculations unveil that the FeN3P2 single‐atom sites not only significantly broaden the photoabsorption region and facilitate the charge separation and interfacial transfer, but also efficiently promote adsorption and activation of H2O. This work paves a promising pathway to design novel single‐atom photocatalysts at the atomic level for achieving highly efficient water‐splitting performance.

Supported Au single atoms and nanoparticles on MoS2 for highly selective CO2-to-CH3COOH photoreduction

Effectively controlling the selective conversion of CO2 photoreduction to C2 products presents a significant challenge. Here, we develop a heterojunction photocatalyst by controllably implanting Au nanoparticles and single atoms into unsaturated Mo atoms of edge-rich MoS2, denoted as Aun/Au1-CMS. Photoreduction of CO2 results in the production of CH3COOH with a selectivity of 86.4%, which represents a 6.4-fold increase compared to samples lacking single atoms, and the overall selectivity for C2 products is 95.1%. Furthermore, the yield of CH3COOH is 22.4 times higher compared to samples containing single atoms and without nanoparticles. Optical experiments demonstrate that the single atoms domains can effectively capture photoexcited electrons by the Au nanoparticles, or the local electric field generated by the nanoparticles promotes the transfer of photogenerated electrons in MoS2 to Au single atoms, prolonging the relaxation time of photogenerated electrons. Mechanistic investigations reveal that the orbital coupling of Au5d and Mo4d strengthens the oxygen affinity of Mo and carbon affinity of Au. The hybridized orbitals reduce energy splitting levels of CO molecular orbitals, aiding C–C coupling. Moreover, the Mo−Au dual-site stabilize the crucial oxygen-associated intermediate *CH2CO, thereby enhancing the selectivity towards CH3COOH. The cross-scale heterojunctions provide an effective strategy to simultaneously address the kinetical and thermodynamical limitations of CO2-to-CH3COOH conversion.

Constructing ultralow-loading Cu single atoms/Fe2O3 particles on Nb2C MXenes for efficient utilization of atomic H to boost electrochemical debromination

Bromate is a commonly identified carcinogenic and genotoxic disinfection byproduct in water. Electrochemical debromination is an environmentally friendly and effective approach but it often suffers the limited reducing atomic H (H*) ability and high metal catalyst dosage. In this study, a unique composite catalyst comprised of ultra-low loading Cu single atoms (0.016 wt%) and Fe2O3 nanoparticles supported on a Nb2C MXene (denoted as Cu0.2/Fe0.1/Nb2C) was synthesized by one-step high-temperature molten salt method. The Cu0.2/Fe0.1/Nb2C significantly outperformed the Nb2C, Cu0.2/Nb2C and Fe0.1/Nb2C counterparts in the electrochemical debromination with a 94.2 % removal efficiency of bromate. It is revealed that the introducing of Cu single atoms, efficiently promotes the adsorption of H* and inhibition of competitive H2 evolution. The incorporation of Fe2O3 nanoparticles significantly increased the electronic metal-support interaction effect between the metal components and Nb2C, thereby forming a noticeable electronic cloud bridge to facilitate efficient charge transfer. Ultimately, the synergistic interplay between Cu single atoms and Fe2O3 nanoparticles plays a crucial role in achieving the remarkable removal performance of bromate. This work not only presents a significant instance of a synergistic catalyst involving metal single atoms and metal nanoparticles for effective electrochemical debromination but also advances the understanding of the electronic metal-support interaction.

Orbital coupling of Pt single crystal via decoration of hetero-diatomic nickel-cobalt for efficient hydrogen evolution

Loading active metals in forms of single atoms or nanocluster is considered as an effective approach for designing catalysts with high atomic utilization efficiency. However, synthesis single atoms or clusters precisely in large quantities is a challenge. In this work, the isolated diatomic sites (Ni, Co) decorated single crystal Pt cluster were synthesized as efficient catalyst for hydrogen evolution. Adjacent Ni and Co atoms optimize the electronic structure of Pt single crystal, effectively lowering the water dissociation barrier and ensuring optimal binding strength of intermediates throughout the reaction process. As results, the mass activity of 2.087 A mg−1 was achieved under 200 mA cm−2, approximately 3 times than that of Pt/C. Theoretical calculations reveal that diatomic Ni, Co decorated Pt cluster reduces the energy barrier for breaking the OH-H bond, as well as facilitating the preferential adsorption and dissociation of H*. This work provides an opportunity for regulation electronic structure of catalytic via decoration single crystal cluster with diatomic sites and provides guidance for designing high efficiency electrocatalysts for promising applications.

Pt-Ru atomic alloys confined in mesoporous carbon hollow spheres for accelerating methanol oxidation

Active and durable electrocatalysts are essential for commercializing direct methanol fuel cells. However, Pt-based catalysts, extensively utilized in the methanol oxidation reaction (MOR), are suffered from resource scarcity and CO poisoning, which degrade MOR activity severely. Herein, Pt1Rux bimetallic catalysts were synthesized by confining Pt1Rux alloys within the shells of mesoporous carbon hollow spheres (MCHS) via a vacuum-assisted impregnation method (Pt1Rux@MCHS). The confinement effect induced by mesoporous carbon hollow spheres resulted in a robust structure of Pt1Ru3@MCHS with an ultrafine dispersion of alloy nanoparticles. The experimental and theoretical results confirmed that the boosting electrocatalytic activity and stability of the MOR over Pt1Ru3@MCHS were contributed to the regulated electronic structure as well as the superior CO tolerance of atomic Pt site caused by the electronic interaction between single Pt atoms and Ru nanoparticles. This strategy is versatile for the rational design of Pt-based bimetallic catalysts and has a positive impact on MOR performance.

Highly Selective Conversion of Carbon Dioxide to Methane by Copper Single Atom Electrocatalysts.

Electrocatalytic carbon dioxide reduction into high-value chemicals is one of the important solutions to the greenhouse effect and energy crisis. However, the slow kinetic process of eight electrons requires the development of efficient catalysts to improve the yields. Single atom catalysts (SACs) with high activity and selectivity have become an emerging research frontier in the field of heterogeneous catalysis. Herein, a catalyst comprised of Cu single atoms loaded on carbon substrate (Cu-NC) is developed for highly selective electrocatalytic reduction of CO2 to methane (CH4). The optimal catalyst (Cu-NC-1-4) exhibits a faradaic efficiency (FE) of over 50 % for CH4 within a wide potential window from -1.3 V to -1.8 V (vs. RHE) and the highest FE of CH4 is up to 67.22 % at -1.6 V (vs. RHE). Meanwhile, the product selectivity of CH4 among all the carbon products reaches 93.00 %, and the activity decay can be negligible via the 70-hour-stability-test. The existence of atomic dispersed Cu-N3 sites was verified by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption near edge structure (XANES). Density functional theory (DFT) calculations show that the effective adsorption of the key intermediate *CO on Cu-N3 sites prompts the generation of CH4.

Single-atom platinum promotes Cu(I)/Cu(II) redox loop of Cu aerogels for efficient glucose electrooxidation

Glucose oxidation reaction (GOR) is emerging as a promising alternative to the sluggish anodic oxygen evolution reaction for hydrogen production in energy-saving water electrolysis. Cu-based electrocatalysts hold natural superiority for GOR, which is limited by the slow Cu(I)/Cu(II) redox loop. Here, we synthesize Cu50Pt aerogels with Pt single atom (SA) to enhance GOR activity with an accelerated Cu(I)/Cu(II) redox loop compared to Cu aerogels. Experimental and theoretical investigations elucidate that Pt SA boosts the adsorption and activation capacity of OHads, promoting the hydroxylation of Cu(I) into Cu(II) active species through hydroxyl spillover. Moreover, the optimized electronic structure of Cu by Pt SA facilitates the glucose adsorption, the dehydrogenation process of C5H11O5CHO* to C5H11O5CO* and the release of products, thus promoting the hydroxyl deintercalation of Cu(II) sites into Cu(I). Notably, the Pt SA-assisted plasma effect of Cu further enhances the GOR activity and reduces the power consumption of hydrogen production by promoting the Cu(I)/Cu(II) redox loop. This work provides new insights into high-performance biomass electrooxidation catalysts via accelerating the redox cycle of reactive metal for electrochemical energy technologies.

Atomically dispersed ruthenium in transition metal double layered hydroxide as a bifunctional catalyst for overall water splitting

Efficient and sustainable energy conversion depends on the rational design of single-atom catalysts. The control of the active sites at the atomic level is vital for electrocatalytic materials in alkaline and acidic electrolytes. Moreover, fabrication of effective catalysts with a well-defined surface structure results in an in-depth understanding of the catalytic mechanism. Herein, a single atom ruthenium dispersed in nickel-cobalt layered hydroxide (Ru-NiCo LDH) is reported. Through the precise controlling of the atomic dispersion and local coordination environment, Ru-NiCo LDH//Ru-NiCo LDH provides an ultra-low overpotential of 1.45 mV at 10 mA cm−2 for the overall water splitting, which surpasses that of the state-of-the-art Pt/C/RuO2 redox couple. Density functional theory calculations show that Ru-NiCo LDH optimizes hydrogen evolution intermediate adsorption energies and promotes O-O coupling at a Ru-O active site for oxygen evolution, while Ni serves as the water dissociation site for effective water splitting. As a potential model, Ru-NiCo LDH shows enhanced water splitting performance with potential for the development of promising water-alkaline catalysts.