Synergistic Ni-W Dimer Sites Induced Stable Compressive Strain for Boosting the Performance of Pt as Electrocatalyst for the Oxygen Reduction Reaction.

Alloying Pt catalysts with transition metal elements is an effective pathway to enhance the performance of oxygen reduction reaction (ORR), but often accompanied with severe metal dissolution issue, resulting in poor stability of alloy catalysts. Here, instead of forming traditional alloy structure, we modify Pt surface with a novel Ni-W dimer structure by the atomic layer deposition (ALD) technique. The obtained NiW@PtC catalyst exhibits superior ORR performance both in liquid half-cell and practical fuel cell compared with initial Pt/C. It is discovered that strong synergistic Ni-W dimer structure arising from short atomic distance induced a stable compressive strain on the Pt surface, thus boosting Pt catalytic performance. This surface modification by synergistic dimer sites offers an effective strategy in tailoring Pt with excellent activity and stability, which provides a significant perspective in boosting the performance of commercial Pt catalyst modified with polymetallic atom sites.

New Insight of Pyrrole-Like Nitrogen for Boosting Hydrogen Evolution Activity and Stability of Pt Single Atoms.

Single atomic Pt catalysts exhibit particularly high hydrogen evolution reaction (HER) activity compared to conventional nanomaterial-based catalysts. However, the enhanced mechanisms between Pt and their coordination environment are not understood in detail. Hence, a systematic study examining the different types of N in the support is essential to clearly demonstrate the relationship between Pt single atoms and N-doped support. Herein, three types of carbon nanotubes with varying types of N (pyridine-like N, pyrrole-like N, and quaternary N) are used as carbon support for Pt single atom atomic layer deposition. The detailed coordination environment of the Pt single atom catalyst is carefully studied by electron microscope and X-ray absorption spectra (XAS). Interestingly, with the increase of pyrrole-like N in the CNT support, the HER activity of the Pt catalyst also improves. First principle calculations results indicate that the interaction between the dyz and s orbitals of H and sp3 hybrid orbital of N should be the origin of the superior HER performance of these Pt single atom catalysts (SACs).

Anhydride Post-Synthetic Modification in a Hierarchical Metal-Organic Framework.

Metal-organic frameworks (MOFs) are important porous materials. Post-synthetic modification (PSM) of MOFs via the pendant groups or secondary functional groups of organic linkers has been widely used to introduce new or enhance existing properties of MOFs for various practical applications. In this work, we have constructed, for the first time, a novel platform for PSM of MOFs by introducing an anhydride functional group into a hierarchically porous MOF (MIL-121) as an effective anchor. We have demonstrated that the combination of the high reactivity of anhydride and hierarchical porosity makes this protocol particularly novel and important, as it led to excellent opportunities of incorporating not only a wide variety of organic molecules with different sizes and chemical nature but also the noble metal complexes in MOFs. Specifically, we show that the anhydride group decorated in the MOF exhibits a high reactivity toward covalently binding 10 different guest molecules including alcohols, amines, thiols, and noble metal (Pt(II)/Pt(IV)) complexes, whereas the hierarchical pores created in the MOF allow the incorporation of guest species varying in size from methanol to larger molecules such as polyaromatic amines. This novel approach provides the community with a new avenue to prepare MOF-based materials for targeted applications. To illustrate this point, we furnish an example of using this new platform to prepare a Pt-based electrocatalyst which shows excellent catalytic activity toward the oxygen reduction reaction (ORR), a pivotal half-reaction in hydrogen-oxygen fuel cells and other energy storage and conversion devices.

Engineering the Low Coordinated Pt Single Atom to Achieve the Superior Electrocatalytic Performance toward Oxygen Reduction.

Configuring metal single-atom catalysts (SACs) with high electrocatalytic activity and stability is one efficient strategy in achieving the cost-competitive catalyst for fuel cells' applications. Herein, the atomic layer deposition (ALD) strategy for synthesis of Pt SACs on the metal-organic framework (MOF)-derived N-doped carbon (NC) is proposed. Through adjusting the ALD exposure time of the Pt precursor, the size-controlled Pt catalysts, from Pt single atoms to subclusters and nanoparticles, are prepared on MOF-NC support. X-ray absorption fine structure spectra determine the increased electron vacancy in Pt SACs and indicate the Pt-N coordination in the as-prepared Pt SACs. Benefiting from the low-coordination environment and anchoring interaction between Pt atoms and nitrogen-doping sites from MOF-NC support, the Pt SACs deliver an enhanced activity and stability with 6.5 times higher mass activity than that of Pt nanoparticle catalysts in boosting the oxygen reduction reaction (ORR). Density functional theory calculations indicate that Pt single atoms prefer to be anchored by the pyridinic N-doped carbon sites. Importantly, it is revealed that the electronic structure of Pt SAs can be adjusted by adsorption of hydroxyl and oxygen, which greatly lowers free energy change for the rate-determining step and enhances the activity of Pt SACs toward the ORR.

Ultrahigh-Capacity and Long-Life Lithium-Metal Batteries Enabled by Engineering Carbon Nanofiber-Stabilized Graphene Aerogel Film Host.

A safe, high-capacity, and long-life Li metal anode is highly desired due to recent developments in high-energy-density Li-metal batteries. However, there are still rigorous challenges associated with the undesirable formation of Li dendrites, lack of suitable host materials, and unstable chemical interfaces. Herein, a carbon nanofiber-stabilized graphene aerogel film (G-CNF film), inspired by constructional engineering, is constructed. As the host material for Li deposition, the G-CNF film features a large surface area, porous structure, and a robust skeleton that can render low local current density. This allows for dendrite-free Li deposition and mitigation of problems associated with large volume change. Importantly, the G-CNF film can keep high Li plating/stripping efficiency at nearly 99% for over 700 h with an areal capacity of 10 mA h cm-2 (the specific capacity up to 2588 mA h g-1 based on the total mass of carbon host and Li metal). The symmetric cells can stably run for more than 1000 h with low voltage hysteresis. The full cell with the LiFePO4 cathode also delivers enhanced capacity and lowered overpotential. As two-in-one host materials for both cathodes and anodes in Li-O2 batteries, the battery exhibits a capacity of 1.2 mA h cm-2 .

Opposite Electron Transfer Induced High Valence Mo Sites for Boosting the Water Splitting Performance of Ir Atoms.

Developing highly efficient and low-cost bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting poses significant challenges. In this study, a novel bifunctional electrocatalyst, Irn-CoMoPOx, was achieved via incorporating low-loading Ir single atoms and clusters with the high-valence Mo6+ modified CoPOx nanosheets. The Irn-CoMoPOx catalyst demonstrates remarkable low overpotentials of 222 mV and 36 mV for the OER and HER, respectively, in delivering a current density of 10 mA cm-2. When employed as both the anode and cathode catalyst in overall water splitting, the Irn-CoMoPOx∥Irn-CoMoPOx configuration exhibits a superior cell voltage of 1.53 V, outperforming the benchmark Pt/C∥IrO2 electrolytic cell (1.60 V) for achieving the current density of 10 mA cm-2. Benefiting from the high-valence of Mo species, the metal-support interaction of Irn-CoMoPOx was greatly strengthened, resulting in an order of magnitude increase in the mass activity of Ir for the HER. The high valence of non-noble metals plays a crucial role in tuning the local electronic configurations and optimizing the adsorption energies of the intermediates, which synergistically improves the overall performance of Ir in water splitting. The study provides valuable insights for future research in the utilization of Ir-based bifunctional catalysts for overall water electrocatalysis applications.

Emerging Applications of Synchrotron Radiation X-Ray Techniques in Single Atomic Catalysts.

Single atom catalysts (SACs) can achieve a maximum atom utilization efficiency of 100%, which provides significantly increased active sites compared with traditional catalysts during catalytic reactions. Synchrotron radiation technology is an important characterization method for identifying single-atom catalysts. Several types of internal information, such as the coordination number, bond length and electronic structure of metals, can all be analyzed. This review will focus on the introduction of synchrotron radiation techniques and their applications in SACs. First, the fundamentals of synchrotron radiation and the corresponding techniques applied in characterization of SACs will be briefly introduced, such as X-ray absorption near edge spectroscopy and extended X-ray absorption fine structure spectroscopy and in situ techniques. The detailed information obtained from synchrotron radiation X-ray characterization is described through four routes: 1) the local environment of a specific atom; 2) the oxidation state of SACs; 3) electronic structures at different orbitals; and 4) the in situ structure modification during catalytic reaction. In addition, a systematic summary of synchrotron radiation X-ray characterization on different types of SACs (noble metals and transition metals) will be discussed.

High-Performance Ammonium Cobalt Phosphate Nanosheet Electrocatalyst for Alkaline Saline Water Oxidation.

The development of highly efficient electrocatalysts toward the oxygen evolution reaction is imperative for advancing water splitting technology to generate clean hydrogen energy. Herein, a two dimensional (2D) nanosheet ammonium cobalt phosphate hydrate (NH4CoPO4·H2O) catalyst based on the earth-abundant non-noble metal is reported. When used for the challenging alkaline saline water electrolysis, the NH4CoPO4·H2O catalyst with the optimal thickness of 30 nm achieves current densities of 10 and 100 mA cm-2 at the record low overpotentials of 252 and 268 mV, respectively, while maintaining remarkable stability during the alkaline saline water oxidation at room temperature. X-ray absorption fine spectra reveal that the activation of Co (II) ions (in NH4CoPO4·H2O) to Co (III) species constructs the electrocatalytic active sites. The 2D nanosheet morphology of NH4CoPO4·H2O provides a larger active surface area and more surface-exposed active sites, which enable the nanosheet catalyst to facilitate the alkaline freshwater and simulated seawater oxidation with excellent activity. The facile and environmentally-benign H2O-mediated synthesis route under mild condition makes NH4CoPO4·H2O catalyst highly feasible for practical manufacturing. In comparison with noble metals, this novel electrocatalyst offers a cost-effective alternative for economic saline water oxidation to advance water electrolysis technology.

Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction.

Single atom catalysts exhibit particularly high catalytic activities in contrast to regular nanomaterial-based catalysts. Until recently, research has been mostly focused on single atom catalysts, and it remains a great challenge to synthesize bimetallic dimer structures. Herein, we successfully prepare high-quality one-to-one A-B bimetallic dimer structures (Pt-Ru dimers) through an atomic layer deposition (ALD) process. The Pt-Ru dimers show much higher hydrogen evolution activity (more than 50 times) and excellent stability compared to commercial Pt/C catalysts. X-ray absorption spectroscopy indicates that the Pt-Ru dimers structure model contains one Pt-Ru bonding configuration. First principle calculations reveal that the Pt-Ru dimer generates a synergy effect by modulating the electronic structure, which results in the enhanced hydrogen evolution activity. This work paves the way for the rational design of bimetallic dimers with good activity and stability, which have a great potential to be applied in various catalytic reactions.

Author Correction: Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.