Structural Ni0-Niδ+ Pair Sites for Highly Active Hydrogenation of Nitriles to Primary Amines.

Supported metal pair sites have sparked interest due to their tremendous potential as bifunctional catalysts. Here, we report the structural Ni0-Niδ+ pair sites constructed in a well-defined nanocrystal phase of Ni3P. These Ni0-Niδ+ pair sites exhibited a remarkable product formation rate of 123 molBA/molmetal/h for the hydrogenation of benzonitrile (BN) to benzylamine (BA). The heterogeneity of surface Ni atoms over the Ni3P crystal created two types of metal centers, Ni0 and Niδ+, with a specific spatial distance of 4-5 Å. The Ni0 site acted as the center for H2 activation, while the Niδ+ site served as the adsorption and activation center for the C ≡ N group. The highly efficient cooperation effect of Ni0-Niδ+ pair sites resulted in a TOF of 2915 h-1 in BN hydrogenation, which is 2.4 and 9.7 times higher than that over the mono-Ni0 and -Niδ+ sites, respectively.

Selective Cleavage of α-Olefins to Produce Acetylene and Hydrogen.

Acetylene production from mixed α-olefins emerges as a potentially green and energy-efficient approach with significant scientific value in the selective cleavage of C-C bonds. On the Pd(100) surface, it is experimentally revealed that C2 to C4 α-olefins undergo selective thermal cleavage to form surface acetylene and hydrogen. The high selectivity toward acetylene is attributed to the 4-fold hollow sites which are adept at severing the terminal double bonds in α-olefins to produce acetylene. A challenge arises, however, because acetylene tends to stay at the Pd(100) surface. By using the surface alloying methodology with alien Au, the surface Pd d-band center has been successfully shifted away from the Fermi level to release surface-generated acetylene from α-olefins as a gaseous product. Our study actually provides a technological strategy to economically produce acetylene and hydrogen from α-olefins.

Activation of MnO6 Units via an Interfacial Electric Field: Electron Injection into Mn t2g for Rapid and Stable Sodium Ion Storage in CeO2/MnOx.

Manganese-based oxides (MnOx) suffer from sluggish charge diffusion kinetics and poor cycling stability in sodium ion storage. Herein, an interfacial electric field (IEF) in CeO2/MnOx is constructed to obtain high electronic/ionic conductivity and structural stability of MnOx. The as-designed CeO2/MnOx exhibits a remarkable capacity of 397 F g-1 and favorable cyclic stability with 92.13% capacity retention after 10,000 cycles. Soft X-ray absorption spectroscopy and partial density of states results reveal that the electrons are substantially injected into the Mn t2g orbitals driven by the formed IEF. Correspondingly, the MnO6 units in MnOx are effectively activated, endowing the CeO2/MnOx with fast charge transfer kinetics and high sodium ion storage capacity. Moreover, In situRaman verifies a remarkably increased structural stability of CeO2/MnOx, which is attributed to the enhanced Mn─O bond strength and efficiently stabilized MnO6 units. Mechanism studies show that the downshift of Mn 3d-band center dramatically increases the Mn 3d-O 2p orbitals overlap, thus inhibiting the Jahn-Teller (J-T) distortion of MnOx during sodium ion insertion/extraction. This work develops an advanced strategy to achieve both fast and sustainable sodium ion storage in metal oxides-based energy materials.

Unlocking Spin Gates of Transition Metal Oxides via Strain Stimuli to Augment Potassium Ion Storage.

Transition metal oxides (TMOs) are key in electrochemical energy storage, offering cost-effectiveness and a broad potential window. However, their full potential is limited by poor understanding of their slow reaction kinetics and stability issues. This study diverges from conventional complex nano-structuring, concentrating instead on spin-related charge transfer and orbital interactions to enhance the reaction dynamics and stability of TMOs during energy storage processes. We successfully reconfigured the orbital degeneracy and spin-dependent electronic occupancy by disrupting the symmetry of magnetic cobalt (Co) sites through straightforward strain stimuli. The key to this approach lies in the unfilled Co 3d shell, which serves as a spin-dependent regulator for carrier transfer and orbital interactions within the reaction. We observed that the opening of these 'spin gates' occurs during a transition from a symmetric low-spin state to an asymmetric high-spin state, resulting in enhanced reaction kinetics and maintained structural stability. Specifically, the spin-rearranged Al-Co3O4 exhibited a specific capacitance of 1371 F g-1, which is 38 % higher than that of unaltered Co3O4. These results not only shed light on the spin effects in magnetic TMOs but also establish a new paradigm for designing electrochemical energy storage materials with improved efficiency.

High Flux and Stability of Cationic Intercalation in Transition-Metal Oxides: Unleashing the Potential of Mn t2g Orbital via Enhanced π-Donation.

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation to activate the t2g orbital, thereby enhancing both electron/ion conductivity and structural stability of TMOs. We engineered Ni-doped layered manganese dioxide (Ni-MnO2), which is characterized by a distinctive Ni-O-Mn bridging configuration. Remarkably, Ni-MnO2 presents an impressive capacitance of 317 F g-1 and exhibits a robust cyclic stability, maintaining 81.58% of its original capacity even after 20,000 cycles. Mechanism investigations reveal that the incorporation of Ni-O-Mn configurations stimulates a heightened π-donation effect, which is beneficial to the π-type orbital hybridization involving the O 2p and the t2g orbital of Mn, thereby accelerating charge-transfer kinetics and activating the redox capacity of the t2g orbital. Additionally, the charge redistribution from Ni to the t2g orbital of Mn effectively elevates the low-energy orbital level of Mn, thus mitigating the undesirable Jahn-Teller distortion. This results in a subsequent decrease in the electron occupancy of the π*-antibonding orbital, which promotes an overall enhancement in structural stability. Our findings pave the way for an innovative paradigm in the development of fast and stable electrode materials for intercalation energy storage by activating the low orbitals of the TM center from a molecular orbital perspective.

Surface Self-Transforming FeTi-LDH Overlayer in Fe2 O3 /Fe2 TiO5 Photoanode for Improved Water Oxidation.

Integrating hematite nanostructures with efficient layer double hydroxides (LDHs) is highly desirable to improve the photoelectrochemical (PEC) water oxidation performance. Here, an innovative and facile strategy is developed to fabricate the FeTi-LDH overlayer decorated Fe2 O3 /Fe2 TiO5 photoanode via a surface self-transformation induced by the co-treatment of hydrazine and NaOH at room temperature. Electrochemical measurements find that this favorable structure can not only facilitate the charge transfer/separation at the electrode/electrolyte interface but also accelerate the surface water oxidation kinetics. Consequently, the as-obtained Fe2 O3 /Fe2 TiO5 /LDH photoanode exhibits a remarkably increased photocurrent density of 3.54 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) accompanied by an obvious cathodic shift (≈140 mV) in the onset potential. This work opens up a new and effective pathway for the design of high-performance hematite photoanodes toward efficient PEC water oxidation.

CoMoO4-modified hematite with oxygen vacancies for high-efficiency solar water splitting.

Hematite is a potential photoelectrode for photoelectrochemical (PEC) water splitting. Nevertheless, its water oxidation efficiency is highly limited by its significant photogenerated carrier recombination, poor conductivity and slow water oxidation kinetics. Herein, under low-vacuum (LV) conditions, we fabricated a CoMoO4 layer on oxygen-vacancy-modified hematite (CoMo-Fe2O3 (LV)) for the first time for efficient solar water splitting. The existence of oxygen vacancies can significantly facilitate the electrical conductivity, while the large onset potential along with oxygen vacancies can be lowered by the CoMoO4 with accelerated water oxidation kinetics. Therefore, a high photocurrent density of 3.53 mA cm-2 at 1.23 VRHE was obtained for the CoMo-Fe2O3 (LV) photoanode. Moreover, it can be further coupled with the FeNiOOH co-catalyst to reach a benchmark photocurrent of 4.18 mA cm-2 at 1.23 VRHE, which is increased around 4-fold compared with bare hematite (0.90 mA cm-2). The combination of CoMoO4, FeNiOOH, and oxygen vacancies may be used as a reasonable strategy for developing high-efficiency hematite-based photoelectrodes for solar water oxidation.

The Doping Mechanism of Halide Perovskite Unveiled by Alkaline Earth Metals.

Halide perovskites are a strong candidate for the next generation of photovoltaics. Chemical doping of halide perovskites is an established strategy to prepare the highest efficiency and most stable perovskite-based solar cells. In this study, we unveil the doping mechanism of halide perovskites using a series of alkaline earth metals. We find that low doping levels enable the incorporation of the dopant within the perovskite lattice, whereas high doping concentrations induce surface segregation. The threshold from low to high doping regime correlates to the size of the doping element. We show that the low doping regime results in a more n-type material, while the high doping regime induces a less n-type doping character. Our work provides a comprehensive picture of the unique doping mechanism of halide perovskites, which differs from classical semiconductors. We proved the effectiveness of the low doping regime for the first time, demonstrating highly efficient methylammonium lead iodide based solar cells in both n-i-p and p-i-n architectures.

Safe and Durable High-Temperature Lithium-Sulfur Batteries via Molecular Layer Deposited Coating.

Lithium-sulfur (Li-S) battery is a promising high energy storage candidate in electric vehicles. However, the commonly employed ether based electrolyte does not enable to realize safe high-temperature Li-S batteries due to the low boiling and flash temperatures. Traditional carbonate based electrolyte obtains safe physical properties at high temperature but does not complete reversible electrochemical reaction for most Li-S batteries. Here we realize safe high temperature Li-S batteries on universal carbon-sulfur electrodes by molecular layer deposited (MLD) alucone coating. Sulfur cathodes with MLD coating complete the reversible electrochemical process in carbonate electrolyte and exhibit a safe and ultrastable cycle life at high temperature, which promise practicable Li-S batteries for electric vehicles and other large-scale energy storage systems.

Operando spectroscopic analysis of an amorphous cobalt sulfide hydrogen evolution electrocatalyst.

The generation of chemical fuel in the form of molecular H2 via the electrolysis of water is regarded to be a promising approach to convert incident solar power into an energy storage medium. Highly efficient and cost-effective catalysts are required to make such an approach practical on a large scale. Recently, a number of amorphous hydrogen evolution reaction (HER) catalysts have emerged that show promise in terms of scalability and reactivity, yet remain poorly understood. In this work, we utilize Raman spectroscopy and X-ray absorption spectroscopy (XAS) as a tool to elucidate the structure and function of an amorphous cobalt sulfide (CoSx) catalyst. Ex situ measurements reveal that the as-deposited CoSx catalyst is composed of small clusters in which the cobalt is surrounded by both sulfur and oxygen. Operando experiments, performed while the CoSx is catalyzing the HER, yield a molecular model in which cobalt is in an octahedral CoS2-like state where the cobalt center is predominantly surrounded by a first shell of sulfur atoms, which, in turn, are preferentially exposed to electrolyte relative to bulk CoS2. We surmise that these CoS2-like clusters form under cathodic polarization and expose a high density of catalytically active sulfur sites for the HER.

In Situ High-Pressure Correlated Transportation of Heavy Rare-Earth Perovskite Nickelates as Batch Synthesized within Eutectic Molten Salts at MPa-pO2.

The multiple magneto-/electrical quantum transitions discovered with d-band correlated metastable perovskite oxides, such as rare-earth nickelate (ReNiO3), enable applications in artificial intelligence and multifunctional sensors. Nevertheless, to date such investigation merely focuses on ReNiO3 with light or middle rare-earth composition, while the analogous explorations toward heavy rare-earth (ReHNiO3, ReH after Gd) are impeded by their ineffective material synthesis relying on GPa pressure. Herein, for the first time we synthesized the powder of ReHNiO3 in grams/batch with ∼1000 times lower pressure and ∼300 °C lower temperature in comparison to the previous ∼101 milligram/batch results, assisted by their eutectic precipitation and heterogeneous growth within alkali-metal halide molten salt at MPa oxygen pressures. Further in situ characterizations under high pressures within a diamond anvil cell reveal a distinguishing pressure predominated bad metal transport within the nonequilibrium state of ReHNiO3 showing high-pressure sensitivity up to 10 GPa, and the temperature dependences in electrical transportations are effectively frozen.

Design Principle of Molybdenum-Based Metal Nitrides for Lattice Nitrogen-Mediated Ammonia Production.

Chemical looping ammonia synthesis (CLAS) is a promising technology for reducing the high energy consumption of the conventional ammonia synthesis process. However, the comprehensive understanding of reaction mechanisms and rational design of novel nitrogen carriers has not been achieved due to the high complexity of catalyst structures and the unrevealed relationship between electronic structure and intrinsic activity. Herein, we propose a multistage strategy to establish the connection between catalyst intrinsic activity and microscopic electronic structure fingerprints using density functional theory computational energetics as bridges and apply it to the rational design of metal nitride catalysts for lattice nitrogen-mediated ammonia production. Molybdenum-based nitride catalysts with well-defined structures are employed as prototypes to elucidate the decoupled effects of electronic and geometrical features. The electron-transfer and spin polarization characteristics of the magnetic metals are constructed as descriptors to disclose the atomic-scale causes of intrinsic activity. Based on this design strategy, it is demonstrated that Ni3Mo3N catalysts possess the highest lattice nitrogen-mediated ammonia synthesis activity. This work reveals the structure-activity relationship of metal nitrides for CLAS and provides a multistage perspective on catalyst rational design.

Significant hydrogen generation via photo-mechanical coupling in flexible methylammonium lead iodide nanowires.

The flexoelectric effect, which refers to the mechanical-electric coupling between strain gradient and charge polarization, should be considered for use in charge production for catalytically driving chemical reactions. We have previously revealed that halide perovskites can generate orders of higher magnitude flexoelectricity under the illumination of light than in the dark. In this study, we report the catalytic hydrogen production by photo-mechanical coupling involving the photoflexoelectric effect of flexible methylammonium lead iodide (MAPbI3) nanowires (NWs) in hydrogen iodide solution. Upon concurrent light illumination and mechanical vibration, large strain gradients were introduced in flexible MAPbI3 NWs, which subsequently induced significant hydrogen generation (at a rate of 756.5 µmol g-1 h-1, surpassing those values from either photo- or piezocatalysis of MAPbI3 nanoparticles). This photo-mechanical coupling strategy of mechanocatalysis, which enables the simultaneous utilization of multiple energy sources, provides a potentially new mechanism in mechanochemistry for highly efficient hydrogen production.

Revealing the Role of the Tetragonal Distortion in the Metal-Insulator Transition of Co- and Fe-Doped NiS.

Although the NiS exhibits the most widely adjustable metal-to-insulator (MIT) properties among the chalcogenides, the mechanisms, with respect to the regulations in their critical temperatures (TMIT), are yet unclear. Herein, we demonstrate the overlooked role associated with the structurally tetragonal distortion in elevating the TMIT of NiS; this is in distinct contrast to the previously expected hybridization and bandwidth regulations that usually reduces TMIT. Compared to the perspective of structure distortions, the orbital hybridization and band regulation of NiS are ∼19 times more effective adjustment in TMIT. As a result, the respective abruptions in both the electrical and thermal resistive switches across the TMIT of NiS can be better preserved in the low-temperature range (<273 K), shedding light on their optimum usage at cryogenic temperatures.

Cu-Modified Palladium Catalysts: Boosting Formate Electrooxidation via Interfacially OHad-Driven Had Removal.

Direct formate fuel cells have gained traction due to their eco-friendly credentials and inherent safety. However, their potential is hampered by the kinetic challenges of the formate oxidation reaction (FOR) on Pd-based catalysts, chiefly due to the unfavorable adsorption of hydrogen species (Had). These species clog the active sites, hindering efficient catalysis. Here, we introduce a straightforward strategy to remedy this bottleneck by incorporating Pd with Cu to expedite the removal of Pd-Had in alkaline media. Notably, Cu plays a pivotal role in bolstering the concentration of hydroxyl adsorbates (OHad) on the surface of catalyst. These OHad species can react with Had, effectively unblocking the active sites for FOR. The as-synthesized catalyst of PdCu/C exhibits a superior FOR performance, boasting a remarkable mass activity of 3.62 A mg-1. Through CO-stripping voltammetry, we discern that the presence of Cu in Pd markedly speeds up the formation of adsorbed hydroxyl species (OHad) at diminished potentials. This, in turn, aids the oxidative removal of Pd-Had, leveraging a synergistic mechanism during FOR. Density functional theory computations further reveal intensified interactions between adsorbed oxygen species and intermediates, underscoring that the Cu-Pd interface exhibits greater oxyphilicity compared to pristine Pd. In this study, we present both experimental and theoretical corroborations, unequivocally highlighting that the integrated copper species markedly amplify the generation of OHad, ensuring efficient removal of Had. This work paves the way, shedding light on the strategic design of high-performing FOR catalysts.

Growth mechanism study and band structure modulation of a manganese doped two-dimensional BlueP-Au network.

Two-dimensional (2D) materials are a very promising material family. The two-dimensional inorganic metal network called BlueP-Au network is rapidly attracting the attention of researchers due to its customizable architecture, adjustable chemical functions and electronic properties. Herein, manganese (Mn) was successfully doped on a BlueP-Au network for the first time, then the doping mechanism and electronic structure evolution was studied by in situ X-ray photoelectron spectroscopy (XPS) based on synchrotron radiation, X-ray absorption spectroscopy (XAS), Scanning Tunneling Microscopy (STM), Density functional theory (DFT), Low-energy electron diffraction (LEED), Angle resolved photoemission spectroscopy (ARPES), etc. Mn atoms tend to be stably adsorbed on two sites of the BlueP-Au network. It was the first observation that atoms can absorb on the two sites stably simultaneously. It is different from the previous adsorption models of BlueP-Au networks. The band structure was also successfully modulated, and overall down about 0.25 eV relative to the Fermi edge. It provided a new strategy for customizing the functional structure of the BlueP-Au network, which has provided new insights into monatomic catalysis, energy storage and nano electronic devices.

Regulation of the Work Function Difference Promotes In Situ Phase Transition of WO3-x for Efficient Formate Electrooxidation.

Direct formate fuel cells (DFFCs) have drawn tremendous attention because they are environmentally benign and have good safety. However, the lack of advanced catalysts for formate electrooxidation hinders the development and applications of DFFCs. Herein, we report a strategy of regulating the metal-substrate work function difference to effectively promote the transfer of adsorbed hydrogen (Had), thus enhancing formate electrooxidation in alkaline solutions. By introducing rich oxygen vacancies, the obtained catalysts of Pd/WO3-x-R show outstanding formate electrooxidation activity, exhibiting an extremely high peak current of 15.50 mA cm-2 with a lower peak potential of 0.63 V. In situ electrochemical Fourier transform infrared and in situ Raman measurements verify an enhanced in situ phase transition from WO3-x to HxWO3-x during the formate oxidation reaction process over the Pd/WO3-x-R catalyst. The results of experimental and density functional theory (DFT) calculations confirm that the work function difference (ΔΦ) between the metal (Pd) and substrate (WO3-x) would be regulated by inducing oxygen vacancies in the substrate, resulting in improved hydrogen spillover at the interface of the catalyst, which is essentially responsible for the observed high performance of formate oxidation. Our findings provide a novel strategy of rationally designing efficient formate electrooxidation catalysts.

Boosting CO2 Electroreduction to C2H4 via Unconventional Hybridization: High-Order Ce4+ 4f and O 2p Interaction in Ce-Cu2O for Stabilizing Cu.

Efficient conversion of carbon dioxide (CO2) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions and close the anthropogenic carbon loop. Recently, there has been intense interest in Cu2O-based catalysts for the CO2 reduction reaction (CO2RR), owing to their capabilities in enhancing C-C coupling. However, the electrochemical instability of Cu+ in Cu2O leads to its inevitable reduction to Cu0, resulting in poor selectivity for C2+ products. Herein, we propose an unconventional and feasible strategy for stabilizing Cu+ through the construction of a Ce4+ 4f-O 2p-Cu+ 3d network structure in Ce-Cu2O. Experimental results and theoretical calculations confirm that the unconventional orbital hybridization near Ef based on the high-order Ce4+ 4f and 2p can more effectively inhibit the leaching of lattice oxygen, thereby stabilizing Cu+ in Ce-Cu2O, compared with traditional d-p hybridization. Compared to pure Cu2O, the Ce-Cu2O catalyst increased the ratio of C2H4/CO by 1.69-fold during the CO2RR at -1.3 V. Furthermore, in situ and ex situ spectroscopic techniques were utilized to track the oxidation valency of copper under CO2RR conditions with time resolution, identifying the well-maintained Cu+ species in the Ce-Cu2O catalyst. This work not only presents an avenue to CO2RR catalyst design involving the high-order 4f and 2p orbital hybridization but also provides deep insights into the metal-oxidation-state-dependent selectivity of catalysts.

Modulating the Interfacial Water Network of Dual-Site Pd/FeOx/C Catalyst for Efficient Formate Electrooxidation.

The rational design of electrocatalysts for formate oxidation reaction (FOR) in alkaline media is crucial to promote the practical applications of direct formate fuel cells (DFFCs). The FOR kinetic on palladium (Pd) based electrocatalysts is strongly hindered by unfavorably adsorbed hydrogen (Had) as the major intermediate species blocking the active sites. Herein, we report a strategy of modulating the interfacial water network of dual-site Pd/FeOx/C catalyst to significantly enhance the desorption kinetics of Had during FOR. Aberration-corrected electron microscopy and synchrotron characterizations revealed the successful construction of Pd/FeOx interfaces on carbon support as a dual-site electrocatalyst for FOR. Electrochemical tests and in situ Raman spectroscopy results showed that Had could be effectively removed from the active sites of the as-designed Pd/FeOx/C catalyst. CO-stripping voltammetry and density functional theory calculations (DFT) demonstrated that the introduced FeOx could effectively accelerate the dissociative adsorption of water molecules on active sites, which accordingly generates adsorbed hydroxyl species (OHad) to facilitate the removal of Had during FOR. This work provides a novel route to develop advanced FOR catalysts for fuel cell applications.

Construction of Novel Bimetallic Oxyphosphide as Advanced Anode for Potassium Ion Hybrid Capacitor.

Potassium ion hybrid capacitors (PIHCs) have attracted considerable interest due to their low cost, competitive power/energy densities, and ultra-long lifespan. However, the more sluggish insertion kinetics of battery-type anodes than capacitor-type cathodes in PIHCs seriously limits their practical application. Therefore, developing advanced anodes with high capacitor and suitable K+ intercalation is imperative and significant. A novel core-shell structure of NiCo oxide/NiCo oxyphosphide (NCOP) nanowires are designed and constructed in this study via efficient and facile strategy. Combining the merits of the core-shell structure and the massive active sites in the oxyphosphide layer, the as-prepared NCOP composites manifest highly reversible capacitors and outstanding rate capability. Meanwhile, the insertion and conversion potassium storage mechanisms of the NCOP are successfully revealed through in situ X-ray diffraction and density functional theory calculations, respectively. Furthermore, the PIHC was assembled with NCOP anode and borocarbonitride cathode, which displays a large energy density and high-power density, along with an exceptional capacity retention of ≈90% over 10 000 cycles at 1.0 A g-1 . This work provides the anion regulation strategy for modifying the transition metal oxide and constructing the advancing electrode materials for next-generation energy storage and beyond.