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Two-dimensional van der Waals heterostructures (vdWHs) have attracted considerable interest1-4. However, most vdWHs reported so far are created by an arduous micromechanical exfoliation and manual restacking process5, which-although versatile for proof-of-concept demonstrations6-16 and fundamental studies17-30-is clearly not scalable for practical technologies. Here we report a general synthetic strategy for two-dimensional vdWH arrays between metallic transition-metal dichalcogenides (m-TMDs) and semiconducting TMDs (s-TMDs). By selectively patterning nucleation sites on monolayer or bilayer s-TMDs, we precisely control the nucleation and growth of diverse m-TMDs with designable periodic arrangements and tunable lateral dimensions at the predesignated spatial locations, producing a series of vdWH arrays, including VSe2/WSe2, NiTe2/WSe2, CoTe2/WSe2, NbTe2/WSe2, VS2/WSe2, VSe2/MoS2 and VSe2/WS2. Systematic scanning transmission electron microscopy studies reveal nearly ideal vdW interfaces with widely tunable moiré superlattices. With the atomically clean vdW interface, we further show that the m-TMDs function as highly reliable synthetic vdW contacts for the underlying WSe2 with excellent device performance and yield, delivering a high ON-current density of up to 900 microamperes per micrometre in bilayer WSe2 transistors. This general synthesis of diverse two-dimensional vdWH arrays provides a versatile material platform for exploring exotic physics and promises a scalable pathway to high-performance devices.
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Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO3RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg-1cat, superior rate capability, excellent cycling stability of ~400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems.
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Electrochemical nitrate reduction reaction (NO3RR) to ammonia has been regarded as a promising strategy to balance the global nitrogen cycle. However, it still suffers from poor Faradaic efficiency (FE) and limited yield rate for ammonia production on heterogeneous electrocatalysts, especially in neutral solutions. Herein, we report one-pot synthesis of ultrathin nanosheet-assembled RuFe nanoflowers with low-coordinated Ru sites to enhance NO3RR performances in neutral electrolyte. Significantly, RuFe nanoflowers exhibit outstanding ammonia FE of 92.9% and yield rate of 38.68 mg h-1 mgcat-1 (64.47 mg h-1 mgRu-1) at -0.30 and -0.65 V (vs. reversible hydrogen electrode), respectively. Experimental studies and theoretical calculations reveal that RuFe nanoflowers with low-coordinated Ru sites are highly electroactive with an increased d-band center to guarantee efficient electron transfer, leading to low energy barriers of nitrate reduction. The demonstration of rechargeable zinc-nitrate batteries with large-specific capacity using RuFe nanoflowers indicates their great potential in next-generation electrochemical energy systems.
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The development of efficient and stable catalysts for hydrogen production from electrolytic water in a wide pH range is of great significance in alleviating the energy crisis. Herein, Pt nanoparticles (NPs) anchored on the vacancy of high entropy rare earth oxides (HEREOs) were prepared for the first time for highly efficient hydrogen production by water electrolysis. The prepared Pt-(LaCeSmYErGdYb)O showed excellent electrochemical performances, which require only 12, 57, and 77 mV to achieve a current density of 100 mA cm-2 in 0.5 M H2SO4, 1.0 M KOH, and 1.0 M PBS environments, respectively. In addition, Pt-(LaCeSmYErGdYb)O has successfully worked at 400 mA cm-2 @ 60 °C for 100 h in 0.5 M H2SO4, presenting the high mass activity of 37.7 A mg-1Pt and turnover frequency (TOF) value of 38.2 s-1 @ 12 mV, which is far superior to the recently reported hydrogen evolution reaction (HER) catalysts. Density functional theory (DFT) calculations have revealed that the interactions between Pt and HEREO have optimized the electronic structures for electron transfer and the binding strength of intermediates. This further leads to optimized proton binding and water dissociation, supporting the highly efficient and robust HER performances in different environments. This work provides a new idea for the design of efficient RE-based electrocatalysts.
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Facet control and phase engineering of metal nanomaterials are both important strategies to regulate their physicochemical properties and improve their applications. However, it is still a challenge to tune the exposed facets of metal nanomaterials with unconventional crystal phases, hindering the exploration of the facet effects on their properties and functions. In this work, by using Pd nanoparticles with unconventional hexagonal close-packed (hcp, 2H type) phase, referred to as 2H-Pd, as seeds, a selective epitaxial growth method is developed to tune the predominant growth directions of secondary materials on 2H-Pd, forming Pd@NiRh nanoplates (NPLs) and nanorods (NRs) with 2H phase, referred to as 2H-Pd@2H-NiRh NPLs and NRs, respectively. The 2H-Pd@2H-NiRh NRs expose more (100)h and (101)h facets on the 2H-NiRh shells compared to the 2H-Pd@2H-NiRh NPLs. Impressively, when used as electrocatalysts toward hydrogen oxidation reaction (HOR), the 2H-Pd@2H-NiRh NRs show superior activity compared to the NiRh alloy with conventional face-centered cubic (fcc) phase (fcc-NiRh) and the 2H-Pd@2H-NiRh NPLs, revealing the crucial role of facet control in enhancing the catalytic performance of unconventional-phase metal nanomaterials. Density functional theory (DFT) calculations further unravel that the excellent HOR activity of 2H-Pd@2H-NiRh NRs can be attributed to the more exposed (100)h and (101)h facets on the 2H-NiRh shells, which possess high electron transfer efficiency, optimized H* binding energy, enhanced OH* binding energy, and a low energy barrier for the rate-determining step during the HOR process.
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The synthesis of nitrate by the electrochemical N2 oxidation reaction (NOR) is currently one of the most promising routes. However, the traditional generation of nitrate depends on the oxidation reaction between N2 and H2O (or ·OH), which involves complex reaction steps and intermediates, showing strong competition from oxygen evolution reaction (OER). Here, an effective NOR method is proposed to directly oxidize N2 by using O3 as a reactive oxygen source to reduce the reaction step. Electrochemical tests demonstrate that the nitrate yield of Pd-Mn3O4/CNT electrocatalyst reaches the milligram level, which is the highest yield reported so far for electrocatalytic NOR. Quantitative characterization is employed to establish a comprehensive set of benchmarks to confirm the intrinsic nature of nitrogen activation and test the O3-mediated reaction mechanism. Density functional theory (DFT) calculations show that the heterostructure Pd-Mn3O4 leads to a strong adsorption preference for N2 and O3, which greatly reduces the activation energy barrier for N2. This accelerates the synthesis of nitrate based on the direct formation mechanism, which reduces energy barriers and the reaction steps, thus increasing the performance of electrocatalytic nitrate production. The techno-economic analysis underscores the promising feasibility and sustainable economic value of the presented method.
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Reaching rapid reaction kinetics of oxygen reduction (ORR) and oxygen evolution reactions (OER) is critical for realizing efficient rechargeable zinc-air batteries (ZABs). Herein, a novel CoNi-CoN3 composite site containing CoNi alloyed nanoparticles and CoN3 moieties is first constructed in N-doped carbon nanosheet matrix (CoNi-CoN3/C). Benefiting from the high electroactivity of CoNi-CoN3 composite sites and large surface area, CoNi-CoN3/C shows a superior half-wave potential (0.88 V versus RHE) for ORR and a small overpotential (360 mV) for OER at 10 mA cm-2. Theoretical calculations have demonstrated that the introduction of CoNi alloys has modulated the electronic distributions near the CoN3 moiety, inducing the d-band center of CoNi-CoN3 composite site to shift down, thus stabilizing the valence state of Co active sites and balancing the adsorption of OER/ORR intermediates. Accordingly, the reaction energy trends exhibit optimized overpotentials for OER/ORR, leading to superior battery performances. For aqueous and flexible quasi-solid-state rechargeable ZABs with CoNi-CoN3/C as catalyst, a large power density (250 mW cm-2) and high specific capacity (804 mAh g-1) are achieved. The in-depth understanding of the electroactivity enhancement mechanism of interactive metal nanoparticles and metal coordinated with nitrogen (MNx) moieties is crucial for designing novel high-performance metal/nitrogen-doped carbon (MâNâC) catalysts.
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It is important to understand the polymorph transition and crystal-amorphous phase transition in In2Se3 to tap the potential of this material for resistive memory storage. By monitoring layer-by-layer growth of ß-In2Se3 during molecular beam epitaxy (MBE), we are able to identify a cyclical order-disorder transition characterized by a periodic alternation between a glassy-like metastable subunit cell film consisting of n < 5 sublayers (nth layers = the number of subunit cell layers), and a highly crystalline ß-In2Se3 at n = 5 layers. The glassy phase shows an odd-even alternation between the indium-cluster layer (n = 1, 3) and an In-Se solid solution (n = 2, 4), which suggests the ability of In and Se atoms to diffuse, aggregate, and intermix. These dynamic natures of In and Se atoms contribute to a defect-driven memory resistive behavior in current-voltage sweeps that is different from the ferroelectric switching of α-In2Se3.
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The controlled synthesis of metal nanomaterials with unconventional phases is of significant importance to develop high-performance catalysts for various applications. However, it remains challenging to modulate the atomic arrangements of metal nanomaterials, especially the alloy nanostructures that involve different metals with distinct redox potentials. Here we report the general one-pot synthesis of IrNi, IrRhNi and IrFeNi alloy nanobranches with unconventional hexagonal close-packed (hcp) phase. Notably, the as-synthesized hcp IrNi nanobranches demonstrate excellent catalytic performance towards electrochemical nitrite reduction reaction (NO2RR), with superior NH3 Faradaic efficiency and yield rate of 98.2 % and 34.6â mg h-1 mgcat -1 (75.5â mg h-1 mgIr -1) at 0 and -0.1â V (vs reversible hydrogen electrode), respectively. Ex/in situ characterizations and theoretical calculations reveal that the Ir-Ni interactions within hcp IrNi alloy improve electron transfer to benefit both nitrite activation and active hydrogen generation, leading to a stronger reaction trend of NO2RR by greatly reducing energy barriers of rate-determining step.
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Electrocatalytic reduction of carbon dioxide into value-added chemical fuels is a promising way to achieve carbon neutrality. Bismuth-based materials have been considered as favorable electrocatalysts for converting carbon dioxide to formic acid. Moreover, size-dependent catalysis offers significant advantages in catalyzed heterogeneous chemical processes. However, the size effects of bismuth nanoparticles on formic acid production have not been fully explored. Here, we prepared Bi nanoparticles uniformly supported on porous TiO2 substrate electrocatalytic materials by in situ segregation of the Bi element from Bi4Ti3O12. The Bi-TiO2 electrocatalyst with Bi nanoparticles of 2.83 nm displays a Faradaic efficiency of greater than 90% over a wide potential range of 400 mV. Theoretical calculations have also demonstrated subtle electronic structural evolutions induced by the size variations of Bi nanoparticles, where the 2.83 nm Bi nanoparticles display the most active p-band and d-band centers to guarantee high electroactivity toward CO2RR.
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Designing efficient and durable bifunctional catalysts for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) and hydrogen evolution reaction (HER) is desirable for the co-production of biomass-upgraded chemicals and sustainable hydrogen, which is limited by the competitive adsorption of hydroxyl species (OHads) and HMF molecules. Here, we report a class of Rh-O5/Ni(Fe) atomic site on nanoporous mesh-type layered double hydroxides with atomic-scale cooperative adsorption centers for highly active and stable alkaline HMFOR and HER catalysis. A low cell voltage of 1.48 V is required to achieve 100 mA cm-2 in an integrated electrolysis system along with excellent stability (>100 h). Operando infrared and X-ray absorption spectroscopic probes unveil that HMF molecules are selectively adsorbed and activated over the single-atom Rh sites and oxidized by in situ-formed electrophilic OHads species on neighboring Ni sites. Theoretical studies further demonstrate that the strong d-d orbital coupling interactions between atomic-level Rh and surrounding Ni atoms in the special Rh-O5/Ni(Fe) structure can greatly facilitate surface electronic exchange-and-transfer capabilities with the adsorbates (OHads and HMF molecules) and intermediates for efficient HMFOR and HER. We also reveal that the Fe sites in Rh-O5/Ni(Fe) structure can promote the electrocatalytic stability of the catalyst. Our findings provide new insights into catalyst design for complex reactions involving competitive adsorptions of multiple intermediates.
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A cross-coupling reaction via the dehydrogenative route over heterogeneous solid atomic catalysts offers practical solutions toward an economical and sustainable elaboration of simple organic substrates. The current utilization of this technology is, however, hampered by limited molecular definition of many solid catalysts. Here, we report the development of Cu-M dual-atom catalysts (where M = Co, Ni, Cu, and Zn) supported on a hierarchical USY zeolite to mediate efficient dehydrogenative cross-coupling of unprotected phenols with amine partners. Over 80% isolated yields have been attained over Cu-Co-USY, which shows much superior reactivity when compared with our Cu1 and other Cu-M analogues. This amination reaction has hence involved simple and non-forceful reaction condition requirements. The superior reactivity can be attributed to (1) the specifically designed bimetallic Cu-Co active sites within the micropore for "co-adsorption-co-activation" of the reaction substrates and (2) the facile intracrystalline (meso/micropore) diffusion of the heterocyclic organic substrates. This study offers critical insights into the engineering of next-generation solid atomic catalysts with complex reaction steps.
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Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet (Co2 )oct O4 nanosheets (NSs) at fixed geometrical sites, including Mnoct , Nioct , and Nitet , to optimize the initial geometrical structure and modulate the CoCo2 O4 surface from oxygen-excess to oxygen-deficiency. The pristine (Ni,Mn)-(Co)tet (Co2 )oct O4 NSs shows excellent OER activity with an overpotential of 281.6â mV at a current density of 10â mA cm-2 . Moreover, without damaging their initial activity, the activated (Act)-(Ni,Mn)-(Co)tet (Co2 )oct O4 NSs after surface reconstruction exhibit long-term stability of 100â h under 10â mA cm-2 , 50â mA cm-2 , or even 100â mA cm-2 . The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.
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Developing highly efficient and stable hydrogen production catalysts for electrochemical water splitting (EWS) at industrial current densities remains a great challenge. Herein, we proposed a heterostructure-induced-strategy to optimize the metal-support interaction (MSI) and the EWS activity of Ru-Ni3 N/NiO. Density functional theory (DFT) calculations firstly predicted that the Ni3 N/NiO-heterostructures can improve the structural stability, electronic distributions, and orbital coupling of Ru-Ni3 N/NiO compared to Ru-Ni3 N and Ru-NiO, which accordingly decreases energy barriers and increases the electroactivity for EWS. As a proof-of-concept, the Ru-Ni3 N/NiO catalyst with a 2D Ni3 N/NiO-heterostructures nanosheet array, uniformly dispersed Ru nanoparticles, and strong MSI, was successfully constructed in the experiment, which exhibited excellent HER and OER activity with overpotentials of 190â mV and 385â mV at 1000â mA cm-2 , respectively. Furthermore, the Ru-Ni3 N/NiO-based EWS device can realize an industrial current density (1000â mA cm-2 ) at 1.74â V and 1.80â V under alkaline pure water and seawater conditions, respectively. Additionally, it also achieves a high durability of 1000â h (@ 500â mA cm-2 ) in alkaline pure water.
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High-entropy alloys (HEAs) are attracting intensive attention due to their broad compositional tunability and interesting catalytic properties. However, precisely shaping the HEAs into suprathin low-dimensional nanostructures for achieving diverse applications remains an enormous challenge owing to their intrinsic thermodynamic instability. Herein we propose a new and general low-temperature method for incorporating up to eight metallic elements into one single-phase subnanometer ribbon to achieve the thinnest HEA metal materials in the world. We experimentally demonstrate that synthetic processes for suprathin HEA subnanometer ribbons (SNRs) include (1) different metal atom nucleation via galvanic exchange reaction between different metal precursors and Ag nanowire template, (2) co-reduction of different metal precursors on nanowire template, and (3) the removal of the inner Ag core. Density functional theory (DFT) calculations reveal that the crystallization and stabilization of HEA SNRs strongly depend on the "highly dynamic" Ag from the template, and the crystallization levels of HEA subnanometer ribbons are closely correlated with the concentration of Pt and Pd. We demonstrate that the present synthetic method enables the flexible control of components and concentrations in HEAs SNRs for achieving a library of HEA SNRs and also superior electrocatalytic properties. The well-designed HEA SNRs show great improvement in catalyzing the oxygen reduction reaction of fuel cells and also high discharge capacity, low charge overpotential, and excellent durability for Li-O2 batteries. DFT calculations reveal the superior electrochemical performances are attributed to the strong reduction capability from high-concentration reductive elements in HEAs, while the other elements guarantee the site-to-site efficient electron transfer.
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Realizing the rational design of perovskite oxides with controllable compositions and nanostructures remains a tremendous challenge for the development of efficient electrocatalysts. Herein, a ligand-assisted synthetic strategy to fabricate perovskite oxides LaCo1- x Fex O3 with yolk-shell nanostructures is developed. Benefiting from the unique structural and compositional merits, LaCo0.75 Fe0.25 O3 exhibits an overpotential of 310 mV at a current density of 10 mA cm-2 and long-term stability of 100 h for the oxygen evolution reaction. In situ Raman spectroscopy demonstrates that Fe substitution facilitates the pre-oxidation of Co sites and induces the surface reconstruction into active Co oxyhydroxides at a relatively lower applied potential, guaranteeing excellent catalytic performances. Density functional theory calculations unravel that the appropriate introduction of Fe into perovskite LaCoO3 leads to the improved electroactivity and durability of the catalyst for the oxygen evolution reaction (OER). Fe-3d orbitals show a pinning effect on Co-3d orbitals to maintain the stable valence state of Co sites at the low overpotential of the OER. Furthermore, Zn-air batteries (ZABs) assembled with LaCo0.75 Fe0.25 O3 display a high open circuit potential of 1.47 V, superior energy density of 905 Wh kg-1 Zn , and excellent stability in a large temperature range. This work supplies novel insights into the future developments of perovskite-based electrocatalysts.
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Engineering multicomponent nanocatalysts is effective to improve electrocatalysis in many applications, yet it remains a challenge in constructing well-defined multimetallic active sites at the atomic level. Herein, the surface inlay of sub-monolayer Pb oxyhydroxide onto hexagonal PtBi intermetallic nanoplates with intrinsically isolated Pt atoms to boost the methanol oxidation reaction (MOR) is reported. The well-defined PtBi@6.7%Pb nanocatalyst exhibits 4.0 and 7.4 times higher mass activity than PtBi nanoplates and commercial Pt/C catalyst toward MOR in the alkaline electrolyte at 30 °C. Meanwhile, it also achieves a record-high mass activity of 51.07 A mg-1 Pt at direct methanol fuel cells operation temperature of 60 °C. DFT calculations reveal that the introduction of Pb oxyhydroxide on the surface not only promotes the electron transfer efficiency but also suppresses the CO poisoning effect, and the efficient p-d coupling optimizes the electroactivity of PtBi@6.7%Pb nanoplates toward the MOR process with low reaction barriers. This work offers a nanoengineering strategy to effectively construct and modulate multimetallic nanocatalysts to improve the electroactivity toward the MOR in future research.
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The electrochemical carbon dioxide reduction reaction (CO2 RR) provides a sustainable strategy to relieve global warming and achieve carbon neutrality. However, the practical application of CO2 RR is still limited by the poor selectivity and low current density. Here, the surface molecular functionalization of unusual phase metal nanomaterials for high-performance CO2 RR under industry-relevant current density is reported. It is observed that 5-mercapto-1-methyltetrazole (MMT)-modified 4H/face-centered cubic (fcc) gold (Au) nanorods demonstrate greatly enhanced CO2 RR performance than original oleylamine (OAm)-capped 4H/fcc Au nanorods in both an H-type cell and flow cell. Significantly, MMT-modified 4H/fcc Au nanorods deliver an excellent carbon monoxide selectivity of 95.6% under the industry-relevant current density of 200 mA cm-2 . Density functional theory calculations reveal distinct electronic modulations by surface ligands, in which MMT improves while OAm suppresses the surface electroactivity of 4H/fcc Au nanorods. Furthermore, this method can be extended to various MMT derivatives and conventional fcc Au nanostructures in boosting CO2 RR performance.
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Rare-earth (RE) solid-state halide electrolytes have been extensively studied recently in the field of lithium (Li) ion all-solid-state batteries (ASSBs) due to their excellent electrochemical performances. Herein, a new RE-based solid halide electrolyte Li3HoBr6 (LHB) has been synthesized and exhibits high Li ion conductivity up to mS cm-1 at room temperature. Theoretical calculations have identified four different Li ion migration pathways, in which the out-of-plane pathways are much more favorable than the direct in-plane pathways. In addition, LHB has a wider electrochemical window in comparison to a sulfide solid electrolyte and good deformability. The LHB-based Li-sulfur ASSB assembled by cold pressing can exhibit good cycling stability with high Coulombic efficiency, which shows that LHB has potential application in ASSBs.
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The Cu-based nanocatalysts have shown a high selectivity toward selective hydrogenation reaction, but the underlying catalytic mechanism is still murky. Herein, we report a new gram-scale strategy for realizing the single atom Cu site incorporated into the melem ring of graphitic carbon nitride (Cu1/CN) for understanding the catalytic mechanism of a hydrogenation reaction. The as-synthesized Cu1/CN exhibits unprecedented selectivity (100%), high activity (TOF = 2.9 × 103 h-1), and outstanding stability for selective hydrogenation of 4-nitrostyrene. We reveal that the presence of hydroxymethyl from trimethylolmelamine is beneficial to atomically disperse Cu atoms in the CN. X-ray absorption fine structure tests reveal that the Cu atom of Cu1/CN is dominated by the quaternary coordination way (Cu-N4) in the melem ring of CN. Density functional theory calculations confirm that the high reactivity and selectivity originate from the anchored Cu sites creating the optimal chemical environment for the highly efficient hydrogenation reaction.