Atomic coordination environment engineering of bimetallic alloy nanostructures for efficient ammonia electrosynthesis from nitrate.

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.

Constructing molecule-metal relay catalysis over heterophase metallene for high-performance rechargeable zinc-nitrate/ethanol batteries.

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.

Boosting the reaction kinetics in aprotic lithium-carbon dioxide batteries with unconventional phase metal nanomaterials.

Given the high energy density and eco-friendly characteristics, lithium-carbon dioxide (Li-CO2) batteries have been considered to be a next-generation energy technology to promote carbon neutral and space exploration. However, Li-CO2 batteries suffer from sluggish reaction kinetics, causing large overpotential and poor energy efficiency. Here, we observe enhanced reaction kinetics in aprotic Li-CO2 batteries with unconventional phase 4H/face-centered cubic (fcc) iridium (Ir) nanostructures grown on gold template. Significantly, 4H/fcc Ir exhibits superior electrochemical performance over fcc Ir in facilitating the round-trip reaction kinetics of Li+-mediated CO2 reduction and evolution, achieving a low charge plateau below 3.61 V and high energy efficiency of 83.8%. Ex situ/in situ studies and theoretical calculations reveal that the boosted reaction kinetics arises from the highly reversible generation of amorphous/low-crystalline discharge products on 4H/fcc Ir via the Ir-O coupling. The demonstration of flexible Li-CO2 pouch cells with 4H/fcc Ir suggests the feasibility of using unconventional phase nanomaterials in practical scenarios.

Steering the Selectivity of Carbon Dioxide Electroreduction from Single-Carbon to Multicarbon Products on Metal-Organic Frameworks via Facet Engineering.

Although metal-organic frameworks (MOFs) have attracted more attention for the electrocatalytic CO2 reduction reaction (CO2RR), obtaining multicarbon products with a high Faradaic efficiency (FE) remains challenging, especially under neutral conditions. Here, we report the controlled synthesis of stable Cu(I) 5-mercapto-1-methyltetrazole framework (Cu-MMT) nanostructures with different facets by rationally modulating the reaction solvents. Significantly, Cu-MMT nanostructures with (001) facets are acquired using isopropanol as a solvent, which favor multicarbon production with an FE of 73.75% and a multicarbon:single-carbon ratio of 3.93 for CO2RR in a neutral electrolyte. In sharp contrast, Cu-MMT nanostructures with (100) facets are obtained utilizing water, promoting single-carbon generation with an FE of 63.98% and a multicarbon: single-carbon ratio of only 0.18. Furthermore, this method can be extended to other Cu-MMT nanostructures with different facets in tuning the CO2 reduction selectivity. This work opens up new opportunities for the highly selective and efficient CO2 electroreduction to multicarbon products on MOFs via facet engineering.

Controlled Synthesis of Unconventional Phase Alloy Nanobranches for Highly Selective Electrocatalytic Nitrite Reduction to Ammonia.

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 34.6 mg h-1 mgcat -1 (75.5 mg h-1 mgIr -1) at 0 and -0.1 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.

Preparation of Au@Pd Core-Shell Nanorods with fcc-2H-fcc Heterophase for Highly Efficient Electrocatalytic Alcohol Oxidation.

Controlled construction of bimetallic nanostructures with a well-defined heterophase is of great significance for developing highly efficient nanocatalysts and investigating the structure-dependent catalytic performance. Here, a wet-chemical synthesis method is used to prepare Au@Pd core-shell nanorods with a unique fcc-2H-fcc heterophase (fcc: face-centered cubic; 2H: hexagonal close-packed with a stacking sequence of "AB"). The obtained fcc-2H-fcc heterophase Au@Pd core-shell nanorods exhibit superior electrocatalytic ethanol oxidation performance with a mass activity as high as 6.82 A mgPd-1, which is 2.44, 6.96, and 6.43 times those of 2H-Pd nanoparticles, fcc-Pd nanoparticles, and commercial Pd/C, respectively. The operando infrared reflection absorption spectroscopy reveals a C2 pathway with fast reaction kinetics for the ethanol oxidation on the prepared heterophase Au@Pd nanorods. Our experimental results together with density functional theory calculations indicate that the enhanced performance of heterophase Au@Pd nanorods can be attributed to the unconventional 2H phase, the 2H/fcc phase boundary, and the lattice expansion of the Pd shell. Moreover, the heterophase Au@Pd nanorods can also serve as an efficient catalyst for the electrochemical oxidation of methanol, ethylene glycol, and glycerol. Our work in the area of phase engineering of nanomaterials (PENs) opens the way for developing high-performance electrocatalysts toward future practical applications.

Transient Solid-State Laser Activation of Indium for High-Performance Reduction of CO2 to Formate.

Deficiencies in understanding the local environment of active sites and limited synthetic skills challenge the delivery of industrially-relevant current densities with low overpotentials and high selectivity for CO2 reduction. Here, a transient laser induction of metal salts can stimulate extreme conditions and rapid kinetics to produce defect-rich indium nanoparticles (L-In) is reported. Atomic-resolution microscopy and X-ray absorption disclose the highly defective and undercoordinated local environment in L-In. In a flow cell, L-In shows a very small onset overpotential of ≈92 mV and delivers a current density of ≈360 mA cm-2 with a formate Faradaic efficiency of 98% at a low potential of -0.62 V versus RHE. The formation rate of formate reaches up to 6364.4 µmol h-1mgIn-1$mg_{{\rm{In}}}^{--1}$ , which is nearly 39 folds higher than that of commercial In (160.7 µmol h-1mgIn-1$mg_{{\rm{In}}}^{--1}$ ), outperforming most of the previous results that have been reported under KHCO3 environments. Density function theory calculations suggest that the defects facilitate the formation of *OCHO intermediate and stabilize the *HCOOH while inhibiting hydrogen adsorption. This study suggests that transient solid-state laser induction provides a facile and cost-effective approach to form ligand-free and defect-rich materials with tailored activities.

Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction.

With the increasingly serious greenhouse effect, the electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, the performance of CO2RR can hardly meet expectations because of the diverse intermediates and complicated reaction processes, necessitating the exploitation of highly efficient catalysts. In recent years, with advanced characterization technologies and theoretical simulations, the exploration of catalytic mechanisms has gradually deepened into the electronic structure of catalysts and their interactions with intermediates, which serve as a bridge to facilitate the deeper comprehension of structure-performance relationships. Transition metal-based catalysts (TMCs), extensively applied in electrochemical CO2RR, demonstrate substantial potential for further electronic structure modulation, given their abundance of d electrons. Herein, we discuss the representative feasible strategies to modulate the electronic structure of catalysts, including doping, vacancy, alloying, heterostructure, strain, and phase engineering. These approaches profoundly alter the inherent properties of TMCs and their interaction with intermediates, thereby greatly affecting the reaction rate and pathway of CO2RR. It is believed that the rational electronic structure design and modulation can fundamentally provide viable directions and strategies for the development of advanced catalysts toward efficient electrochemical conversion of CO2 and many other small molecules.

Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia.

Electrocatalytic nitrate reduction reaction (NO3RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains a great challenge to achieve highly efficient ammonia production due to the complex proton-coupled electron transfer process in NO3RR. Here, the controlled synthesis of RuMo alloy nanoflowers (NFs) with unconventional face-centered cubic (fcc) phase and hexagonal close-packed/fcc heterophase for highly efficient NO3RR is reported. Significantly, fcc RuMo NFs demonstrate high Faradaic efficiency of 95.2% and a large yield rate of 32.7 mg h-1 mgcat -1 toward ammonia production at 0 and -0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations and theoretical calculations have unraveled that fcc RuMo NFs possess the highest d-band center with superior electroactivity, which originates from the strong Ru─Mo interactions and the high intrinsic activity of the unconventional fcc phase. The optimal electronic structures of fcc RuMo NFs supply strong adsorption of key intermediates with suppression of the competitive hydrogen evolution, which further determines the remarkable NO3RR performance. The successful demonstration of high-performance zinc-nitrate batteries with fcc RuMo NFs suggests their substantial application potential in electrochemical energy supply systems.

Site-Selective Growth of fcc-2H-fcc Copper on Unconventional Phase Metal Nanomaterials for Highly Efficient Tandem CO2 Electroreduction.

Copper (Cu) nanomaterials are a unique kind of electrocatalysts for high-value multi-carbon production in carbon dioxide reduction reaction (CO2RR), which holds enormous potential in attaining carbon neutrality. However, phase engineering of Cu nanomaterials remains challenging, especially for the construction of unconventional phase Cu-based asymmetric heteronanostructures. Here the site-selective growth of Cu on unusual phase gold (Au) nanorods, obtaining three kinds of heterophase fcc-2H-fcc Au-Cu heteronanostructures is reported. Significantly, the resultant fcc-2H-fcc Au-Cu Janus nanostructures (JNSs) break the symmetric growth mode of Cu on Au. In electrocatalytic CO2RR, the fcc-2H-fcc Au-Cu JNSs exhibit excellent performance in both H-type and flow cells, with Faradaic efficiencies of 55.5% and 84.3% for ethylene and multi-carbon products, respectively. In situ characterizations and theoretical calculations reveal the co-exposure of 2H-Au and 2H-Cu domains in Au-Cu JNSs diversifies the CO* adsorption configurations and promotes the CO* spillover and subsequent C-C coupling toward ethylene generation with reduced energy barriers.

Metal functionalization of two-dimensional nanomaterials for electrochemical carbon dioxide reduction.

With the mechanical exfoliation of graphene in 2004, researchers around the world have devoted significant efforts to the study of two-dimensional (2D) nanomaterials. Nowadays, 2D nanomaterials are being developed into a large family with varieties of structures and derivatives. Due to their fascinating electronic, chemical, and physical properties, 2D nanomaterials are becoming an important type of catalyst for the electrochemical carbon dioxide reduction reaction (CO2RR). Here, we review the recent progress in electrochemical CO2RR using 2D nanomaterial-based catalysts. First, we briefly describe the reaction mechanism of electrochemical CO2 reduction to single-carbon (C1) and multi-carbon (C2+) products. Then, we discuss the strategies and principles for applying metal materials to functionalize 2D nanomaterials, such as graphene-based materials, metal-organic frameworks (MOFs), and transition metal dichalcogenides (TMDs), as well as applications of resultant materials in the electrocatalytic CO2RR. Finally, we summarize the present research advances and highlight the current challenges and future opportunities of using metal-functionalized 2D nanomaterials in the electrochemical CO2RR.

Accelerating multielectron reduction at CuxO nanograins interfaces with controlled local electric field.

Regulating electron transport rate and ion concentrations in the local microenvironment of active site can overcome the slow kinetics and unfavorable thermodynamics of CO2 electroreduction. However, simultaneous optimization of both kinetics and thermodynamics is hindered by synthetic constraints and poor mechanistic understanding. Here we leverage laser-assisted manufacturing for synthesizing CuxO bipyramids with controlled tip angles and abundant nanograins, and elucidate the mechanism of the relationship between electron transport/ion concentrations and electrocatalytic performance. Potassium/OH- adsorption tests and finite element simulations corroborate the contributions from strong electric field at the sharp tip. In situ Fourier transform infrared spectrometry and differential electrochemical mass spectrometry unveil the dynamic evolution of critical *CO/*OCCOH intermediates and product profiles, complemented with theoretical calculations that elucidate the thermodynamic contributions from improved coupling at the Cu+/Cu2+ interfaces. Through modulating the electron transport and ion concentrations, we achieve high Faradaic efficiency of 81% at ~900 mA cm-2 for C2+ products via CO2RR. Similar enhancement is also observed for nitrate reduction reaction (NITRR), achieving 81.83 mg h-1 ammonia yield rate per milligram catalyst. Coupling the CO2RR and NITRR systems demonstrates the potential for valorizing flue gases and nitrate wastes, which suggests a practical approach for carbon-nitrogen cycling.

Controlled Synthesis of 2D Prussian Blue Analog Nanosheets with Low Coordinated Water Content for High-Performance Lithium Storage.

Prussian blue analogs (PBAs) with open and porous frameworks have attracted wide attention in alkali metal ion batteries due to their high theoretical specific capacities and fast ion insertion/extraction kinetics. However, abundant coordinated water usually exists in traditional PBAs synthesized in aqueous systems. Consequently, the competition between coordinated water and alkali ions easily causes the rapid structural collapse of PBAs during the repeated discharge/charge cycles, lowering the cycling stability, and rate performance of batteries. Besides, most reported PBAs adopt the cubic/particle-like morphologies with large sizes, which usually suffer from insufficient ion diffusion especially at high rates. Herein, a facile and general strategy for the synthesis of 2D CoCo, CuFe, CuCeFe, and CuCeCo-based PBA nanosheets is reported. As a proof-of-concept application, Co3 [Co(CN)6 ]2 nanosheets are evaluated as anode materials for lithium-ion batteries. Thanks to the lower coordinated water content, smaller impedance and higher lithium-ion diffusion coefficient, Co3 [Co(CN)6 ]2 nanosheets deliver a superior reversible capacity of 810.4 mAh g-1 at 100 mA g-1 , better rate performance, and higher cycling stability compared to common Co3 [Co(CN)6 ]2 cubes. Further studies indicate that the capacitance-controlled electrochemical behaviors dominate in the Co3 [Co(CN)6 ]2 nanosheets, giving rise to their excellent structural stability and superior lithium storage performance even at high rates.

Confined Growth of Silver-Copper Janus Nanostructures with {100} Facets for Highly Selective Tandem Electrocatalytic Carbon Dioxide Reduction.

Electrocatalytic carbon dioxide reduction reaction (CO2 RR) holds significant potential to promote carbon neutrality. However, the selectivity toward multicarbon products in CO2 RR is still too low to meet practical applications. Here the authors report the delicate synthesis of three kinds of Ag-Cu Janus nanostructures with {100} facets (JNS-100) for highly selective tandem electrocatalytic reduction of CO2 to multicarbon products. By controlling the surfactant and reduction kinetics of Cu precursor, the confined growth of Cu with {100} facets on one of the six equal faces of Ag nanocubes is realized. Compared with Cu nanocubes, Ag65 -Cu35 JNS-100 demonstrates much superior selectivity for both ethylene and multicarbon products in CO2 RR at less negative potentials. Density functional theory calculations reveal that the compensating electronic structure and carbon monoxide spillover in Ag65 -Cu35 JNS-100 contribute to the enhanced CO2 RR performance. This study provides an effective strategy to design advanced tandem catalysts toward the extensive application of CO2 RR.

Influence of Metal-Ligand Coordination on the Elemental Growth and Alloying Composition of Pt-Ni Octahedral Nanoparticles for Oxygen Reduction Electrocatalysis.

Understanding the role of surfactants or ligands on the growth mechanism of metal/alloy nanoparticles (NPs) is important for controlled synthesis of functional metallic NPs with tailored structures and properties. There have been a number of works showing the significant impact of surfactants/ligands on the shape-controlled synthesis of nanocrystals with well-defined surfaces. Beyond the morphological shape control, impact of the surfactants/ligands on the alloying structure of bimetallic nanocrystals, however, still remains largely unaddressed. We reveal here a significant effect of benzoic acid ligand on the elemental growth and alloying phase structure of octahedral Pt-Ni NPs, a class of highly active electrocatalyst for oxygen reduction reaction in fuel cells. Contrary to previous reports showing the critical role of benzoic acid in directing the growth of octahedral Pt-Ni NPs, we found that benzoic acid played a minor role in forming the octahedral shape; instead, it can strongly coordinate with Ni cation and significantly slows down its reduction rate, leading to a phase separation in the Pt-Ni NP products (a mixture of Pt-rich octahedral NPs and nearly pure Ni NPs). Such phase separation further resulted in a lower catalytic activity and stability. These results help us comprehensively understand the effect of metal-ligand coordination chemistry on the elemental growth mechanism and alloying phase structure of bimetallic NPs, complementing previous emphasis on the role of surfactants in purely morphological shape control.