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.

Rapid production of kilogram-scale graphene nanoribbons with tunable interlayer spacing for an array of renewable energy.

Graphene nanoribbons (GNRs) are widely recognized as intriguing building blocks for high-performance electronics and catalysis owing to their unique width-dependent bandgap and ample lone pair electrons on both sides of GNR, respectively, over the graphene nanosheet counterpart. However, it remains challenging to mass-produce kilogram-scale GNRs to render their practical applications. More importantly, the ability to intercalate nanofillers of interest within GNR enables in-situ large-scale dispersion and retains structural stability and properties of nanofillers for enhanced energy conversion and storage. This, however, has yet to be largely explored. Herein, we report a rapid, low-cost freezing-rolling-capillary compression strategy to yield GNRs at a kilogram scale with tunable interlayer spacing for situating a set of functional nanomaterials for electrochemical energy conversion and storage. Specifically, GNRs are created by sequential freezing, rolling, and capillary compression of large-sized graphene oxide nanosheets in liquid nitrogen, followed by pyrolysis. The interlayer spacing of GNRs can be conveniently regulated by tuning the amount of nanofillers of different dimensions added. As such, heteroatoms; metal single atoms; and 0D, 1D, and 2D nanomaterials can be readily in-situ intercalated into the GNR matrix, producing a rich variety of functional nanofiller-dispersed GNR nanocomposites. They manifest promising performance in electrocatalysis, battery, and supercapacitor due to excellent electronic conductivity, catalytic activity, and structural stability of the resulting GNR nanocomposites. The freezing-rolling-capillary compression strategy is facile, robust, and generalizable. It renders the creation of versatile GNR-derived nanocomposites with adjustable interlay spacing of GNR, thereby underpinning future advances in electronics and clean energy applications.

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.

Metal Doped Unconventional Phase IrNi Nanobranches: Tunable Electrochemical Nitrate Reduction Performance and Pollutants Upcycling.

Electrochemical nitrate reduction (NO3RR) provides a new option to abate nitrate contamination with a low carbon footprint. Restricted by competitive hydrogen evolution, achieving satisfied nitrate reduction performance in neutral media is still a challenge, especially for the regulation of this multielectron multiproton reaction. Herein, facile element doping is adopted to tune the catalytic behavior of IrNi alloy nanobranches with an unconventional hexagonal close-packed (hcp) phase toward NO3RR. In particular, the obtained hcp IrNiCu nanobranches favor the ammonia production and suppress byproduct formation in a neutral electrolyte indicated by in situ differential electrochemical mass spectrometry, with a high Faradaic efficiency (FE) of 85.6% and a large yield rate of 1253 µg cm-2 h-1 at -0.4 and -0.6 V (vs reversible hydrogen electrode (RHE)), respectively. In contrast, the resultant hcp IrNiCo nanobranches promote the formation of nitrite, with a peak FE of 33.1% at -0.1 V (vs RHE). Furthermore, a hybrid electrolysis cell consisting of NO3RR and formaldehyde oxidation is constructed, which are both catalyzed by hcp IrNiCu nanobranches. This electrolyzer exhibits lower overpotential and holds the potential to treat polluted air and wastewater simultaneously, shedding light on green chemical production based on contaminate degradation.

Defect engineering of two-dimensional materials for advanced energy conversion and storage.

In the global trend towards carbon neutrality, sustainable energy conversion and storage technologies are of vital significance to tackle the energy crisis and climate change. However, traditional electrode materials gradually reach their property limits. Two-dimensional (2D) materials featuring large aspect ratios and tunable surface properties exhibit tremendous potential for improving the performance of energy conversion and storage devices. To rationally control the physical and chemical properties for specific applications, defect engineering of 2D materials has been investigated extensively, and is becoming a versatile strategy to promote the electrode reaction kinetics. Simultaneously, exploring the in-depth mechanisms underlying defect action in electrode reactions is crucial to provide profound insight into structure tailoring and property optimization. In this review, we highlight the cutting-edge advances in defect engineering in 2D materials as well as their considerable effects in energy-related applications. Moreover, the confronting challenges and promising directions are discussed for the development of advanced energy conversion and storage systems.

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.

Freestanding 2D NiFe Metal-Organic Framework Nanosheets: Facilitating Proton Transfer via Organic Ligands for Efficient Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) is crucial to electrochemical hydrogen production. However, designing and fabricating efficient electrocatalysts still remains challenging. By confinedly coordinating organic ligands with metal species in layered double hydroxides (LDHs), an innovative LDHs-assisted approach is developed to facilely synthesize freestanding bimetallic 2D metal-organic framework nanosheets (2D MOF NSs), preserving the metallic components and activities in OER. Furthermore, the research has demonstrated that the incorporation of carboxyl organic ligands coordinated with metal atoms as proton transfer mediators endow 2D MOF NSs with efficient proton transfer during the electrochemical OHads  â†’ Oads transition. These freestanding NiFe-2D MOF NSs require a small overpotential of 260 mV for a current density of 10 mA cm-2 . When this strategy is applied to LDH nanosheets grown on nickel foam, the overpotential can be reduced to 221 mV. This outstanding OER activity supports the capability of multimetallic organic frameworks for the rational design of water oxidation electrocatalysts. This strategy provides a universal path to the synthesis of 2D MOF NSs that can be used as electrocatalysts directly.

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.

Surface Molecular Functionalization of Unusual Phase Metal Nanomaterials for Highly Efficient Electrochemical Carbon Dioxide Reduction under Industry-Relevant Current Density.

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.

Crystal Phase Control of Gold Nanomaterials by Wet-Chemical Synthesis.

Gold (Au), a transition metal with an atomic number of 79 in the periodic table of elements, was discovered in approximately 3000 B.C. Due to the ultrahigh chemical stability and brilliant golden color, Au had long been thought to be a most inert material and was widely utilized in art, jewelry, and finance. However, it has been found that Au becomes exceptionally active as a catalyst when its size shrinks to the nanometer scale. With continuous efforts toward the exploration of catalytic applications over the past decades, Au nanomaterials show critical importance in many catalytic processes. Besides catalysis, Au nanomaterials also possess other promising applications in plasmonics, sensing, biology and medicine, due to their unique localized surface plasmon resonance, intriguing biocompatibility, and superior stability. Unfortunately, the practical applications of Au nanomaterials could be limited because of the scarce reserves and high price of Au. Therefore, it is quite essential to further explore novel physicochemical properties and functions of Au nanomaterials so as to enhance their performance in different types of applications.Recently, phase engineering of nanomaterials (PEN), which involves the rearrangement of atoms in the unit cell, has emerged as a fantastic and effective strategy to adjust the intrinsic physicochemical properties of nanomaterials. In this Account, we give an overview of the recent progress on crystal phase control of Au nanomaterials using wet-chemical synthesis. Starting from a brief introduction of the research background, we first describe the development history of wet-chemical synthesis of Au nanomaterials and especially emphasize the key research findings. Subsequently, we introduce the typical Au nanomaterials with untraditional crystal phases and heterophases that have been observed, such as 2H, 4H, body-centered phases, and crystal-phase heterostructures. Importantly, crystal phase control of Au nanomaterials by wet-chemical synthesis is systematically described. After that, we highlight the importance of crystal phase control in Au nanomaterials by demonstrating the remarkable effect of crystal phases on their physicochemical properties (e.g., electronic and optical properties) and potential applications (e.g., catalysis). Finally, after a concise summary of recent advances in this emerging research field, some personal perspectives are provided on the challenges, opportunities, and research directions in the future.

Undercoordinated Active Sites on 4H Gold Nanostructures for CO2 Reduction.

Electroreduction of CO2 is a promising approach toward artificial carbon recycling. The rate and product selectivity of this reaction are highly sensitive to the surface structures of electrocatalysts. We report here 4H Au nanostructures as advanced electrocatalysts for highly active and selective reduction of CO2 to CO. Au nanoribbons in the pure 4H phase, Au nanorods in the hybrid 4H/fcc phase, and those in the fcc phase are comparatively studied for the electroreduction of CO2. Both the activity and selectivity for CO production were found to exhibit the trend 4H-nanoribbons > 4H/fcc-nanorods > fcc-nanorods, with the 4H-nanoribbons achieving >90% Faradaic efficiency toward CO. Electrochemical probing and cluster expansion simulations are combined to elucidate the surface structures of these nanocrystals. The combination of crystal phase and shape control gives rise to the preferential exposure of undercoordinated sites. Further density functional theory calculations confirm the high reactivity of such undercoordinated sites.

General Synthesis of Ordered Mesoporous Carbonaceous Hybrid Nanostructures with Molecularly Dispersed Polyoxometallates.

Hybrid nanomaterials with controlled dimensions, intriguing components and ordered structures have attracted significant attention in nanoscience and technology. Herein, we report a facile and green polyoxometallate (POM)-assisted hydrothermal carbonization strategy for synthesis of carbonaceous hybrid nanomaterials with molecularly dispersed POMs and ordered mesopores. By using various polyoxometallates such as ammonium phosphomolybdate, silicotungstic acid, and phosphotungstic acid, our approach can be generalized to synthesize ordered mesoporous hybrid nanostructures with diverse compositions and morphologies (nanosheet-assembled hierarchical architectures, nanospheres, and nanorods). Moreover, the ordered mesoporous nanosheet-assembled hierarchical hybrids with molecularly dispersed POMs exhibit remarkable catalytic activity toward the dehydration of tert-butanol with the high isobutene selectivity (100 %) and long-term catalytic durability (80 h).

Ethylene Selectivity in Electrocatalytic CO2 Reduction on Cu Nanomaterials: A Crystal Phase-Dependent Study.

The crystal phase of metal nanocatalysts significantly affects their catalytic performance. Cu-based nanomaterials are unique electrocatalysts for CO2 reduction reaction (CO2RR) to produce high-value hydrocarbons. However, studies to date are limited to the conventional face-centered cubic (fcc) Cu. Here, we report a crystal phase-dependent catalytic behavior of Cu, after the successful synthesis of high-purity 4H Cu and heterophase 4H/fcc Cu using the 4H and 4H/fcc Au as templates, respectively. Remarkably, the obtained unconventional crystal structures of Cu exhibit enhanced overall activity and higher ethylene (C2H4) selectivity in CO2RR compared to the fcc Cu. Density functional theory calculations suggest that the 4H phase and 4H/fcc interface of Cu favor the C2H4 formation pathway compared to the fcc Cu, leading to the crystal phase-dependent C2H4 selectivity. This study demonstrates the importance of crystal phase engineering of metal nanocatalysts for electrocatalytic reactions, offering a new strategy to prepare novel catalysts with unconventional phases for various applications.

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles.

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO2RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochemical cells.

Two-Dimensional Metal Nanomaterials: Synthesis, Properties, and Applications.

As one unique group of two-dimensional (2D) nanomaterials, 2D metal nanomaterials have drawn increasing attention owing to their intriguing physiochemical properties and broad range of promising applications. In this Review, we briefly introduce the general synthetic strategies applied to 2D metal nanomaterials, followed by describing in detail the various synthetic methods classified in two categories, i.e. bottom-up methods and top-down methods. After introducing the unique physical and chemical properties of 2D metal nanomaterials, the potential applications of 2D metal nanomaterials in catalysis, surface enhanced Raman scattering, sensing, bioimaging, solar cells, and photothermal therapy are discussed in detail. Finally, the challenges and opportunities in this promising research area are proposed.

Molecular-Level Design of Hierarchically Porous Carbons Codoped with Nitrogen and Phosphorus Capable of In Situ Self-Activation for Sustainable Energy Systems.

Hierarchically porous carbons are attracting tremendous attention in sustainable energy systems, such as lithium ion battery (LIB) and fuel cell, due to their excellent transport properties that arise from the high surface area and rich porosity. The state-of-the-art approaches for synthesizing hierarchically porous carbons normally require chemical- and/or template-assisted activation techniques, which is complicate, time consuming, and not feasible for large scale production. Here, a molecular-level design principle toward large-scale synthesis of nitrogen and phosphorus codoped hierarchically porous carbon (NPHPC) through an in situ self-activation process is proposed. The material is fabricated based on the direct pyrolysis of a well-designed polymer, melamine polyphosphate, which is capable of in situ self-activation to generate large specific surface area (1479 m2 g-1 ) and hierarchical pores in the final NPHPC. As an anode material for LIB, NPHPC delivers a high reversible capacity of 1073 mAh g-1 and an excellent cyclic stability for 300 cycles with negligible capacity decay. The peculiar structural properties and synergistic effect of N and P codopants also enable NPHPC a promising electrocatalyst for oxygen reduction reaction, a key cathodic reaction process of many energy conversion devices (for example, fuel cells and metal air batteries). Electrochemical measurements show NPHPC a comparable electrocatalytic performance to commercial Pt/C catalyst (onset potential of 0.88 V vs reversible hydrogen electrode in alkaline medium) with excellent stability (89.8% retention after 20 000 s continuous operation) and superior methanol tolerance.

Template Synthesis of Noble Metal Nanocrystals with Unusual Crystal Structures and Their Catalytic Applications.

Noble metal nanocrystals own high chemical stability, unique plasmonic and distinctive catalytic properties, making them outstanding in many applications. However, their practical applications are limited by their high cost and scarcity on the earth. One promising strategy to solve these problems is to boost their catalytic performance in order to reduce their usage amount. To realize this target, great research efforts have been devoted to the size-, composition-, shape- and/or architecture-controlled syntheses of noble metal nanocrystals during the past two decades. Impressively, recent experimental studies have revealed that the crystal structure of noble metal nanocrystals can also significantly affect their physicochemical properties, such as optical, magnetic, catalytic, mechanical, electrical and electronic properties. Therefore, besides the well-established size, composition, shape, and architecture control, the rise of crystal structure-controlled synthesis of noble metal nanocrystals will open up new opportunities to further improve their functional properties, and thus promote their potential applications in energy conversion, catalysis, biosensing, information storage, surface enhanced Raman scattering, waveguide, near-infrared photothermal therapy, controlled release, bioimaging, biomedicine, and so on. In this Account, we review the recent research progress on the crystal structure control of noble metal nanocrystals with a template synthetic approach and their crystal structure-dependent catalytic properties. We first describe the template synthetic methods, such as epitaxial growth and galvanic replacement reaction methods, in which a presynthesized noble metal nanocrystal with either new or common crystal structure is used as the template to direct the growth of unusual crystal structures of other noble metals. Significantly, the template synthetic strategy described here provides an efficient, simple and straightforward way to synthesize unusual crystal structures of noble metal nanocrystals, which might not be easily synthesized by commonly used chemical synthesis. To be specific, by using the epitaxial growth method, a series of noble metal nanocrystals with unusual crystal structures has been obtained, such as hexagonal close-packed Ag, 4H Ag, Pd, Pt, Ir, Rh, Os, and Ru, and face-centered cubic Ru nanostructures. Meanwhile, the galvanic replacement reaction method offers an efficient way to synthesize noble metal alloy nanocrystals with unusual crystal structures, such as 4H PdAg, PtAg, and PtPdAg nanostructures. We then briefly introduce the stability of noble metal nanocrystals with unusual crystal structures. After that, we demonstrate the catalytic applications of the resultant noble metal nanocrystals with unusual crystal structures toward different chemical reactions like hydrogen evolution reaction, hydrogen oxidation reaction and organic reactions. The relationship between crystal structures of noble metal nanocrystals and their catalytic performances is discussed. Finally, we summarize the whole paper, and address the current challenges and future opportunities for the template synthesis of noble metal nanocrystals with unusual crystal structures. We expect that this Account will promote the crystal structure-controlled synthesis of noble metal nanocrystals, which can provide a new way to further improve their advanced functional properties toward their practical applications.