Phase Engineering of Nanomaterials: Transition Metal Dichalcogenides.

Crystal phase, a critical structural characteristic beyond the morphology, size, dimension, facet, etc., determines the physicochemical properties of nanomaterials. As a group of layered nanomaterials with polymorphs, transition metal dichalcogenides (TMDs) have attracted intensive research attention due to their phase-dependent properties. Therefore, great efforts have been devoted to the phase engineering of TMDs to synthesize TMDs with controlled phases, especially unconventional/metastable phases, for various applications in electronics, optoelectronics, catalysis, biomedicine, energy storage and conversion, and ferroelectrics. Considering the significant progress in the synthesis and applications of TMDs, we believe that a comprehensive review on the phase engineering of TMDs is critical to promote their fundamental studies and practical applications. This Review aims to provide a comprehensive introduction and discussion on the crystal structures, synthetic strategies, and phase-dependent properties and applications of TMDs. Finally, our perspectives on the challenges and opportunities in phase engineering of TMDs will also be discussed.

Recent Progress on Phase Engineering of Nanomaterials.

As a key structural parameter, phase depicts the arrangement of atoms in materials. Normally, a nanomaterial exists in its thermodynamically stable crystal phase. With the development of nanotechnology, nanomaterials with unconventional crystal phases, which rarely exist in their bulk counterparts, or amorphous phase have been prepared using carefully controlled reaction conditions. Together these methods are beginning to enable phase engineering of nanomaterials (PEN), i.e., the synthesis of nanomaterials with unconventional phases and the transformation between different phases, to obtain desired properties and functions. This Review summarizes the research progress in the field of PEN. First, we present representative strategies for the direct synthesis of unconventional phases and modulation of phase transformation in diverse kinds of nanomaterials. We cover the synthesis of nanomaterials ranging from metal nanostructures such as Au, Ag, Cu, Pd, and Ru, and their alloys; metal oxides, borides, and carbides; to transition metal dichalcogenides (TMDs) and 2D layered materials. We review synthesis and growth methods ranging from wet-chemical reduction and seed-mediated epitaxial growth to chemical vapor deposition (CVD), high pressure phase transformation, and electron and ion-beam irradiation. After that, we summarize the significant influence of phase on the various properties of unconventional-phase nanomaterials. We also discuss the potential applications of the developed unconventional-phase nanomaterials in different areas including catalysis, electrochemical energy storage (batteries and supercapacitors), solar cells, optoelectronics, and sensing. Finally, we discuss existing challenges and future research directions in PEN.

Ligand-Assisted Phase Engineering of Nanomaterials.

ConspectusThe synthesis of monodisperse colloidal nanomaterials with well-defined structures is important for both fundamental research and practical application. To achieve it, wet-chemical methods with the usage of various ligands have been extensively explored to finely control the structure of nanomaterials. During the synthesis, ligands cap the surface and thus modulate the size, shape, and stability of nanomaterials in solvents. Besides these widely investigated roles of ligands, it has been recently discovered that ligands can affect the phase of nanomaterials, i.e., their atomic arrangement, providing an effective strategy to realize the phase engineering of nanomaterials (PEN) by selecting appropriate ligands. Nanomaterials normally exist in the phases that are thermodynamically stable in their bulk states. Previous studies have shown that under high temperature or high pressure, nanomaterials can exist in unconventional phases which are unattainable in the bulks. Importantly, nanomaterials with unconventional phases exhibit unique properties and functions different from conventional-phase ones. Consequently, it is feasible to utilize the PEN to tune the physicochemical properties and application performance of nanomaterials. During wet-chemical synthesis, ligands binding to the surface of nanomaterials can modify their surface energy, which could significantly affect the Gibbs free energy of nanomaterials and thus determine the stability of different phases, making it possible to obtain nanomaterials with unconventional phases at mild reaction conditions. For instance, a series of Au nanomaterials with unconventional hexagonal phases have been prepared with the assistance of oleylamine. Therefore, the rational design and selection of different ligands and deep understanding of their effect on the phase of nanomaterials would significantly accelerate the development of PEN and the discovery of novel functional nanomaterials for diverse applications.In this Account, we briefly summarize the recent progress in ligand-assisted PEN, elaborating the important roles of different ligands in the direct synthesis of nanomaterials with unconventional crystal phases and amorphous phase as well as the phase transformation of nanomaterials. We first introduce the background of this research topic, highlighting the concept of PEN and why ligands can modulate the phase of nanomaterials. Then we discuss the usage of four kinds of ligands, i.e., amines, fatty acids, sulfur-containing ligands, and phosphorus-containing ligands, in phase engineering of different nanomaterials, especially metal, metal chalcogenide, and metal oxide nanomaterials. Finally, we provide our personal views of the challenges and future promising research directions in this exciting field.

Metal-Organic Framework-Based Hetero-Phase Nanostructure Photocatalysts with Molecular-Scale Tunable Energy Levels.

As an effective method to modulate the physicochemical properties of materials, crystal phase engineering, especially hetero-phase, plays an important role in developing high-performance photocatalysts. However, it is still a huge challenge but significant to construct porous hetero-phase nanostructures with adjustable band structures. As a kind of unique porous crystalline materials, metal-organic frameworks (MOFs) might be the appropriate candidate, but the MOF-based hetero-phase is rarely reported. Herein, we developed a secondary building unit (SBU) regulating strategy to prepare two crystal phases of Ti-MOFs constructed by titanium and 1,4-dicarboxybenzene, i.e., COK and MIL-125. Besides, COK/MIL-125 hetero-phase was further constructed. In the photocatalytic hydrogen evolution reaction, COK/MIL-125 possessed the highest H2 yield compared to COK and MIL-125, ascribing to the Z-Scheme homojunction at hetero-phase interface. Furthermore, by decorating with amino groups (i.e., NH2-COK/NH2-MIL-125), the light absorbing capacity was broadened to visible-light region, and the visible-light-driven H2 yield was greatly improved. Briefly, the MOF-based hetero-phase possesses periodic channel structures and molecularly adjustable band structures, which is scarce in traditional organic or inorganic materials. As a proof of concept, our work not only highlights the development of MOF-based hetero-phase nanostructures, but also paves a novel avenue for designing high-performance photocatalysts.

Breaking Highly Ordered PtPbBi Intermetallic with Disordered Amorphous Phase for Boosting Electrocatalytic Hydrogen Evolution and Alcohol Oxidation.

Constructing amorphous/intermetallic (A/IMC) heterophase structures by breaking the highly ordered IMC phase with disordered amorphous phase is an effective way to improve the electrocatalytic performance of noble metal-based IMC electrocatalysts because of the optimized electronic structure and abundant heterophase boundaries as active sites. In this study, we report the synthesis of ultrathin A/IMC PtPbBi nanosheets (NSs) for boosting hydrogen evolution reaction (HER) and alcohol oxidation reactions. The resulting A/IMC PtPbBi NSs exhibit a remarkably low overpotential of only 25 mV at 10 mA cm-2 for the HER in an acidic electrolyte, together with outstanding stability for 100 h. In addition, the PtPbBi NSs show high mass activities for methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR), which are 13.2 and 14.5 times higher than those of commercial Pt/C, respectively. Density functional theory calculations demonstrate that the synergistic effect of amorphous/intermetallic components and multimetallic composition facilitate the electron transfer from the catalyst to key intermediates, thus improving the catalytic activity of MOR. This work establishes a novel pathway for the synthesis of heterophase two-dimensional nanomaterials with high electrocatalytic performance across a wide range of electrochemical applications.

Two-Dimensional Nanomaterial-Templated Composites.

ConspectusTwo-dimensional (2D) nanomaterials have attracted increasing research interest since mechanically exfoliated graphene was obtained in 2004. The ultrathin thickness and relatively large lateral size of 2D nanomaterials render them various intriguing properties such as compelling electronic properties, ultrahigh specific surface area, excellent mechanical properties, and so on. A wide range of 2D nanomaterials, including graphene and its derivatives, transition metal dichalcogenides (TMDs), metals, etc., have been prepared with different compositions, structures and (crystal) phases. Simultaneously, extensive research efforts have been devoted to exploring the potential applications of these 2D nanomaterials with enhanced performances. Hybridization of two or more nanomaterials to prepare novel composites could efficiently integrate the advantages of the individual components and thus optimize their performances for specific applications. Among various hybridization approaches, the templated synthesis method, i.e., using a presynthesized nanomaterial as a template to direct the growth of a secondary nanostructure, provides an efficient way to prepare composites with high controllability. The ultrathin thickness, large specific surface area, and versatile physiochemical properties of 2D nanomaterials make them ideal templates for constructing composites with desired structures, properties, and functions. Until now, various 2D nanomaterials have been used as templates to grow different kinds of nanomaterials, including metals, metal oxides, metal chalcogenides, metal-organic frameworks (MOFs), etc., to form 2D nanomaterial-templated composites that show potentials in various applications. In this Account, we first briefly introduce the general research background of 2D nanomaterials and the motivation for the preparation of 2D nanomaterial-templated composites. Then we summarize our progress and some other representative work on 2D nanomaterial-templated composites, with a particular emphasis on graphene-templated composites, 2D TMD-templated composites, and 2D metal-templated composites. Specifically, representative examples of the graphene-templated zero-dimensional (0D), one-dimensional (1D), and 2D composites and the emerging graphene-templated van der Waals heterostructures are described. Subsequently, typical 2D TMD-templated composites such as metal oxides, metals, and metal chalcogenides are also presented. In addition, we introduce 2D metal-templated composites and highlight that the crystal phase of the 2D metal template can play an important role in the controlled synthesis of heterostructures. Other composites constructed using 2D metal oxides, metal hydroxides, metal sulfides, and MOFs as templates are also introduced. After that, we demonstrate the potential applications of 2D nanomaterial-templated composites, including electrocatalysis, electronic devices, batteries, and so on. Finally, after a brief summary, our personal insights on the challenges and future research directions in this emerging field are also proposed.

Isolated Electron-Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia.

The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH3 with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body-centered cubic RuGa intermetallic compounds (i.e., bcc RuGa IMCs) via a substrate-anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH4 + yield rate of 320.6 µmol h-1 mg-1 Ru with the corresponding Faradaic efficiency of 72.3 % at very low potential of -0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron-rich Ru atoms in bcc RuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potential-determining step in NORR could be greatly reduced.

Isoreticular Series of Two-Dimensional Covalent Organic Frameworks with the kgd Topology and Controllable Micropores.

Two-dimensional (2D) covalent organic frameworks (COFs) possess designable pore architectures but limited framework topologies. Until now, 2D COFs adopting the kgd topology with ordered and rhombic pore geometry have rarely been reported. Here, an isoreticular series of 2D COFs with the kgd topology and controllable pore size is synthesized by employing a C6-symmetric aldehyde, i.e., hexa(4-formylphenyl)benzene (HFPB), and C3-symmetric amines i.e., tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)trazine (TAPT), and 1,3,5-tris[4-amino(1,1-biphenyl-4-yl)]benzene (TABPB), as building units, referred to as HFPB-TAPA, HFPB-TAPT, and HFPB-TABPB, respectively. The micropore dimension down to 6.7 Å is achieved in HFPB-TAPA, which is among the smallest pore size of reported 2D COFs. Impressively, both the in-plane network and stacking sequence of the 2D COFs can be clearly observed by low-dose electron microscopy. Integrating the unique kgd topology with small rhombic micropores, these 2D COFs are endowed with both short molecular diffusion length and favorable host-guest interaction, exhibiting potential for drug delivery with high loading and good release control of ibuprofen.

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.

Hydrogen-Intercalation-Induced Lattice Expansion of Pd@Pt Core-Shell Nanoparticles for Highly Efficient Electrocatalytic Alcohol Oxidation.

Lattice engineering on specific facets of metal catalysts is critically important not only for the enhancement of their catalytic performance but also for deeply understanding the effect of facet-based lattice engineering on catalytic reactions. Here, we develop a facile two-step method for the lattice expansion on specific facets, i.e., Pt(100) and Pt(111), of Pt catalysts. We first prepare the Pd@Pt core-shell nanoparticles exposed with the Pt(100) and Pt(111) facets, respectively, via the Pd-seeded epitaxial growth, and then convert the Pd core to PdH0.43 by hydrogen intercalation. The lattice expansion of the Pd core induces the lattice enlargement of the Pt shell, which can significantly promote the alcohol oxidation reaction (AOR) on both Pt(100) and Pt(111) facets. Impressively, Pt mass specific activities of 32.51 A mgPt-1 for methanol oxidation and 14.86 A mgPt-1 for ethanol oxidation, which are 41.15 and 25.19 times those of the commercial Pt/C catalyst, respectively, have been achieved on the Pt(111) facet. Density functional theory (DFT) calculations indicate that the remarkably improved catalytic performance on both the Pt(100) and the Pt(111) facets through lattice expansion arises from the enhanced OH adsorption. This work not only paves the way for lattice engineering on specific facets of nanomaterials to enhance their electrocatalytic activity but also offers a promising strategy toward the rational design and preparation of highly efficient catalysts.

Seeded Synthesis of Unconventional 2H-Phase Pd Alloy Nanomaterials for Highly Efficient Oxygen Reduction.

Crystal phase engineering of noble-metal-based alloy nanomaterials paves a new way to the rational synthesis of high-performance catalysts for various applications. However, the controlled preparation of noble-metal-based alloy nanomaterials with unconventional crystal phases still remains a great challenge due to their thermodynamically unstable nature. Herein, we develop a robust and general seeded method to synthesize PdCu alloy nanomaterials with unconventional hexagonal close-packed (hcp, 2H type) phase and also tunable Cu contents. Moreover, galvanic replacement of Cu by Pt can be further conducted to prepare unconventional trimetallic 2H-PdCuPt nanomaterials. Impressively, 2H-Pd67Cu33 nanoparticles possess a high mass activity of 0.87 A mg-1Pd at 0.9 V (vs reversible hydrogen electrode (RHE)) in electrochemical oxygen reduction reaction (ORR) under alkaline condition, which is 2.5 times that of the conventional face-centered cubic (fcc) Pd69Cu31 counterpart, revealing the important role of crystal phase on determining the ORR performance. After the incorporation of Pt, the obtained 2H-Pd71Cu22Pt7 catalyst shows a significantly enhanced mass activity of 1.92 A mg-1Pd+Pt at 0.9 V (vs RHE), which is 19.2 and 8.7 times those of commercial Pt/C and Pd/C, placing it among the best reported Pd-based ORR electrocatalysts under alkaline conditions.

Bromide Ions Triggered Synthesis of Noble Metal-Based Intermetallic Nanocrystals.

Ordered intermetallic nanomaterials with a well-defined crystal structure and fixed stoichiometry facilitate the predictable control of their electronic structure and catalytic performance. To obtain the thermodynamically stable intermetallic structures, the conventional approaches with high-temperature annealing are still far from satisfactory, because of annealing-induced aggregation and sintering of nanomaterials. Herein, a general wet-chemical method is developed to synthesize a series of noble metal-based intermetallic nanocrystals, including hexagonal close-packed (hcp) PtBi nanoplates, face-centered cubic (fcc) Pd3 Pb nanocubes, and hcp Pd2.5 Bi1.5 nanoparticles. During the synthetic process, Br- ions play two important roles for the formation of ordered intermetallic structures: i) Br- ions can coordinate with the metal ions to decrease their reduction potentials thus slowing down the reduction kinetics. ii) Br- ions can combine with molecular oxygen to generate an oxidative etching effect, hence reconstructing the atom arrangement, which is beneficial for the formation of the intermetallic structure. As a proof-of-concept application, Pd3 Pb nanocubes are used as electrocatalysts for ethanol and methanol oxidation reactions, which exhibit significantly improved electrochemical performance compared with the commercial Pd black catalyst.

Elemental Segregation in Multimetallic Core-Shell Nanoplates.

In this work, we report an element segregation phenomenon in two-dimensional (2D) core-shell nanoplates, subsequently resulting in the formation of yolk-cage nanostructures after selective electrochemical etching. By using PtCu nanoplates as templates, PtCu@Pd core-shell nanoplates are formed. Interestingly, during the growth of Ru on the PtCu@Pd core-shell nanoplates, due to the selective element diffusion, PtCuPd@PdCu@Ru nanoplates are obtained. After selectively etching of PdCu in PtCuPd@PdCu@Ru using electrochemical method, the PtCuPd@Ru yolk-cage nanostructures are obtained. As a proof-of-concept application, this unique nanostructure shows superior electrocatalytic activity and stability toward the methanol oxidation reaction as compared to the PtCu nanoplates and commercial Pt/C catalyst.

Synthesis of Hierarchical 4H/fcc Ru Nanotubes for Highly Efficient Hydrogen Evolution in Alkaline Media.

Hierarchical metal nanostructures containing 1D nanobuilding blocks have stimulated great interest due to their abundant active sites for catalysis. Herein, hierarchical 4H/face-centered cubic (fcc) Ru nanotubes (NTs) are synthesized by a hard template-mediated method, in which 4H/fcc Au nanowires (NWs) serve as sacrificial templates which are then etched by copper ions (Cu2+ ) in dimethylformamide. The obtained hierarchical 4H/fcc Ru NTs contain ultrathin Ru shells (5-9 atomic layers) and tiny Ru nanorods with length of 4.2 ± 1.1 nm and diameter of 2.2 ± 0.5 nm vertically decorated on the surface of Ru shells. As an electrocatalyst for the hydrogen evolution reaction in alkaline media, the hierarchical 4H/fcc Ru NTs exhibit excellent electrocatalytic performance, which is better than 4H/fcc Au-Ru NWs, commercial Pt/C, Ru/C, and most of the reported electrocatalysts.

Three-Dimensional Architectures Constructed from Transition-Metal Dichalcogenide Nanomaterials for Electrochemical Energy Storage and Conversion.

Transition-metal dichalcogenides (TMDs) have attracted considerable attention in recent years because of their unique properties and promising applications in electrochemical energy storage and conversion. However, the limited number of active sites as well as blocked ion and mass transport severely impair their electrochemical performance. The construction of three-dimensional (3D) architectures from TMD nanomaterials has been proven to be an effective strategy to solve the aforementioned problems as a result of their large specific surface areas and short ion and mass transport distances. This Review summarizes the commonly used routes to build 3D TMD architectures and highlights their applications in electrochemical energy storage and conversion, including batteries, supercapacitors, and electrocatalytic hydrogen evolution. The challenges and outlook in this research area are also discussed.

A Novel Lithiated Silicon-Sulfur Battery Exploiting an Optimized Solid-Like Electrolyte to Enhance Safety and Cycle Life.

Anovel lithiated Si-S battery exploiting an optimized solid-like electrolyte is presented. This electrolyte is fabricated by integrating ether-based liquid electrolyte with SiO2 hollow nanosphere layer to suppress the shuttle effect and fluoroethylene carbonate additive to optimize the anodic solid electrolyte interface. The prepared lithiated Si-S batteries exhibit enhanced cycle life, low flammability, and strong recovery ability against short-circuit.

3D Noble-Metal Nanostructures Approaching Atomic Efficiency and Atomic Density Limits.

Noble metals have been widely used in catalysis, however, the scarcity and high cost of noble metal motivate researchers to balance the atomic efficiency and atomic density, which is formidably challenging. This article proposes a robust strategy for fabricating 3D amorphous noble metal-based oxides with simultaneous enhancement on atomic efficiency and density with the assistance of atomic channels, where the atomic utilization increases from 18.2% to 59.4%. The unique properties of amorphous bimetallic oxides and formation of atomic channels have been evidenced by detailed experimental characterizations and theoretical simulations. Moreover, the universality of the current strategy is validated by other binary oxides. When Cu2IrOx with atomic channels (Cu2IrOx-AE) is used as catalyst for oxygen evolution reaction (OER), the mass activity and turnover frequency value of Cu2IrOx-AE are 1-2 orders of magnitude higher than CuO/IrO2 and Cu2IrOx without atomic channels, largely outperforming the reported OER catalysts. Theoretical calculations reveal that the formation of atomic channels leads to various Ir sites, on which the proton of adsorbed *OH can transfer to adjacent O atoms of [IrO6]. This work may attract immediate interest of researchers in material science, chemistry, catalysis, and beyond.

Crystal-Phase-Selective Etching of Heterophase Au Nanostructures.

Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures. However, the synthesis of hollow multimetallic nanostructures based on crystal-phase-selective etching has been rarely studied. Here, a crystal-phase-selective etching method is reported to selectively etch the unconventional 4H and 2H phases in the heterophase Au nanostructures. Due to the coating of Pt-based alloy and the crystal-phase-selective etching of 4H-Au in 4H/face-centered cubic (fcc) Au nanowires, the well-defined ladder-like Au@PtAg nanoframes are prepared. In addition, the 2H-Au in the fcc-2H-fcc Au nanorods and 2H/fcc Au nanosheets can also be selectively etched using the same method. As a proof-of-concept application, the ladder-like Au@PtAg nanoframes are used for the electrocatalytic hydrogen evolution reaction (HER) in acidic media, showing excellent performance that is comparable to the commercial Pt/C catalyst.

Structural Transformation of Unconventional-Phase Materials.

The structural transformation of materials, which involves the evolution of different structural features, including phase, composition, morphology, etc., under external conditions, represents an important fundamental phenomenon and has drawn substantial research interest. Recently, materials with unconventional phases that are different from their thermodynamically stable ones have been demonstrated to possess distinct properties and compelling functions and can further serve as starting materials for structural transformation studies. The identification and mechanism study of the structural transformation process of unconventional-phase starting materials can not only provide deep insights into their thermodynamic stability in potential applications but also offer effective approaches for the synthesis of other unconventional structures. Here, we briefly summarize the recent research progress on the structural transformation of some typical starting materials with various unconventional phases, including the metastable crystalline phase, amorphous phase, and heterophase, induced by different approaches. The importance of unconventional-phase starting materials in the structural modulation of resultant intermediates and products will be highlighted. The employment of diverse in situ/operando characterization techniques and theoretical simulations in studying the mechanism of the structural transformation process will also be introduced. Finally, we discuss the existing challenges in this emerging research field and provide some future research directions.

Seeded Synthesis of Hollow PdSn Intermetallic Nanomaterials for Highly Efficient Electrocatalytic Glycerol Oxidation.

Intermetallic nanomaterials have shown promising potential as high-performance catalysts in various catalytic reactions due to their unconventional crystal phases with ordered atomic arrangements. However, controlled synthesis of intermetallic nanomaterials with tunable crystal phases and unique hollow morphologies remains a challenge. Here, a seeded method is developed to synthesize hollow PdSn intermetallic nanoparticles (NPs) with two different intermetallic phases, that is, orthorhombic Pd2 Sn and monoclinic Pd3 Sn2 . Benefiting from the rational regulation of the crystal phase and morphology, the obtained hollow orthorhombic Pd2 Sn NPs deliver excellent electrocatalytic performance toward glycerol oxidation reaction (GOR), outperforming solid orthorhombic Pd2 Sn NPs, hollow monoclinic Pd3 Sn2 NPs, and commercial Pd/C, which places it among the best reported Pd-based GOR electrocatalysts. The reaction mechanism of GOR using the hollow orthorhombic Pd2 Sn as the catalyst is investigated by operando infrared reflection absorption spectroscopy, which reveals that the hollow orthorhombic Pd2 Sn catalyst cleaves the CC bond more easily compared to the commercial Pd/C. This work can pave an appealing route to the controlled synthesis of diverse novel intermetallic nanomaterials with hollow morphology for various promising applications.