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.

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.

Syntheses of η1 -Alkyl-η3 -Allyl-η5 -Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low-temperature Atomic Layer Deposition of Cobalt-Containing Thin Films.

Herein, we report the design and scalable synthesis of three new Co(III) complexes, which have an unusual hydrocarbon η1 -alkyl-η3 -allyl-η5 -cyclopentadienyl ligation structure, from the reactions of readily available cobalt(II) compound CoCl2 (PPh3 )2 and biomass material ß-pinene via C-C bond activation. These Co(III) complexes are air-stable, fairly volatile, and thermally stable, so they are excellent candidates as the metal precursors for the vapor deposition of cobalt-containing thin films. As a demonstration, we show that the Co(III) complex of [(3'-5'-η,1-σ)-methylene(2,2,4-trimethyl-4-cyclohexene-1,3-diyl)](η5 -methylcyclopentadienyl)Co (i. e. (seco-pinene)(MeCp)Co) is well suited for the atomic layer deposition (ALD) of Co3 O4 and CoS2 thin films, and the deposited Co3 O4 and CoS2 films are able to conformally cover trench structures with a fairly high aspect ratio of 10 : 1.

Atomic Design of Copper Active Sites in Pristine Metal-Organic Coordination Compounds for Electrocatalytic Carbon Dioxide Reduction.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) has emerged as a promising and sustainable approach to cut carbon emissions by converting greenhouse gas CO2 to value-added chemicals and fuels. Metal-organic coordination compounds, especially the copper (Cu)-based coordination compounds, which feature well-defined crystalline structures and designable metal active sites, have attracted much research attention in electrocatalytic CO2RR. Herein, the recent advances of electrochemical CO2RR on pristine Cu-based coordination compounds with different types of Cu active sites are reviewed. First, the general reaction pathways of electrocatalytic CO2RR on Cu-based coordination compounds are briefly introduced. Then the highly efficient conversion of CO2 on various kinds of Cu active sites (e.g., single-Cu site, dimeric-Cu site, multi-Cu site, and heterometallic site) is systematically discussed, along with the corresponding catalytic reaction mechanisms. Finally, some existing challenges and potential opportunities for this research direction are provided to guide the rational design of metal-organic coordination compounds for their practical application in electrochemical CO2RR.

Coordination Environment Engineering of Metal Centers in Coordination Polymers for Selective Carbon Dioxide Electroreduction toward Multicarbon Products.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) toward value-added chemicals/fuels has offered a sustainable strategy to achieve a carbon-neutral energy cycle. However, it remains a great challenge to controllably and precisely regulate the coordination environment of active sites in catalysts for efficient generation of targeted products, especially the multicarbon (C2+) products. Herein we report the coordination environment engineering of metal centers in coordination polymers for efficient electroreduction of CO2 to C2+ products under neutral conditions. Significantly, the Cu coordination polymer with Cu-N2S2 coordination configuration (Cu-N-S) demonstrates superior Faradaic efficiencies of 61.2% and 82.2% for ethylene and C2+ products, respectively, compared to the selective formic acid generation on an analogous polymer with the Cu-I2S2 coordination mode (Cu-I-S). In situ studies reveal the balanced formation of atop and bridge *CO intermediates on Cu-N-S, promoting C-C coupling for C2+ production. Theoretical calculations suggest that coordination environment engineering can induce electronic modulations in Cu active sites, where the d-band center of Cu is upshifted in Cu-N-S with stronger selectivity to the C2+ products. Consequently, Cu-N-S displays a stronger reaction trend toward the generation of C2+ products, while Cu-I-S favors the formation of formic acid due to the suppression of C-C couplings for C2+ pathways with large energy barriers.

Synthesis of 2H/fcc-Heterophase AuCu Nanostructures for Highly Efficient Electrochemical CO2 Reduction at Industrial Current Densities.

Structural engineering of nanomaterials offers a promising way for developing high-performance catalysts toward catalysis. However, the delicate modulation of thermodynamically unfavorable nanostructures with unconventional phases still remains a challenge. Here, the synthesis of hierarchical AuCu nanostructures is reported with hexagonal close-packed (2H-type)/face-centered cubic (fcc) heterophase, high-index facets, planar defects (e.g., stacking faults, twin boundaries, and grain boundaries), and tunable Cu content. The obtained 2H/fcc Au99 Cu1 hierarchical nanosheets exhibit excellent performance for the electrocatalytic CO2 reduction to produce CO, outperforming the 2H/fcc Au91 Cu9 and fcc Au99 Cu1 . The experimental results, especially those obtained by in-situ differential electrochemical mass spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy, suggest that the enhanced catalytic performance of 2H/fcc Au99 Cu1 arises from the unconventional 2H/fcc heterophase, high-index facets, planar defects, and appropriate alloying of Cu. Impressively, the 2H/fcc Au99 Cu1 shows CO Faradaic efficiencies of 96.6% and 92.6% at industrial current densities of 300 and 500 mA cm-2 , respectively, as well as good durability, placing it among the best CO2 reduction electrocatalysts for CO production. The atomically structural regulation based on phase engineering of nanomaterials (PEN) provides an avenue for the rational design and preparation of high-performance electrocatalysts for various catalytic applications.

The Restructuring-Induced CoO x Catalyst for Electrochemical Water Splitting.

Restructuring is an important yet less understood phenomenon in the catalysis community. Recent studies have shown that a group of transition metal sulfide catalysts can completely or partially restructure during electrochemical reactions which then exhibit high activity even better than the best commercial standards. However, such restructuring processes and the final structures of the new catalysts are elusive, mainly due to the difficulty from the reaction-induced changes that cannot be captured by ex situ characterizations. To establish the true structure-property relationship in these in situ generated catalysts, we use multimodel operando characterizations including Raman spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity to investigate the restructuring of a representative catalyst, Co9S8, that shows better activity compared to the commercial standard RuO2 during the oxygen evolution reaction (OER), a key half reaction in water-splitting for hydrogen generation. We find that Co9S8 ultimately converts to oxide cluster (CoO x ) containing six oxygen coordinated Co octahedra as the basic unit which is the true catalytic center to promote high OER activity. The density functional theory calculations verify the in situ generated CoO x consisting of edge-sharing CoO6 octahedral clusters as the actual active sites. Our results also provide insights to design other transition-metal-based materials as efficient electrocatalysts that experience a similar restructuring in OER.