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.

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.

Reduction of Backward Scatterings at the Low-Coherence Kunwu Laser Facility.

We report the first experimental observation on the reduction of backward scatterings by an instantaneous broadband laser with 0.6% bandwidth in conditions of interest for inertial confinement fusion at the low-coherence Kunwu laser facility. The backscatter of stimulated Brillouin scattering (SBS) was robustly reduced by half at intensities of 1-5×10^{14} W/cm^{2} with the 0.53-µm broadband laser in comparison with the monochromatic laser. As SBS dominates energy loss of laser-plasma interactions, the reduction of that demonstrates the enhancement of laser-target coupling by the use of broadband laser. The mitigation of filamentation leads to the reduction of stimulated Raman backscattering at low intensities. In addition, the three-halves harmonic emission was reduced with the broadband laser as well.

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.

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.

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.

Phase-Controlled Growth of 1T'-MoS2 Nanoribbons on 1H-MoS2 Nanosheets.

2D heterostructures are emerging as alternatives to conventional semiconductors, such as silicon, germanium, and gallium nitride, for next-generation electronics and optoelectronics. However, the direct growth of 2D heterostructures, especially for those with metastable phases still remains challenging. To obtain 2D transition metal dichalcogenides (TMDs) with designed phases, it is highly desired to develop phase-controlled synthetic strategies. Here, a facile chemical vapor deposition method is reported to prepare vertical 1H/1T' MoS2 heterophase structures. By simply changing the growth atmosphere, semimetallic 1T'-MoS2 can be in situ grown on the top of semiconducting 1H-MoS2 , forming vertical semiconductor/semimetal 1H/1T' heterophase structures with a sharp interface. The integrated device based on the 1H/1T' MoS2 heterophase structure displays a typical rectifying behavior with a current rectifying ratio of ≈103 . Moreover, the 1H/1T' MoS2 -based photodetector achieves a responsivity of 1.07 A W-1 at 532 nm with an ultralow dark current of less than 10-11 A. The aforementioned results indicate that 1H/1T' MoS2 heterophase structures can be a promising candidate for future rectifiers and photodetectors. Importantly, the approach may pave the way toward tailoring the phases of TMDs, which can help us utilize phase engineering strategies to promote the performance of electronic devices.

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.

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.

Riemannian geometry-based transfer learning for reducing training time in c-VEP BCIs.

One of the main problems that a brain-computer interface (BCI) face is that a training stage is required for acquiring training data to calibrate its classification model just before every use. Transfer learning is a promising method for addressing the problem. In this paper, we propose a Riemannian geometry-based transfer learning algorithm for code modulated visual evoked potential (c-VEP)-based BCIs, which can effectively reduce the calibration time without sacrificing the classification accuracy. The algorithm includes the main procedures of log-Euclidean data alignment (LEDA), super-trial construction, covariance matrix estimation, training accuracy-based subject selection (TSS) and minimum distance to mean classification. Among them, the LEDA reduces the difference in data distribution between subjects, whereas the TSS promotes the similarity between a target subject and the source subjects. The resulting performance of transfer learning is improved significantly. Sixteen subjects participated in a c-VEP BCI experiment and the recorded data were used in offline analysis. Leave-one subject-out (LOSO) cross-validation was used to evaluate the proposed algorithm on the data set. The results showed that the algorithm achieved much higher classification accuracy than the subject-specific (baseline) algorithm with the same number of training trials. Equivalently, the algorithm reduces the training time of the BCI at the same performance level and thus facilitates its application in real world.

Promoting nickel oxidation state transitions in single-layer NiFeB hydroxide nanosheets for efficient oxygen evolution.

Promoting the formation of high-oxidation-state transition metal species in a hydroxide catalyst may improve its catalytic activity in the oxygen evolution reaction, which remains difficult to achieve with current synthetic strategies. Herein, we present a synthesis of single-layer NiFeB hydroxide nanosheets and demonstrate the efficacy of electron-deficient boron in promoting the formation of high-oxidation-state Ni for improved oxygen evolution activity. Raman spectroscopy, X-ray absorption spectroscopy, and electrochemical analyses show that incorporation of B into a NiFe hydroxide causes a cathodic shift of the Ni2+(OH)2 → Ni3+δOOH transition potential. Density functional theory calculations suggest an elevated oxidation state for Ni and decreased energy barriers for the reaction with the NiFeB hydroxide catalyst. Consequently, a current density of 100 mA cm-2 was achieved in 1 M KOH at an overpotential of 252 mV, placing it among the best Ni-based catalysts for this reaction. This work opens new opportunities in electronic engineering of metal hydroxides (or oxides) for efficient oxygen evolution in water-splitting applications.

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.

Design of Driving Waveform for Shortening Red Particles Response Time in Three-Color Electrophoretic Displays.

Three-color electrophoretic displays (EPDs) have the advantages of multi-color display and low power consumption. However, their red particles have the disadvantage of long response time. In this paper, a driving waveform, which is based on electrophoresis theory and reference gray scale optimization, was proposed to shorten the response time of red particles in three-color EPDs. The driving waveform was composed of erasing stage, reference gray scale forming stage, red driving stage, and white or black driving stage. Firstly, the characteristics of particle motion were analyzed by electrophoresis theory and Stokes law. Secondly, the reference gray scale of the driving waveform was optimized to shorten the distance between red particles and a common electrode plate. Finally, an experimental platform was developed to test the performance of the driving waveform. Experimental results showed that the proposed driving waveform can shorten the response time of red particles by 65.57% and reduce the number of flickers by 66.67% compared with the traditional driving waveform.

A Driving Method for Reducing Oil Film Splitting in Electrowetting Displays.

Electrowetting displays (EWDs) are one of the most potential electronic papers. However, they have the problem of oil film splitting, which could lead to a low aperture ratio of EWDs. In this paper, a driving waveform was proposed to reduce oil film splitting. The driving waveform was composed of a rising stage and a driving stage. First, the rupture voltage of oil film was analyzed by testing the voltage characteristic curve of EWDs. Then, a quadratic function waveform with an initial voltage was applied at the rising stage to suppress oil film splitting. Finally, a square wave was applied at the driving stage to maintain the aperture ratio of EWDs. The experimental results show that the luminance was increased by 8.78% and the aperture ratio was increased by 4.47% compared with an exponential function driving waveform.

Iron-cobalt bimetal oxide nanorods as efficient and robust water oxidation catalysts.

Cobalt-based oxides are considered as potential water oxidation catalysts for future artificial photosynthetic systems because of their high abundance, strong stability and efficient performance. Herein, a series of cobalt-based oxides, MnCo3-nO4 (M = Mn, Fe, Co) samples, were synthesized through changing the metal sources by a low-temperature coprecipitation method. These catalysts were investigated under photochemical and electrochemical water oxidation conditions. And they all exhibited efficient activity for water oxidation under alkaline, acidic and neutral conditions under visible light irradiation. An excellent O2 yield of 90.4% for Fe-Co bimetal oxide (Fe1.1Co1.9O4) nanorods was obtained under optimal conditions (photoirradiation at λ ≥ 420 nm, [Ru(bpy)3](ClO4)2 as the photosensitizer, Na2S2O8 as the oxidant in borate buffer at pH = 9.0, bpy = 2,2-bipyridine). Among MnCo3-nO4 samples, Fe1.1Co1.9O4 nanorods were proved to be the optimal electrocatalytic water oxidation catalyst as well. Multiple experiments (SEM, FT-IR, XRD, XPS, Bulk electrolysis) were used to test the stability of Fe1.1CO1.9O4 and these results indicate that Fe1.1CO1.9O4 nanorods are highly stable. Furthermore, based on Mott-Schottky and cyclic voltammetry analysis, the best balanced flat-band potential of Fe1.1CO1.9O4 nanorods is just located at the middle position between the oxidation potential of O2/H2O and the half-wave potential of [Ru(bpy)3]3+/2+, which was probably responsible for their superior photocatalytic water oxidation performance.