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Defective two-dimensional (2D) materials show huge potential for energy-related fields. This review overviews the formation/evolution mechanisms and engineering strategies of defects in 2D materials, which enable enhanced electrode reaction kinetics.

Electrochemical carbon dioxide reduction offers a promising strategy to achieve carbon neutrality. Here we review the latest important advances of metal-functionalized 2D nanomaterials for electrocatalytic carbon dioxide reduction reaction (CO2RR).

The mechanical stability of metallic nanomaterials has been intensively studied due to their unique structures and promising applications. Although extensive investigations have been carried out on the deformation behaviors of metallic nanomaterials, the atomic-scale deformation mechanism of metallic nanomaterials with unconventional hexagonal structures remains unclear because of the lack of direct experimental observation. Here, we conduct an atomic-resolution in situ tensile-straining transmission electron microscopy investigation on the deformation mechanism of gold nanoribbons with the 4H (hexagonal) phase. Our results reveal that plastic deformation in the 4H gold nanoribbons comprises three stages, in which both full and partial dislocations are involved. At the early deformation stage, plastic deformation is governed by full dislocation activities. Partial dislocations are subsequently activated in regions that have undergone full dislocation gliding, leading to phase transformation from the 4H phase to the face-centered cubic (FCC) phase. At the last stage of the deformation process, the volume fraction of the FCC phase increases, and full dislocation activities in the FCC regions also play an important role.

Electrochemical carbon dioxide (CO2) reduction is emerging as a promising technique to decrease atmospheric CO2 concentration and relieve energy pressure. Besides the single-carbon (C1) species, multi-carbon (C2+) products are more preferred because of their elevated energy density and/or larger economic value. Single atom catalysts (SACs) have been widely used in the field of catalysis due to their tunable active center and unique electronic structure. So far, extensive research progresses have been achieved in utilizing SACs to promote the CO2 reduction toward C1 products, but little attention is paid to the formation of high-value C2+ products. In this review, we present the recent advances of electrochemical reduction of CO2 to C2+ products with SACs. Firstly, the reaction mechanism of converting CO2 to C2+ products is briefly introduced. Then the general design principles of SACs toward C2+ products are systematically discussed. After that, we highlight the representative studies on the C2+ generation and the corresponding mechanism with SACs, including the copper and non-copper based SACs. Finally, we summarize the latest progresses and provide personal perspectives for the future design and target preparation of advanced SACs for the high-performance CO2 electrolysis to specific C2+ products.

Given the high energy density and eco-friendly characteristics, lithium-carbon dioxide (Li-CO 2 ) batteries have been considered to be a next-generation energy technology to promote carbon neutral and space exploration. However, Li-CO 2 batteries suffer from sluggish reaction kinetics, causing large overpotential and poor energy efficiency. Here, we observe enhanced reaction kinetics in aprotic Li-CO 2 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 CO 2 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-CO 2 pouch cells with 4H/fcc Ir suggests the feasibility of using unconventional phase nanomaterials in practical scenarios.

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, Co

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).

Electrochemical CO2 reduction reaction (CO2RR) is an attractive pathway for closing the anthropogenic carbon cycle and storing intermittent renewable energy by converting CO2 to valuable chemicals and fuels. The production of highly reduced carbon compounds beyond CO and formate, such as hydrocarbon and oxygenate products with higher energy density, is particularly desirable for practical applications. However, the productivity towards highly reduced chemicals is typically limited by high overpotential and poor selectivity due to the multiple electron-proton transfer steps. Tandem catalysis, which is extensively utilized by nature for producing biological macromolecules with multiple enzymes via coupled reaction steps, represents a promising strategy for enhancing the CO2RR performance. Improving the efficiency of CO2RR via tandem catalysis has recently emerged as an exciting research frontier and achieved significant advances. Here we describe the general principles and also considerations for designing tandem catalysis for CO2RR. Recent advances in constructing tandem catalysts, mainly including bimetallic alloy nanostructures, bimetallic heterostructures, bimetallic core-shell nanostructures, bimetallic mixture catalysts, metal-metal organic framework (MOF) and metal-metallic complexes, metal-nonmetal hybrid nanomaterials and copper-free hybrid nanomaterials for boosting the CO2RR performance are systematically summarized. The study of tandem catalysis for CO2RR is still at the early stage, and future research challenges and opportunities are also discussed.

Summary Electrocatalytic CO2 reduction reaction (CO2RR) has attained great attention as it can transform the greenhouse gas CO2 to value-added chemicals, such as carbon monoxide, formic acid, ethylene, ethanol, and n-propanol. However, the electrocatalytic performance of materials, especially the metal materials, toward the CO2RR is still limited due to the complex reaction processes and broad product distribution. Very recently, surface modification of metal materials has emerged as an effective way to boost their electrocatalytic CO2RR performance. Herein, recent advances in the surface modification of metal materials, which includes surface molecular functionalization, surface elemental doping, and surface plasma treatment, for CO2RR are presented. The surface modification-induced variations of surface states and electrocatalytic performances of metal materials, together with the underlying mechanisms, are highlighted. It is believed that the development of surface modification could promote the rational design and preparation of advanced CO2RR electrocatalysts toward practical applications.

Over the past few decades, gold-based materials have drawn extensive attention due to their intriguing physical/chemical properties and excellent performance in a broad range of applications. In particular, the remarkable technical progress in synthesis and characterization is promoting the rapid development of gold-based nanoalloys, which are of great significance in catalysis. In this review, we provide a brief overview of the recently reported gold-based nanoalloys, focusing on their general synthetic methods and potential catalytic applications. In particular, the general relationships between material structures/compositions and catalytic performances are discussed in representative chemical reactions, such as the carbon dioxide reduction reaction (CO2RR), oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), oxygen evolution reaction (OER), small organic molecule oxidation reaction, carbon monoxide oxidation reaction, and typical heterogeneous catalytic reactions in chemical engineering. Furthermore, critical challenges and potential opportunities facing gold-based nanoalloys are proposed to provide possible inspiration for future material design towards high performance applications.

Because of the distinct electronic structures and stable chemical properties, rhodium materials are one of the most important noble metal catalysts for various kinds of industrial chemical processe...

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 OH

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 CO

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.

ConspectusGold (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.

The crystal phase-based heterostructures of noble metal nanomaterials are of great research interest for various applications, such as plasmonics and catalysis. However, the synthesis of unusual crystal phases of noble metals still remains a great challenge, making the construction of heterophase noble metal nanostructures difficult. Here, we report a one-pot wet-chemical synthesis of well-defined heterophase fcc-2H-fcc gold nanorods (fcc: face-centred cubic; 2H: hexagonal close-packed with stacking sequence of “AB”) at mild conditions. Single particle-level experiments and theoretical investigations reveal that the heterophase gold nanorods demonstrate a distinct optical property compared to that of the conventional fcc gold nanorods. Moreover, the heterophase gold nanorods possess superior electrocatalytic activity for the carbon dioxide reduction reaction over their fcc counterparts under ambient conditions. First-principles calculations suggest that the boosted catalytic performance stems from the energetically favourable adsorption of reaction intermediates, endowed by the unique heterophase characteristic of gold nanorods., The crystal phase-based heterostructures of noble metal nanomaterials are of interest for various applications. Here, the authors report the wet-chemical synthesis of gold nanorods with a well-defined fcc-2H-fcc heterophase, which possess unique optical and catalytic properties.

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.

Crystal phase can greatly affect the physicochemical properties and applications of nanomaterials. However, it still remains a great challenge to synthesize nanostructures with the same composition and morphology but different phases in order to explore the phase-dependent properties and applications. Herein, we report the crystal phase-controlled synthesis of PtCu alloy shells on 4H Au nanoribbons (NRBs), referred to as 4H-Au NRBs, to form the 4H-Au@PtCu core-shell NRBs. By tuning the thickness of PtCu, 4H-PtCu and face-centered cubic (fcc) phase PtCu (fcc-PtCu) alloy shells are successfully grown on the 4H-Au NRB cores. This thickness-dependent phase-controlled growth strategy can also be used to grow PtCo alloys with 4H or fcc phase on 4H-Au NRBs. Significantly, when used as electrocatalysts for the ethanol oxidation reaction (EOR) in alkaline media, the 4H-Au@4H-PtCu NRBs show much better EOR performance than the 4H-Au@fcc-PtCu NRBs, and both of them possess superior performance compared to the commercial Pt black. Our study provides a strategy on phase-controlled synthesis of nanomaterials used for crystal phase-dependent applications.

Summary Recently, gold nanoribbons (Au NRBs) with hexagonal (4H) phase have emerged as a new kind of ultrathin Au nanostructure with unusual metastable crystal phase, which could possess unique physiochemical properties and various promising applications. However, its geometric structure and phase stability under realistic service conditions, like Joule heating or external thermal loading, have not been well studied. Here, we systematically investigated the thermal responses in geometries and crystalline phases of ultrathin 4H Au NRBs under controlled in situ heating. It is found that upon moderate electron beam irradiation heating below 400 K, “Rayleigh instability” can be gradually observed, showing an obvious geometric effect, but the 4H phase remains stable. However, phase transition from 4H to face-centered cubic phases occurs when heating temperature approaches 800 K by using a dedicated microelectromechanical system heating chip, which agrees well with the result obtained by molecular dynamics simulations.

The crystal phase of nanomaterials is one of the key parameters determining their physicochemical properties and performance in various applications. However, it still remains a great challenge to synthesize nanomaterials with different crystal phases while maintaining the same composition, size, and morphology. Here, a facile, one-pot, wet-chemical method is reported to synthesize Pd3 Sn nanorods with comparable size and morphology but different crystal phases, that is, an ordered intermetallic and a disordered alloy with L12 and face-centered cubic (fcc) phases, respectively. The crystal phase of the as-synthesized Pd3 Sn nanorods is easily tuned by altering the types of tin precursors and solvents. Moreover, the approach can also be used to synthesize ternary PdCuSn nanorods with the L12 crystal phase. When used as electrocatalysts, the L12 Pd3 Sn nanorods exhibit superior electrocatalytic performance toward the ethanol oxidation reaction (EOR) compared to their fcc counterpart. Impressively, compared to the L12 Pd3 Sn nanorods, the ternary L12 PdCuSn nanorods exhibit more enhanced electrocatalytic performance toward the EOR, yielding a high mass current density up to 6.22 A mgPd -1 , which is superior to the commercial Pd/C catalyst and among the best reported Pd-based EOR electrocatalysts. The authors would like to acknowledge the Facility for Analysis, Characterization, Testing, and Simulation, Nanyang Technological University, Singapore, for their electron microscopy (and/or X-ray) facilities. Z.F. and H.Z. thank the financial support from ITC via Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), and the Start-Up Grants (Project Nos. 9610480, 9380100, and 7200651) and grants (Project Nos. 9610478, 9680314, 7020013 and 1886921) in City University of Hong Kong. The authors thank the computational resources from the Big Data Center of Southeast University and National Supercomputing Center of Tianjin.

The crystal phase of nanomaterials is one of the key parameters determining their physicochemical properties and performance in various applications. However, it still remains a great challenge to synthesize nanomaterials with different crystal phases while maintaining the same composition, size, and morphology. Here, a facile, one-pot, wet-chemical method is reported to synthesize Pd

Rh nanostructures composed of nanosheets embedded with nanodomains adopt vacated Barlow packing with ordered vacancies., Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H2O in the HER.

The traditional energy consumption mode has caused many environmental problems and the rise of the energy crisis as well. On the one hand, the reserves of unrenewable fossil energies, such as coal, oil, and natural gas, are quite limited. On the other hand, the excessive consumption of fossil energies has emitted too many environmental unfriendly products, such as the greenhouse gas CO2. In the past decade, the average CO2 emissions in the world was as high as about 32.53 billion tons per year. In 2019, the CO2 concentration in the atmosphere reached 412 ppm. The large concentration of CO2 in the atmosphere has caused many serious environmental problems, such as global warming, ocean acidification, sea-level rise, glacier melting, and climate change. To solve these problems, one way is to replace the fossil energies with renewable clean energies like wind and solar electricity, which can decrease the CO2 emissions. However, wind and solar electricity suffer from an intermittent supply, unstable frequency, and hard delivery. Another way is to directly convert CO2 to other high-value chemicals and fuels with proper physicochemical methods, like thermochemical conversion, electrochemical reduction, and photocatalytic reduction. Very recently, with the combination of the aforementioned two ways, electrochemical CO2 reduction reaction (eCO2RR) powered by clean wind and solar electricity has become the most promising solution to address the CO2-caused environmental problems. Firstly, eCO2RR can be well coupled to the local clean energy power plants to fully utilize the clean electricity by converting CO2 to value-added chemicals and fuels. Secondly, eCO2RR is an efficient technique to achieve a carbon neutral cycle. Thirdly, the eCO2RR system runs under mild conditions with relative high energy efficiency.

Electrocatalytic carbon dioxide reduction reaction (CO

Electroreduction of CO

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.

The crystal phase of metal nanocatalysts significantly affects their catalytic performance. Cu-based nanomaterials are unique electrocatalysts for CO

Rayleigh instability was originally used to describe the phenomenon of a cylindrical fluid jet that transforms into a chain of droplets. Very recently, it has been extended to metallic nanostructures like gold (Au) and silver (Ag) nanowires (NWs), as well as mixed alloy NWs by some thermodynamic processes. To date, the key factors affecting the Rayleigh instability have not been well studied. To clarify this, we systematically investigate the features of Rayleigh instability in ultrathin 4H hexagonal Au nanoribbons (NRBs) under electron beam (E-beam) irradiation. We prove that by decreasing the initial widths of 4H Au NRBs and the E-beam current density, as well as the irradiation time and intensity per unit area, the Rayleigh instability can be effectively restrained. Our work thus sheds light on how to effectively reduce or even eliminate the Rayleigh instability of one dimensional nanomaterials.

Phase has emerged as an important structural parameter — in addition to composition, morphology, architecture, facet, size and dimensionality — that determines the properties and functionalities of nanomaterials. In particular, unconventional phases in nanomaterials that are unattainable in the bulk state can potentially endow nanomaterials with intriguing properties and innovative applications. Great progress has been made in the phase engineering of nanomaterials (PEN), including synthesis of nanomaterials with unconventional phases and phase transformation of nanomaterials. This Review provides an overview on the recent progress in PEN. We discuss various strategies used to synthesize nanomaterials with unconventional phases and induce phase transformation of nanomaterials, by taking noble metals and layered transition metal dichalcogenides as typical examples. Moreover, we also highlight recent advances in the preparation of amorphous nanomaterials, amorphous–crystalline and crystal phase-based hetero-nanostructures. We also provide personal perspectives on challenges and opportunities in this emerging field, including exploration of phase-dependent properties and applications, rational design of phase-based heterostructures and extension of the concept of phase engineering to a wider range of materials. Ministry of Education (MOE) Accepted version This work was supported by MOE under AcRF Tier 2 (MOE2016-T2-2-103; MOE2017-T2-1-162) and AcRF Tier 1 (2017-T1-001-150; 2017-T1-002-119), NTU under Start-Up Grant (M4081296.070.500000), and Agency for Science, Technology and Research (A*STAR) under its AME IRG (Project No. A1783c0009) in Singapore. H.Z. thanks the support from ITC via Hong Kong Branch of National Precious Metals Material Engineering Research Center. Z.F., Q.H. and H.Z. thank the support from the Start-Up Grant in City University of Hong Kong.

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. MOE (Min. of Education, S’pore)

Two-dimensional (2D) organic-inorganic hybrid perovskite nanosheets (NSs) are attracting increasing research interest due to their unique properties and promising applications. Here, for the first time, we report the facile synthesis of single- and few-layer free-standing phenylethylammonium lead halide perovskite NSs, that is, (PEA)2 PbX4 (PEA=C8 H9 NH3 , X=Cl, Br, I). Importantly, their lateral size can be tuned by changing solvents. Moreover, these ultrathin 2D perovskite NSs exhibit highly efficient and tunable photoluminescence, as well as superior stability. Our study provides a simple and general method for the controlled synthesis of 2D perovskite NSs, which may offer a new avenue for their fundamental studies and optoelectronic applications.