Conversion of non-van der Waals solids to 2D transition-metal chalcogenides.

Although two-dimensional (2D) atomic layers, such as transition-metal chalcogenides, have been widely synthesized using techniques such as exfoliation1-3 and vapour-phase growth4,5, it is still challenging to obtain phase-controlled 2D structures6-8. Here we demonstrate an effective synthesis strategy via the progressive transformation of non-van der Waals (non-vdW) solids to 2D vdW transition-metal chalcogenide layers with identified 2H (trigonal prismatic)/1T (octahedral) phases. The transformation, achieved by exposing non-vdW solids to chalcogen vapours, can be controlled using the enthalpies and vapour pressures of the reaction products. Heteroatom-substituted (such as yttrium and phosphorus) transition-metal chalcogenides can also be synthesized in this way, thus enabling a generic synthesis approach to engineering phase-selected 2D transition-metal chalcogenide structures with good stability at high temperatures (up to 1,373 kelvin) and achieving high-throughput production of monolayers. We anticipate that these 2D transition-metal chalcogenides will have broad applications for electronics, catalysis and energy storage.

Ampere-Level Current Density CO2 Reduction with High C2+ Selectivity on La(OH)3-Modified Cu Catalysts.

The carbon dioxide reduction reaction (CO2RR) driven by electricity can transform CO2 into high-value multi-carbon (C2+) products. Copper (Cu)-based catalysts are efficient but suffer from low C2+ selectivity at high current densities. Here La(OH)3 in Cu catalyst is introduced to modify its electronic structure towards efficient CO2RR to C2+ products at ampere-level current densities. The La(OH)3/Cu catalyst has a remarkable C2+ Faradaic efficiency (FEC2+) of 71.2% which is 2.2 times that of the pure Cu catalyst at a current density of 1,000 mA cm-2 and keeps stable for 8 h. In situ spectroscopy and density functional theory calculations both show that La(OH)3 modifies the electronic structure of Cu. This modification favors *CO adsorption, subsequent hydrogenation, *CO─*COH coupling, and consequently increases C2+ selectivity. This work provides a guidance on facilitating C2+ product formation, and suppressing hydrogen evolution by La(OH)3 modification, enabling efficient CO2RR at ampere-level current densities.

Single-Atom Pt Anchored on Oxygen Vacancy of Monolayer Ti3C2Tx for Superior Hydrogen Evolution.

Two-dimensional (2D) MXene-loaded single-atom (SA) catalysts have drawn increasing attention. SAs immobilized on oxygen vacancies (OV) of MXene are predicted to have excellent catalytic performance; however, they have not yet been realized experimentally. Here Pt SAs immobilized on the OV of monolayer Ti3C2Tx flakes are constructed by a rapid thermal shock technique under a H2 atmosphere. The resultant Ti3C2Tx-PtSA catalyst exhibits excellent hydrogen evolution reaction (HER) performance, including a small overpotential of 38 mV at 10 mA cm-2, a high mass activity of 23.21 A mgPt-1, and a large turnover frequency of 23.45 s-1 at an overpotential of 100 mV. Furthermore, density functional theory calculations demonstrate that anchoring the Pt SA on the OV of Ti3C2Tx helps to decrease the binding energy and the hybridization strength between H atoms and the supports, contributing to rapid hydrogen adsorption-desorption kinetics and high activity for the HER.

Freestanding and Sandwich MXene-Based Cathode with Suppressed Lithium Polysulfides Shuttle for Flexible Lithium-Sulfur Batteries.

Flexible lithium-sulfur (Li-S) batteries with high mechanical compliance and energy density are highly desired. This manuscript reported that large-area freestanding MXene (Ti3C2Tx) film has been obtained through a scalable drop-casting method, significantly improving adhesion to the sulfur layer under the continuously bent. Titanium oxide anchored on holey Ti3C2Tx (TiO2/H-Ti3C2Tx) was also produced by the well-controlled oxidation of few-layer Ti3C2Tx, which greatly facilitates lithium ion transport as well as prevents the shuttling of lithium polysulfides. Therefore, the obtained sandwich electrode has demonstrated a high capacity of 740 mAh g-1 at 2 C and a high capacity retention of 81% at 1 C after 500 cycles. Flexible Li-S batteries based on this sandwich electrode have a capacity retention as high as 95% after bending 500 times. This work provides effective design strategies of MXene for flexible batteries and wearable electronics.

Photoluminescence Lightening: Extraordinary Oxygen Modulated Dynamics in WS2 Monolayers.

Transition metal dichalcogenide monolayers exhibit ultrahigh surface sensitivity since they expose all atoms to the surface and thereby influence their optoelectronic properties. Here, we report an intriguing lightening of the photoluminescence (PL) from the edge to the interior over time in the WS2 monolayers grown by physical vapor deposition method, with the whole monolayer brightened eventually. Comprehensive optical studies reveal that the PL enhancement arises from the p doping induced by oxygen adsorption. First-principles calculations unveil that the dissociation of chemisorbed oxygen molecule plays a significant role; i.e., the dissociation at one site can largely promote the dissociation at a nearby site, facilitating the photoluminescence lightening. In addition, we further manipulate such PL brightening rate by controlling the oxygen concentration and the temperature. The presented results uncover the extraordinary surface chemistry and related mechanism in WS2 monolayers, which deepens our insight into their unique PL evolution behavior.

Designing Electrophilic and Nucleophilic Dual Centers in the ReS2 Plane toward Efficient Bifunctional Catalysts for Li-CO2 Batteries.

Two-dimensional transition metal dichalcogenides (TMDCs) show great potential as efficient catalysts for Li-CO2 batteries. However, the basal plane engineering on TMDCs toward bifunctional catalysts for Li-CO2 batteries is still poorly understood. In this work, density functional theory calculations reveal that nucleophilic N dopants and electrophilic S vacancies in the ReS2 plane tailor the interactions with Li atoms and C/O atoms in intermediates, respectively. The electrophilic and nucleophilic dual centers show suitable adsorption with all intermediates during discharge and charge, resulting in a small energy barrier for the rate-determining step. Thus, an efficient bifunctional catalyst is produced toward Li-CO2 batteries. As a result, the optimal catalyst achieves an ultrasmall voltage gap of 0.66 V and an ultrahigh energy efficiency of 81.1% at 20 µA cm-2, which is superior to those of previous catalysts under similar conditions. The introduction of electrophilic and nucleophilic dual centers provides new avenues for designing excellent bifunctional catalysts for Li-CO2 batteries.

Pressure-Enhanced Ferromagnetism in Layered CrSiTe3 Flakes.

Despite recent advances in layered ferromagnets, ferromagnetic interactions in these materials are rather weak. Here, we report pressure-enhanced ferromagnetism in layered CrSiTe3 flakes revealed by high-pressure magnetic circular dichroism measurements. Below ∼3 GPa, CrSiTe3 undergoes a paramagnetic-to-ferromagnetic phase transition at ∼32 K, and the field-induced spin-flip in the ferromagnetic phase produces nearly zero hysteresis loops, demonstrating soft ferromagnetism. Above ∼4 GPa, a soft-to-hard ferromagnetic transition occurs, signaled by rectangular-shaped hysteresis loops with finite coercivity and remanent magnetization. Interestingly, as pressure increases, the Curie temperature and coercivity dramatically increase up to ∼138 K and 0.17 T at 7.8 GPa, respectively, in contrast to ∼36 K and 0.02 T at 4.6 GPa. It indicates a remarkable influence of pressure on exchange interactions, which is consistent with DFT calculations. The effective interaction between magnetic couplings and external pressure offers new opportunities in pursuit of high-temperature layered ferromagnets.

Synthesis of Ultrahigh-Quality Monolayer Molybdenum Disulfide through In Situ Defect Healing with Thiol Molecules.

Monolayer transition metal dichalcogenides are 2D materials with many potential applications. Chemical vapor deposition (CVD) is a promising method to synthesize these materials. However, CVD-grown materials generally have poorer quality than mechanically exfoliated ones and contain more defects due to the difficulties in controlling precursors' distribution and concentration during growth where solid precursors are used. Here, thiol is proposed to be used as a liquid precursor for CVD growth of high quality and uniform 2D MoS2 . Atomic-resolved structure characterizations indicate that the concentration of sulfur vacancies in the MoS2 grown from thiol is the lowest among all reported CVD samples. Low temperature spectroscopic characterization further reveals the ultrahigh optical quality of the grown MoS2 . Density functional theory simulations indicate that thiol molecules could interact with sulfur vacancies in MoS2 and repair these defects during the growth of MoS2 , resulting in high-quality MoS2 . This work provides a facile and controllable method for the growth of high-quality 2D materials with ultralow sulfur vacancies and high optical quality, which will benefit their optoelectronic applications.

Chemical Vapor Deposition Growth and Applications of Two-Dimensional Materials and Their Heterostructures.

Two-dimensional (2D) materials have attracted increasing research interest because of the abundant choice of materials with diverse and tunable electronic, optical, and chemical properties. Moreover, 2D material based heterostructures combining several individual 2D materials provide unique platforms to create an almost infinite number of materials and show exotic physical phenomena as well as new properties and applications. To achieve these high expectations, methods for the scalable preparation of 2D materials and 2D heterostructures of high quality and low cost must be developed. Chemical vapor deposition (CVD) is a powerful method which may meet the above requirements, and has been extensively used to grow 2D materials and their heterostructures in recent years, despite several challenges remaining. In this review of the challenges in the CVD growth of 2D materials, we highlight recent advances in the controlled growth of single crystal 2D materials, with an emphasis on semiconducting transition metal dichalcogenides. We provide insight into the growth mechanisms of single crystal 2D domains and the key technologies used to realize wafer-scale growth of continuous and homogeneous 2D films which are important for practical applications. Meanwhile, strategies to design and grow various kinds of 2D material based heterostructures are thoroughly discussed. The applications of CVD-grown 2D materials and their heterostructures in electronics, optoelectronics, sensors, flexible devices, and electrocatalysis are also discussed. Finally, we suggest solutions to these challenges and ideas concerning future developments in this emerging field.

Relationship between periodontal disease and lung cancer: A systematic review and meta-analysis.

Periodontal disease (PD), as a chronic bacterial infection, might cause cardiovascular and some other systemic diseases, with recent studies reporting that it exhibits some connection with lung cancer. While studies have shown that poor oral health might increase the risk of lung cancer, the veracity of these reports is questionable. Therefore, this meta-analysis was undertaken to investigate the association between PD and the risk of lung cancer. A search was run in PubMed, EMBASE, MEDLINE, CENTRAL, and ClinicalTrials.gov databases up to January 1, 2020. Cohort and case-control studies investigating the correlation between PD and lung cancer were included. Eligibility assessment and data extraction were conducted independently, and a meta-analysis was performed to synthesize the data. The association between PD, edentulism, and lung cancer was measured by the adjusted hazard ratios (HRs) or odds ratios (ORs) and their 95% confidence intervals (CIs) provided in articles. We employed appropriate effect model in terms of I2 (a fixed-effect model for PD and a random-effect model for edentulism) to obtain summary effect estimates. Statistical heterogeneity was investigated by chi-square test and I2 statistics. Newcastle-Ottawa Scale (NOS) was used to assess the quality of their method. Six cohort studies (eight references) and two case-control studies, assessed as high-quality, involving 167 256 participants, were included in the review. The summary estimates based on adjusted data showed an association between PD and a significant risk of lung cancer both in cohort studies (HR = 1.40, 95% CI = 1.25-1.58; I2  = 8.7%) and case-control studies (OR = 1.51, 95% CI = 1.16-1.98; I2  = 36.5%). Similar features were found in the sensitivity analysis and subgroups for six cohort studies, of male only (HR = 1.36, 95% CI = 1.15-2.60), setting the lung cancer incidence as endpoint (HR = 1.39, 95% CI = 1.24-1.57; I2  = 23.9%), and adjusting alcohol for multifactorial HR (HR = 1.38, 95% CI = 1.21-1.57; I2  = 39.9%). The summary HR for edentulism was 1.93 (95% CI = 1.05-3.57; I2  = 55.3%). No obvious publication bias was detected. This systematic review and meta-analysis demonstrated a significant association between PD and the incidence of lung cancer. Further observational studies are required by using standardized measurements to assess the periodontal status and by eliminating confounding factors, such as alcohol and diabetes, to verify such a relationship.

Factors associated with the publication outcomes of paediatric proceedings presented at 2010-2016 the International Associations for Dental Research annual meetings.

The International Associations for Dental Research (IADR) annual meeting is one of the most important dental meetings throughout the world, and researches about paediatric dentistry presented in this platform are often used to guide clinical work. To evaluate the publication outcomes of oral and poster paediatric proceedings, which were accepted by the International Associations for Dental Research (IADR), annual meetings from 2010 to 2016 and to analyse the possible factors influencing an abstract's progression to publication. Oral and poster abstracts were retrieved from the official website of IADR (2010-2016). Searching for subsequent publications was conducted in PubMed and Google Scholar (up to March 2019). Two authors independently selected studies, collected, and analysed data. A total of 1396 abstracts were identified, including 275 oral presentations and 1121 poster presentations. Finally, 606 were published in peer-reviewed journals, with a publication rate of 43.41%. Abstracts were published earlier if it is from Europe, well funded, presented orally, or with large sample size. The high publication rate of the IADR proceedings supported the impact of IADR annual meetings on paediatric dentistry in the last 10 years.

Soft Porous Crystal Based upon Organic Cages That Exhibit Guest-Induced Breathing and Selective Gas Separation.

Soft porous crystals (SPCs) that exhibit stimuli-responsive dynamic sorption behavior are attracting interest for gas storage/separation applications. However, the design and synthesis of SPCs is challenging. Herein, we report a new type of SPC based on a [2 + 3] imide-based organic cage (NKPOC-1) and find that it exhibits guest-induced breathing behavior. Various gases were found to induce activated NKPOC-1 crystals to reversibly switch from a "closed" nonporous phase (α) to two porous "open" phases (ß and γ). The net effect is gate-opening behavior induced by CO2 and C3 hydrocarbons. Interestingly, NKPOC-1-α selectively adsorbs propyne over propylene and propane under ambient conditions. Thus, NKPOC-1-α has the potential to separate binary and ternary C3 hydrocarbon mixtures, and the performance was subsequently verified by fixed bed column breakthrough experiments. In addition, molecular dynamics calculations and in situ X-ray diffraction experiments indicate that the gate-opening effect is accompanied by reversible structural transformations. The adsorption energies from molecular dynamics simulations aid are consistent with the experimentally observed selective adsorption phenomena. The understanding gained from this study of NKPOC-1 supports the further development of SPCs for applications in gas separation/storage because SPCs do not inherently suffer from the recyclability problems often encountered with rigid materials.

Scalable Production of Two-Dimensional Metallic Transition Metal Dichalcogenide Nanosheet Powders Using NaCl Templates toward Electrocatalytic Applications.

Two-dimensional (2D) metallic transition metal dichalcogenides (MTMDCs) have attracted tremendous interest due to their intriguing physical properties and broad application potential. However, batch production of high-quality 2D MTMDCs based on existing synthesis on 2D surfaces remains a huge challenge. Herein, a universal synthetic route for the scalable synthesis of high-quality 2D MTMDC (e.g., TaS2, V5S8, and NbS2) nanosheets using microcrystalline NaCl crystals as templates via a facile chemical vapor deposition method is reported. Obviously, this synthetic route is perfectly compatible with a facile water dissolution-filtration process for obtaining high-purity MTMDC nanosheet powders. Representatively, a thickness-uniform 1T-TaS2 nanosheet product can be achieved that shows unexceptionable dispersibility in ethanol, which allows its assembly onto arbitrary substrates/electrodes for high-performance energy-related applications, herein serving as a high-performance electrocatalyst for the hydrogen evolution reaction. This work sheds light on the batch production, green transfer, and energy-related application of 2D MTMDC materials.

Electronic Doping Controlled Migration of Dislocations in Polycrystalline 2D WS2.

Migration of dislocations not only determines the durability of large-scale nanoelectronic and opto-electronic devices based on polycrystalline 2D transition-metal dichalcogenides (TMDCs), but also plays an important role in enhancing the performance of novel memristors. However, a fundamental question of the migration dependence on the electronic effects, which are inevitable in practical field-effect transistors based on 2D TMDCs, and its interplay with different dislocations, remains unexplored. Here, taking WS2 as an example, first-principle calculations are used to show that the electronic contributions arising from defect states can greatly influence the migration barriers of dislocations. The barrier height can be reduced by as much as 50%, which is mainly attributed to the change in electronic occupation and the band energy of defect levels controlled by electronic chemical potential (Fermi level). The reduced barriers in turn lead to significantly enhanced migration, and thus the plasticity. Since defect levels from dislocations locate deep inside the bandgap, the doping-induced tuning of barrier height can be achieved at relatively low doping concentration through either chemical doping or electrode gating. The effective electromechanical coupling in 2D TMDCs can provide new opportunities in material engineering for various potential applications.

Anisotropic Growth and Scanning Tunneling Microscopy Identification of Ultrathin Even-Layered PdSe2 Ribbons.

Palladium diselenide (PdSe2 ) is an emerging 2D layered material with anisotropic optical/electrical properties, extra-high carrier mobility, excellent air stability, etc. So far, ultrathin PdSe2 is mainly achieved via mechanical exfoliation from its bulk counterpart, and the direct synthesis is still challenging. Herein, the synthesis of ultrathin 2D PdSe2 on conductive Au foil substrates via a facile chemical vapor deposition route is reported. Intriguingly, an anisotropic growth behavior is detected from the evolution of ribboned flakes with large length/width ratios, which is well explained from the orthorhombic symmetry of PdSe2 . A unique even-layered growth mode from 2 to 20 layers is also confirmed by the perfect combination of onsite scanning tunneling microscopy characterizations, through deliberately scratching the flake edge to expose both even and odd layers. This even-layered, ribboned 2D material is expected to serve as a perfect platform for exploring unique physical properties, and for developing high-performance electronic and optoelectronic devices.

Atomic Layers of MoO2 with Exposed High-Energy (010) Facets for Efficient Oxygen Reduction.

Although 2D nanocrystals with exposed high-energy facets are highly desired in the field of catalysts due to their anticipant high catalytic activities, they are difficult to be gained. Here, atomic layers of metallic molybdenum dioxide (MoO2 ) with primarily exposed high-energy (010) facet are achieved via a facile carbothermic reduction approach. The resultant MoO2 exhibits single-crystalline, monoclinic, and ultrathin features with nearly 100% exposed (010) facet, which can significantly reduce reaction barriers toward the oxygen reduction reaction. As a consequence, the atomic layers of MoO2 exhibit high electrocatalytic activity, excellent tolerance to methanol, and good stability for the oxygen reduction reaction in alkaline electrolyte, superior to commercial Pt/C catalysts. It is believed that such new transition metal oxide catalysts with exposed high-energy facets have broad applications in the areas of energy storage and conversions.

Incorporation of Nitrogen Defects for Efficient Reduction of CO2 via Two-Electron Pathway on Three-Dimensional Graphene Foam.

The practical recycling of carbon dioxide (CO2) by the electrochemical reduction route requires an active, stable, and affordable catalyst system. Although noble metals such as gold and silver have been demonstrated to reduce CO2 into carbon monoxide (CO) efficiently, they suffer from poor durability and scarcity. Here we report three-dimensional (3D) graphene foam incorporated with nitrogen defects as a metal-free catalyst for CO2 reduction. The nitrogen-doped 3D graphene foam requires negligible onset overpotential (-0.19 V) for CO formation, and it exhibits superior activity over Au and Ag, achieving similar maximum Faradaic efficiency for CO production (∼85%) at a lower overpotential (-0.47 V) and better stability for at least 5 h. The dependence of catalytic activity on N-defect structures is unraveled by systematic experimental investigations. Indeed, the density functional theory calculations confirm pyridinic N as the most active site for CO2 reduction, consistent with experimental results.

Strain-Induced Electronic Structure Changes in Stacked van der Waals Heterostructures.

Vertically stacked van der Waals heterostructures composed of compositionally different two-dimensional atomic layers give rise to interesting properties due to substantial interactions between the layers. However, these interactions can be easily obscured by the twisting of atomic layers or cross-contamination introduced by transfer processes, rendering their experimental demonstration challenging. Here, we explore the electronic structure and its strain dependence of stacked MoSe2/WSe2 heterostructures directly synthesized by chemical vapor deposition, which unambiguously reveal strong electronic coupling between the atomic layers. The direct and indirect band gaps (1.48 and 1.28 eV) of the heterostructures are measured to be lower than the band gaps of individual MoSe2 (1.50 eV) and WSe2 (1.60 eV) layers. Photoluminescence measurements further show that both the direct and indirect band gaps undergo redshifts with applied tensile strain to the heterostructures, with the change of the indirect gap being particularly more sensitive to strain. This demonstration of strain engineering in van der Waals heterostructures opens a new route toward fabricating flexible electronics.

An open canvas--2D materials with defects, disorder, and functionality.

CONSPECTUS: While some exceptional properties are unique to graphene only (its signature Dirac-cone gapless dispersion, carrier mobility, record strength), other features are common to other two-dimensional materials. The broader family "beyond graphene" offers greater choices to be explored and tailored for various applications. Transition metal dichalcogenides (TMDCs), hexagonal boron nitride (h-BN), and 2D layers of pure elements, like phosphorus or boron, can complement or even surpass graphene in many ways and uses, ranging from electronics and optoelectronics to catalysis and energy storage. Their availability greatly relies on chemical vapor deposition growth of large samples, which are highly polycrystalline and include interfaces such as edges, heterostructures, and grain boundaries, as well as dislocations and point defects. These imperfections do not always degrade the material properties, but they often bring new physics and even useful functionality. It turns particularly interesting in combination with the sheer openness of all 2D sheets, fully exposed to the environment, which, as we show herein, can change and tune the defect structures and consequently all their qualities, from electronic levels, conductivity, magnetism, and optics to structural mobility of dislocations and catalytic activities. In this Account, we review our progress in understanding of various defects. We begin by expressing the energy of an arbitrary graphene edge analytically, so that the environment is regarded by "chemical phase shift". This has profound implications for graphene and carbon nanotube growth. Generalization of this equation to heteroelemental BN gives a method to determine the energy for arbitrary edges of BN, depending on the partial chemical potentials. This facilitates the tuning of the morphology and electronic and magnetic properties of pure BN or hybrid BN|C systems. Applying a similar method to three-atomic-layer TMDCs reveals more diverse edge structures for thermodynamically stable flakes. Moreover, CVD samples show new types of edge reconstruction, providing insight into the nonequilibrium growth process. Combining dislocation theory with first-principles computations, we could predict the dislocation cores for BN and TMDC and reveal their variable chemical makeup. This lays the foundation for the unique sensitivity to ambient conditions. For example, partial occupation of the defect states for dislocations in TMDCs renders them intrinsically magnetic. The exchange coupling between electrons from neighboring dislocations in grain boundaries further makes them half-metallic, which may find its applications in spintronics. Finally, brief discussion of monoelemental 2D-layer phosphorus and especially the structures and growth routes of 2D boron shows how theoretical assessment can help the quest for new synthetic routes.

Environment-Controlled Dislocation Migration and Superplasticity in Monolayer MoS2.

The two-dimensional (2D) transition metal dichalcogenides (TMDC, of generic formula MX2) monolayer displays the "triple-decker" structure with the chemical bond organization much more complex than in well-studied monatomic layers of graphene or boron nitride. Accordingly, the makeup of the dislocations in TMDC permits chemical variability, depending sensitively on the equilibrium with the environment. In particular, first-principles calculations show that dislocations state can be switched to highly mobile, profoundly changing the lattice relaxation and leading to superplastic behavior. With 2D MoS2 as an example, we construct full map for dislocation dynamics, at different chemical potentials, for both the M- and X-oriented dislocations. Depending on the structure of the migrating dislocation, two different dynamic mechanisms are revealed: either the direct rebonding (RB) mechanism where only a single metal atom shifts slightly, or generalized Stone-Wales (SW(g)) rotation in which several atoms undergo significant displacements. The migration barriers for RB mechanism can be 2-4 times lower than for the SW(g). Our analyses show that within a range of chemical potentials, highly mobile dislocations could at the same time be thermodynamically favored, that is statistically dominating the overall material property. This demonstrates remarkable possibility of changing material basic property such as plasticity by changing elemental chemical potentials of the environment.