Suppressed charge recombination via defect engineering of confined semiconducting quantum dots for photoelectrocatalysis.

Confined semiconducting CuSe quantum dots with abundant Se vacancies are synthesized by pulsed laser deposition with in situ vacuum annealing. With the presence of Se vacancies, the photogenerated charge recombination is suppressed by the self-introduced in-gap trapping states, thus enhancing the photoelectrocatalytic activity under solar illumination.

In-situ construction of direct Z-scheme NiO/Bi2MoO6 heterostructure arrays with enhanced room temperature ether sensing properties under visible light irradiation.

Light irradiation has emerged as a promising strategy to promote room temperature sensing of resistive-type semiconductor gas sensors recently. However, high recombination rate of photo-generated carriers and poor visible light response of conventional semiconductor sensing materials have greatly limited the further performance improvement. It is urgent to develop gas sensing materials with high photo-generated carrier separation efficiency and excellent visible light response. Herein, a novel direct Z-scheme NiO/Bi2MoO6 heterostructure arrays were designed and in-situ constructed on alumina flat substrate to form thin film sensors, which realized excellent room temperature gas response towards ether under irradiation of visible light for the first time, together with excellent stability and selectivity. Based on density functional theory calculation and experimental characterization, it was demonstrated that the construction of Z-scheme heterostructure could greatly promote the separation of photo-generated carriers and adsorption of ether. Moreover, the excellent visible light response characteristics of NiO/Bi2MoO6 could improve the utilization of visible light. In addition, the in-situ construction of array structure could avoid a series of problems caused by the conventional thick film devices. The work not only provides a promising guideline for Z-scheme heterostructure arrays in promoting the room temperature sensing performance of semiconductors gas sensors under visible light irradiation, but also clarifies the gas sensing mechanism of Z-scheme heterostructure at the atomic and electronic level.

Interlayer-Confined NiFe Dual Atoms within MoS2 Electrocatalyst for Ultra-Efficient Acidic Overall Water Splitting.

Confining dual atoms (DAs) within the van der Waals gap of 2D layered materials is expected to expedite the kinetic and energetic strength in catalytic process, yet is a huge challenge in atomic-scale precise assembling DAs within two adjacent layers in the 2D limit. Here, an ingenious approach is proposed to assemble DAs of Ni and Fe into the interlayer of MoS2 . While inheriting the exceptional merits of diatomic species, this interlayer-confined structure arms itself with confinement effect, displaying the more favorable adsorption strength on the confined metal active center and higher catalytic activity towards acidic water splitting, as verified by intensive research efforts of theoretical calculations and experimental measurements. Moreover, the interlayer-confined structure also renders metal DAs a protective shelter to survive in harsh acidic environment. The findings embodied the confinement effects at the atom level, and interlayer-confined assembling of multiple species highlights a general pathway to advance interlayer-confined DAs catalysts within various 2D materials.

External Fields Assisted Highly Efficient Oxygen Evolution Reaction of Confined 1T-VSe2 Ferromagnetic Nanoparticles.

As a clean and effective approach, the introduction of external magnetic fields to improve the performance of catalysts has attracted extensive attention. Owing to its room-temperature ferromagnetism, chemical stability, and earth abundance, VSe2 is expected to be a promising and cost-effective ferromagnetic electrocatalyst for the accomplishment of high-efficient spin-related OER kinetics. In this work, a facile pulsed laser deposition (PLD) method combined with rapid thermal annealing (RTA) treatment is used to successfully confine monodispersed 1T-VSe2 nanoparticles in amorphous carbon matrix. As expected, with external magnetic fields of 800 mT stimulation, the confined 1T-VSe2 nanoparticles exhibit highly efficient oxygen evolution reaction (OER) catalytic activity with an overpotential of 228 mV for 10 mA cm-2 and remarkable durability without deactivation after >100 h OER operation. The experimental results together with theoretical calculations illustrate that magnetic fields can facilitate the surface charge transfer dynamics of 1T-VSe2 , and modify the adsorption-free energy of *OOH, thus finally improving the intrinsic activity of the catalysts. This work realizes the application of ferromagnetic VSe2 electrocatalyst in highly efficient spin-dependent OER kinetics, which is expected to promote the application of transition metal chalcogenides (TMCs) in external magnetic field-assisted electrocatalysis.

Atomic Magnetic Heating Effect Enhanced Hydrogen Evolution Reaction of Gd@MoS2 Single-Atom Catalysts.

Atomic heating on single atoms (SAs) to maximize the catalytic efficiency of each active site would be a fascinating solution to break the bottleneck for the performance improvement of single-atom catalysts (SACs) but highly challenging task. Here, based on the Gd@MoS2 SACs synthesized by a facile laser molecular beam epitaxy method, high-frequency alternating magnetic field (AMF) technology is employed to induce atomic magnetic heating on Gd SAs that is meanwhile demonstrated to be the catalytic active center. Significant improvement in catalytic kinetics under AMF excitation (3.9 mT) is achieved, yielding a remarkable enhancement of hydrogen evolution reaction magnetothermal-current by ≈924%. Through theoretical calculations and spin-related electrochemical experiments, such promotion in catalyst activity can be attributed to spin flip (or canting) in Gd SAs leading to the atomic magnetic heating effect on catalytic active center. Together with the embodied high stability, the implement of AMF to the SAs field is demonstrated in this work, and the precisely atomic magnetic heating on specific SAs offers unprecedented thinking for further improvement of SACs performance in the future.

Electrochemical Reconstruction of NiFe/NiFeOOH Superparamagnetic Core/Catalytic Shell Heterostructure for Magnetic Heating Enhancement of Oxygen Evolution Reaction.

Although (oxy)hydroxides generated by electrochemical reconstruction (EC-reconstruction) of transition-metal catalysts exhibit highly catalytic activities, the amorphous nature fundamentally impedes the electrochemical kinetics due to its poor electrical conductivity. Here, EC-reconstructed NiFe/NiFeOOH core/shell nanoparticles in highly conductive carbon matrix based on the pulsed laser deposition prepared NiFe nanoparticles is successfully confined. Electrochemical characterizations and first-principles calculations demonstrate that the reconstructed NiFe/NiFeOOH core/shell nanoparticles exhibit high oxygen evolution reaction (OER) electrocatalytic activity (a low overpotential of 342.2 mV for 10 mA cm-2 ) and remarkable durability due to the efficient charge transfer in the highly conductive confined heterostructure. More importantly, benefit from the superparamagnetic nature of the reconstructed NiFe/NiFeOOH core/shell nanoparticles, a large OER improvement is achieved (an ultralow overpotential of 209.2 mV for 10 mA cm-2 ) with an alternating magnetic field stimulation. Such OER improvement can be attributed to the Néel relaxation related magnetic heating effect functionalized superparamagnetic NiFe cores, which are generally underutilized in reconstructed core/shell nanoparticles. This work demonstrates that the designed superparamagnetic core/shell nanoparticles, combined with the large improvement by magnetic heating effect, are expected to be highly efficient OER catalysts along with the confined structure guaranteed high conductivity and catalytic stability.

Alternating Magnetic Field Induced Magnetic Heating in Ferromagnetic Cobalt Single-Atom Catalysts for Efficient Oxygen Evolution Reaction.

Alternating magnetic field (AMF) is a promising methodology for further improving magnetic single-atom catalyst (SAC) activity toward oxygen evolution reaction (OER). Herein, the anchoring of Co single atoms on MoS2 support (Co@MoS2), leading to the appearance of in-plane room-temperature ferromagnetic properties, is favorable for the parallel spin arrangement of oxygen atoms when a magnetic field is applied. Moreover, field-assisted electrocatalytic experiments confirmed that the spin direction of Co@MoS2 is changing with the applied magnetic field. On this basis, under AMF, the active sites in ferromagnetic Co@MoS2 were heated by exploiting the magnetic heating generated from spin polarization flip of these SACs to further expedite OER efficiency, with overpotential at 10 mA cm-2 reduced from 317 mV to 250 mV. This work introduces a feasible and efficient approach to enhance the OER performance of Co@MoS2 by AMF, shedding some light on the further development of magnetic SACs for energy conversion.

Efficient Charge Transfers in Highly Conductive Copper Selenide Quantum Dot-Confined Catalysts for Robust Oxygen Evolution Reaction.

Defective quantum dots (QDs) are the emerging materials for catalysis by virtue of their atomic-scale size, high monodispersity, and ultra-high specific surface area. However, the dispersed nature of QDs fundamentally prohibits the efficient charge transfer in various catalytic processes. Here, we report efficient and robust electrocatalytic oxygen evolution based on defective and highly conductive copper selenide (CuSe) QDs confined in an amorphous carbon matrix with good uniformity (average diameter 4.25 nm) and a high areal density (1.8 × 1012 cm-2). The CuSe QD-confined catalysts with abundant selenide vacancies were prepared by using a pulsed laser deposition system benefitted by high substrate temperature and ultrahigh vacuum growth conditions, as evidenced by electron paramagnetic resonance characterizations. An ultra-low charge transfer resistance (about 7 Ω) determined by electrochemical impedance spectroscopy measurement indicates the efficient charge transfer of CuSe quantum-confined catalysts, which is guaranteed by its high conductivity (with a low resistivity of 2.33 µΩ·m), as revealed by electrical transport measurements. Our work provides a universal design scheme of the dispersed QD-based composite catalysts and demonstrates the CuSe QD-confined catalysts as an efficient and robust electrocatalyst for oxygen evolution reaction.

Synergistically Coupling of Manganese-Doped CoP Nanowires Arrays with Highly Dispersed Ni(PO3)2 Nanoclusters toward Efficient Overall Water Splitting.

Co-based phosphides are considered to be highly promising electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, their electrocatalytic efficiencies are greatly limited by the weak water dissociation process and unsatisfactory adsorption ability toward reaction intermediates. Herein, novel Mn-doped CoP/Ni(PO3)2 heterostructure array electrocatalysts which are composed of highly dispersed Ni(PO3)2 nanoclusters that are tightly wrapped on Mn-doped CoP nanowire arrays are designed. An electrocatalytic performance test suggested that the heterostructure arrays exhibited competitive electrocatalytic performance toward both HER and OER, which needed overpotentials of 116 and 245 mV to drive a current of 10 mA/cm2, respectively. Encouragingly, a symmetric two electrode water splitting system constructed by the heterostructure arrays required an ultralow cell voltage, suggesting the potential in overall water splitting. First-principles calculations combined with experimental characterization were further performed to clarify the electrocatalytic mechanism. On the one hand, effective doping of Mn atoms could optimize the surface electronic structure of CoP and promote the intrinsic activity. On the other hand, the compact and abundant heterogeneous interface between Ni(PO3)2 and CoP not only made more active sites exposed but also promoted the effective adsorption of intermediate reaction species on the catalyst surface. This work provides a new strategy to improve electrocatalytic performance of Co-based phosphides through the synergistic coupling of metal-doping and phosphate surface decoration, which will greatly promote the development of highly efficient electrocatalysts for overall water splitting.

Light-assisted room temperature gas sensing performance and mechanism of direct Z-scheme MoS2/SnO2 crystal faceted heterojunctions.

Light assistance and construction of heterojunctions are both promising means to improve the room temperature gas sensing performance of MoS2 recently. However, enhancing the separation efficiency of photo-generated carriers at interface and adsorption ability of surface have become the bottleneck problem to further improve the room temperature gas sensing performance of MoS2-based heterojunctions under light assistance. In the present study, a novel direct Z-scheme MoS2/SnO2 heterojunction was designed through crystal facets engineering and its room temperature gas sensing properties under light assistance was studied. It was found that the heterojunction showed outstanding room temperature NO2 sensing performance with a high response of 208.66 toward 10 ppm NO2, together with excellent recovery characteristics and selectivity. The gas sensing mechanism study suggested that high-energy {221} crystal facets of SnO2 and MoS2 directly formed Z-scheme heterojunction, which could greatly improve the separation efficiency of photo-generated carriers with high redox capacity. Moreover, {221} facets greatly enhanced adsorption ability towards NO2. This work not only opens up the application of Z-scheme heterojunctions in gas sensing, which will greatly promotes the development of room temperature light-assisted gas sensors, but also provides a new idea for the construction of direct Z-scheme heterojunctions through crystal facets engineering.

Antiferromagnetic Phase Induced by Nitrogen Doping in 2D Cr2S3.

Exploration for the new members of air-stable 2D antiferromagnetic magnets to widen the magnetic families has drawn great attention due to its potential applications in spintronic devices. In addition to seeking the intrinsic antiferromagnets, externally introducing antiferromagnetic ordering in existing 2D materials, such as structural regulation and phase engineering, may be a promising way to modulate antiferromagnetism in the 2D limit. In this work, the in situ nitrogen doping growth of ultrathin 2D Cr2S3 nanoflakes has been achieved. Antiferromagnetic ordering in 2D Cr2S3 nanoflakes can be triggered by nitrogen doping induced new phase (space group P3¯1c). This work provides a new route to realize antiferromagnetism in atomically thin 2D magnets and greatly extend applications of 2D magnets in valleytronics and spintronics.

Interfacial Effect on Photo-Modulated Magnetic Properties of Core/Shell-Structured NiFe/NiFe2O4 Nanoparticles.

Photo-modulated magnetism has become an emerging method for technological applications, such as magneto-optical devices. In this work, by introducing oxygen during rapid thermal annealing, NiFe/NiFe2O4 core/shell nanoparticles were successfully fabricated by pulsed laser deposition. Obvious photo-modulated ferromagnetism was observed in core/shell nanoparticles confined in Al2O3 film. Theoretical and experimental investigations indicate much more photogenerated electrons are captured at the interface of NiFe/NiFe2O4 compared with NiFe nanoparticles due to interfacial effect, resulting in the improved ferromagnetism under light irradiation. This work provides a promising strategy for optical engineering design of optical information storage, high-speed wireless communication, and magneto-optical semiconductor devices.

Boosting the OER Performance of Nitrogen-Doped Ni Nanoclusters Confined in an Amorphous Carbon Matrix.

Nanoclusters are ideal electrocatalysts due to their high surface activity. However, their high activities also lead to serious agglomeration and performance attenuation during the catalytic process. Here, highly dispersed Ni nanoclusters (∼3 nm) confined in an amorphous carbon matrix are successfully fabricated by pulsed laser deposition, followed by rapid temperature annealing treatment. Then, the Ni nanoclusters are further doped with nitrogen element through a clean N2 radio frequency plasma technology. It is found that the nitrogen-doped Ni nanoclusters obtained under optimized conditions showed superior OER performance with a very low overpotential of 240 mV at a current density of 10 mA/cm2, together with good stability. The excellent OER performance of the nanoclusters can be attributed to the unique confined structure and nitrogen doping, which not only provide more active sites but also improve the conductivity. Our work provides a controllable method for the construction of a novel confined structure with controllable nitrogen doping, which can be used as a high-efficiency OER electrocatalyst.

Porous N-doped carbon with confined Fe-doped CoP grown on CNTs for superefficient oxygen evolution electrocatalysis.

Herein, Fe-doped CoP nanoparticles (Fe-CoP NPs) encapsulated in porous N-doped carbon (PNC)/carbon nanotubes (CNTs) have been successfully synthesized. The Fe doping and confined structures resulted in enhanced charge transfer and improved active sites for intermediates adsorption. The obtained Fe-CoP@PNC/CNTs materials exhibited superefficient OER performance.

Revealing the synergistic mechanism of multiply nanostructured V2O3 hollow nanospheres integrated with doped N, Ni heteroatoms, in-situ grown carbon nanotubes and coated carbon nanolayers for the enhancement of lithium-sulfur batteries.

Lithium sulfur (Li-S) batteries are regarded as one of the most promising future energy storage candidates on account of high theoretical specific capacity of 1675 mAh g-1 and energy density of 2600 Wh kg-1. However, their practical application is seriously hindered due to the poor conductivity and volume expansion of sulfur, the weak redox kinetics of lithium polysulfide (LPS), and the severe shuttle effect of LPS. Herein, V2O3@N,Ni-C nanostructures, multiply integrated with zero-dimensional (0D) V2O3 nanoparticles, 1D carbon nanotubes, 2D carbon coating layers and graphene, 3D hollow spheres, and doped N and Ni heteroatoms, were synthesized via a solvothermal method followed by chemical vapor deposition. After being used as a modifier for traditional commercial separator of Li-S batteries, the shuttle effect of LPS can be effectively suppressed owing to the abundant active physical and chemical adsorption sites derived from large specific surface area, rich porosity, and tremendous polarity of the V2O3 nanoparticles with multiple secondary nanostructure integration. Meanwhile, the transfer of Li+ ions and electrons can be effectively enhanced by the highly conductive 2D carbon network, and the kinetics of redox reaction (Li2Sn â†” Li2S) can be accelerated by the doped N and Ni heteroatoms, leading to a synergistic promotion on the reutilization of the adsorbed LPS. Additionally, the unique 3D hollow structure can not only enhance the penetration of electrolyte, but also buffer the volume expansion of sulfur to some extent. Therefore, the rate capacity and cycling performance can be significantly enhanced by the multifunction synergism of adsorption, conductivity, catalysis, and volume buffering. An initial discharge capacity of 1590.4 mAh g-1can be achieved at 0.1C, and the discharge capacity of 803.5 mAh g-1can be still exhibited when increasing to 2C. After a long period of 500 cycles, additionally, the discharge specific capacity of 1142.2 mAh g-1 and capacity attenuation of 0.0617% per cycle can be obtained at 1C.

An individual sandwich hybrid nanostructure of cobalt disulfide in-situ grown on N doped carbon layer wrapped on multi-walled carbon nanotubes for high-efficiency lithium sulfur batteries.

Binding and trapping of lithium polysulfide (LPS) are being conceived as the most effective strategies to improve lithium-sulfur (Li-S) battery performance. Therefore, exploiting a simple but cost-effective approach for the absorption and conversion of LPS and the transfer of electrons and Li+ ions is of paramount importance. Herein, sandwich structure MWCNTs@N-doped-C@CoS2 integrated with multiple nanostructures of zero-dimensional (0D) CoS2 nanoparticles, 1D carbon nanotubes (CNTs), and 2D N-doped amorphous carbon layer was obtained, where MWCNTs was firstly uniformly attached with a polydopamine (PDA) of excellent adhesion, followed by hydrothermal method, the Co2+ nanoparticles were in-situ grown on the PDA by the formation of complex compound of Co2+ and N atoms in PDA, and then the CoS2 nanoparticles were in-situ grown on CNTs in a point-surface contact way by a bridging of N-doped amorphous carbon layer derived from the carbonization of attached PDA after the vulcanization at 500 °C under Ar atmosphere. The multifunction synergism of absorption, conductivity, and the kinetics of LPS redox is significantly improved, consequently effectively suppressing the shuttle effect and tremendously increasing the utilization rate of active substance. For the Li-S battery assembled with MWCNTs@N-doped-C@CoS2-modified separator, its rate capacity and cycling performance can be greatly enhanced. It can exhibit a high initial discharge capacity of 1590 mAh g-1 at 0.1 C, a stable long-term cycling performance with a relatively low capacity decay of 0.07% per cycle during 500 cycles at 1 C, and a reversible capacity of 772 mAh g-1 and a capacity decay of 0.04% per cycle during 250 cycles at 2 C. Even at a large current density of 4 C, an initial specific discharge capacity of 634 mAh g-1 can still be delivered. With a high sulfur loading of 5.0 mg cm-2, additionally, an outstanding cycling stability can also be well maintained at 685 mAh g-1 at 0.1 C after 50 cycles. This work provides a novel and simple but effective strategy to develop such sandwich hybrid materials comprised of polar metal sulfides and conductive networks via an effective bridging to help realize durable and stable Li-S battery.

Field-Free Improvement of Oxygen Evolution Reaction in Magnetic Two-Dimensional Heterostructures.

Ferromagnetic (FM) electrocatalysts have been demonstrated to reduce the kinetic barrier of oxygen evolution reaction (OER) by spin-dependent kinetics and thus enhance the efficiency fundamentally. Accordingly, FM two-dimensional (2D) materials with unique physicochemical properties are expected to be promising oxygen-evolution catalysts; however, related research is yet to be reported due to their air-instabilities and low Curie temperatures (TC). Here, based on the synthesis of 2D air-stable FM Cr2Te3 nanosheets with a low TC around 200 K, room-temperature ferromagnetism is achieved in Cr2Te3 by proximity to an antiferromagnetic (AFM) CrOOH, demonstrating the accomplishment of long-ranged FM ordering in Cr2Te3 because the magnetic proximity effect stems from paramagnetic (PM)/AFM heterostructure. Therefore, the OER performance can be permanently promoted (without applied magnetic field due to nonvolatile nature of spin) after magnetization. This work demonstrates that a representative PM/AFM 2D heterostructure, Cr2Te3/CrOOH, is expected to be a high-efficient magnetic heterostructure catalysts for oxygen-evolution.

Highly Mesoporous Cobalt-Hybridized 2D Cu3P Nanosheet Arrays as Boosting Janus Electrocatalysts for Water Splitting.

Recently, developing economical electrocatalysts with high performance in water decomposition has become a research hotspot. Herein, two kinds of cobalt-hybridized Cu3P nanostructure array electrocatalysts (including highly mesoporous 2D nanosheets and sugar gourd-like 1D nanowires) were controllably grown on a nickel foam substrate through a simple hydrothermal method combined with a subsequent phosphating treatment method. An electrocatalytic test indicated that the as-prepared 2D nanosheet array exhibited excellent activity and stability toward hydrogen evolution reaction under alkaline conditions, which offered a low overpotential of 99 mV at 10 mA/cm2 and a small Tafel slope of 70.4 mV/dec, whereas a competitive overpotential of 272 mV was required for oxygen evolution reaction. In addition, the 2D nanosheet array delivered a low cell voltage of 1.66 V at 10 mA/cm2 in a symmetric two-electrode system, implying its huge potential in overall water decomposition. The electrocatalytic performance is superior to the as-prepared 1D nanowire array and most of the Cu3P-related electrocatalysts previously reported. Experimental measurements and first-principles calculations show that the excellent performance of the 2D nanosheet array can be attributed to its unique 2D mesoporous structure and hybridization of cobalt, which not only provide a large electrochemically active surface and fast electrocatalytic reaction kinetics but also weaken the binding strength of electrocatalytic reaction intermediates. The present study provides a simple and controllable approach to synthesize Cu3P-based bimetallic phosphide nanostructures, which can be used as boosting Janus electrocatalysts for water decomposition.

Active Site Engineering in CoP@NC/Graphene Heterostructures Enabling Enhanced Hydrogen Evolution.

As the core of an electrocatalyst, the active site is critical to determine its catalytic performance in the hydrogen evolution reaction (HER). In this work, porous N-doped carbon-encapsulated CoP nanoparticles on both sides of graphene (CoP@NC/GR) are derived from a bimetallic metal-organic framework (MOF)@graphene oxide composite. Through active site engineering by tailoring the environment around CoP and engineering the structure, the HER activity of CoP@NC/GR heterostructures is significantly enhanced. Both X-ray photoelectron spectroscopy (XPS) results and density functional theory (DFT) calculations manifest that the electronic structure of CoP can be modulated by the carbon matrix of NC/GR, resulting in electron redistribution and a reduction in the adsorption energy of hydrogen (ΔGH*) from -0.53 to 0.04 eV. By engineering the sandwich-like structure, active sites in CoP@NC/GR are further increased by optimizing the Zn/Co ratio in the bimetallic MOF. Benefiting from this active site engineering, the CoP@NC/GR electrocatalyst exhibits small overpotentials of 105 mV in 0.5 M H2SO4 (or 125 mV in 1 M KOH) to 10 mA cm-2, accelerated HER kinetics with a low Tafel slope of 47.5 mV dec-1, and remarkable structural and HER stability.

General synthesis of mixed-dimensional van der Waals heterostructures with hexagonal symmetry.

The combination of two-dimensional (2D) materials with non-2D materials (quantum dots, nanowires and bulk materials), i.e. mixed-dimensional van der Waals (md-vdW) heterostructures endow 2D materials with remarkable electronics properties. However, it remains a big challenge to synthesize md-vdW heterostructures because of the difference of crystal symmetry between 2D and non-2D materials. Meanwhile, it is difficult to initiate the nucleation due to the lack of chemical active sites on chemical inert surfaces of 2D materials. Herein, we design a general chemical vapor deposition method for synthesizing a broad class of md-vdW heterostructures with well-aligned hexagonal symmetry including MoS2/FeS, MoS2/CoS, MoS2/MnS, MoS2/ZnS, Mo(SxSe1-x)2/ZnSxSe1-x, Mo(SxSe1-x)2/CdSxSe1-x. Combining with DFT calculation, we find that the hexagonal symmetry and the centered clusters of MoS2and Mo(SxSe1-x)2nanoflakes are two crucial factors to launch the hexagonally oriented growth and nucleation of non-2D materials on 2D materials. Our discovery opens an opportunity for the versatile hetero-integration of 2D materials and allows systematic investigation of physical properties in a wide variety of md-vdW heterostructures.