Nanoscale Laser Metallurgy and Patterning in Air Using MOFs

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Nanoscale Laser Metallurgy and Patterning in Air Using MOFs Haoqing Jiang, Shengyu Jin, Chao Wang, Ruiqian Ma, Yinyin Song, Mengyue Gao, Xingtao Liu, Aiguo Shen, Gary J. Cheng, and Hexiang Deng J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b00355 • Publication Date (Web): 01 Mar 2019 Downloaded from http://pubs.acs.org on March 1, 2019

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Journal of the American Chemical Society

Nanoscale Laser Metallurgy and Patterning in Air Using MOFs Haoqing Jiang,†,⊥ Shengyu Jin, Liu, †

,‡

,‡

Chao Wang,† Ruiqian Ma,† Yinyin Song,† Mengyue Gao,§ Xingtao

Aiguo Shen,§ Gary J. Cheng,*,⊥,

,‡

Hexiang Deng*,†,#

Key Laboratory of Biomedical Polymers-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan

University, Wuhan 430072, China ⊥

#

The Institute of Technological Sciences, Wuhan University, Wuhan 430072, China

The Institute for Advanced Studies, Wuhan University, Wuhan 430072, China. Brick Nanotechnology Center, Purdue University, West Lafayette, IN, USA

‡

School of Industrial Engineering, Purdue University, West Lafayette, IN, USA

§

Key Laboratory of Analytical Chemistry for Biology and Medicine-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China Supporting Information Placeholder

ABSTRACT: We report metallurgy in nanoscale to generate metal nanoparticles, and their simultaneous patterning in one single step. This is achieved by the self-reduction of porous metal-organic framework crystals using nanosecond pulsed laser irradiation. Metal nanoparticles of Fe, Co, Ni, Cu, Zn, Cd, In, Bi, and Pb with uniform sizes (controllable between 3 to 200 nm) and gaps (as narrow as 2 nm) are produced by nine different metal-organic frameworks, where atomically dispersed non-noble metal ions are reduced and gathered across the pores. The instant light absorption and cooling at local positions by laser allows for precise and efficient patterning of metal nanoparticles. This new method is suitable for device fabrication with a speed of 15 mm2s-1 on glass, consuming only 1.5-watt power. A large variety of metal nanoparticle three dimensional architectures are demonstrated, among which one architecture exhibits enhanced plasmonic effect homogenously across the entire pattern for the detection of molecules with extremely low concentration (10-12 M). These architectures are extremely stable in air and humidity during production, usage and storage, without altering oxidation state for 6 months.

INTRODUCTION Chemical reduction of ores to produce bulk metals, known as metallurgy, is a key revolution in human history.1 It continues to serve as an attractive modern technology in the production of metal nanoparticles (MNPs) with unique electrical, magnetic, catalytic and optical properties.2-8 The realization and optimization of these properties bring out three critical scientific challenges: (1) precise control of size and shape of MNPs, (2) spatial arrangement of MNPs to form designable architectures, and (3) obviation of undesirable aggregation and oxidation in air. Each of these challenges has been successfully handled seperately,9-13 however, methods addressing all three aspects are rare. Theoretically, it could be achieved by combining multiple consecutive steps, but at the cost of complicating the production process and sacrificing the reproducibility. Here, we show that metallurgy in nanoscale and patterning of the resulting uniform MNPs can be achieved in one single step, where porous metal-organic frameworks (MOFs) are used as the metal containing precursor and laser as the energy source, a method termed as nanoscale laser metallurgy and patterning (nano-LaMP) (Figure 1). The typical size of MNPs are 13 nm with narrow size distribution (±3 nm). These MNPs are accurately arranged to form a three-dimensional (3D) architecture for the construction of designable patterns. The thickness of the pattern is 30 nm, measuring up to two layers of MNPs, where the conductivity of metals is preserved. The precision of nano-LaMP method allows for the generation of uniform gaps between MNPs, as narrow as 2 nm, leading to enhanced plasmonic effect for the detection of molecules with extremely

low concentration (10-12 M). A large variety of MNPs including Fe, Co, Ni, Cu, Zn, Cd, In, Pb, Bi can be generated using this method, each having a uniform particle size (tunable between 3 to 200 nm) and gap (between 2 to 50 nm). These MNPs are produced in air, and can be stored and manipulated in humidity without aggregation or oxidation. Patterns of these MNPs can be produced with fast speed, high reproducibility and low power consuming. This method is suitable for device fabrication and largescale production taking the physical advantage of efficient and scalable laser processing,14-16 while precise control in the size and gap of MNPs is achieved by the chemistry of MOFs. MOF, as the key component in nano-LaMP method, is a class of porous crystalline material constructed by linking metal ions with organic linkers.17-19 The coordination between metal ions and organic linkers forms secondary building units (SBUs), which allows for the efficient absorption of light with the wavelength covering ultraviolent to near infrared.20,21 In nano-LaMP method, laser accurately delivers patches of highly concentrated energy to the metal ions in MOF crystals that are transferred to the carbonaceous organic linkers (Figure 1B), resulting in the formation of reductive species, which in turn reduce the metal ions to atoms. These atoms are sputtered out from the pores of MOF crystals and gathered to MNPs with uniform sizes and gaps at the specific site of laser irradiation (Figure 1D). The reduction sites of the MOFs to MNPs are controlled by the movement of the laser spot, leading to the generation of desirable patterns (Figure 1C and 1D).

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Figure 1. Conversion of MOF to MNPs in air using nanosecond pulsed laser. (A) HKSUT-1, composed of Cu2+ clusters and benzene1,3,5-tricarboxylate, was used as precursor for nano-LaMP method. Cu2+, C and O are marked in blue, gray and red, respectively. Illustrations of (B) experimental setup and (C) beam scribing process in nano-LaMP method. (D) Mechanism for the production of MNPs by laser irradiation on MOFs in air. Pulses in red represent photos in the laser, while the irradiation in blue represents instant cooling on glass. Cu atoms are marked in yellow. (E, F) Reflective optical images of a circuit and Chinese traditional phoenix paper-cut pattern written by nano-LaMP on glass. (G) SEM images reveal the clear-cut corner and edge in the details of patterns from (E) and (H). (H) Optical image of the samples ready for nano-LaMP. Scale bar is 2 mm in (E, F), 20 µm in (H), and 200 µm in (G). Different from metal precursors dispensed in solution, commonly used in “bottom-up” methods,9-13 MOFs, as solid-state materials, are ideally suited for storage and transportation. Previous studies have demonstrated that MOFs could be converted to zero-oxidation state metals through pyrolysis.22 In contrast, the

nano-LaMP method uses laser as energy source, where energies are precisely focused at desirable positions, thus making it possible to generate patterns locally without affecting the adjacent area. Such capability is unavailable in any other energy sources for the production of MNPs. In practice, extra protections such as vacu-


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Figure 2. Structure characterizations of MNP 3D nanostructure produced by nano-LaMP method. (A) Optical image of Cu nanoparticlebased grids as nanodevices. (B) Electrical conductivity test of the nanodevice with different line width in the pattern. (C) SEM image of Cu nanoparticle patterns deposited on glass in cross-section view from backscattered electron signals. The thickness of the pattern is ~30 nm. (D) SEM image of Cu nanoparticles revealing their uniform particle sizes and gaps. (E) High resolution TEM image shows that each Cu nanoparticle is wrapped by thin layers of graphene. (F) TEM image in relatively low magnification, and (G) nanogaps clearly displayed in the map of electric field enhancement generated by FTDT method based on TEM image. (H) Selected area electron diffraction pattern of the Cu nanoparticles matched well with metallic Cu. (I) PXRD and (J) XPS patterns of freshly prepared Cu nanoparticle patterns and the corresponding sample after exposure in air for 6 months. Scale bar is 2 mm in (A), 200 nm in (C), 100 nm in (D), 4 nm in (E), 20 nm in (F, G) and 5 nm-1 in (H). um, solvent, inert or reductive gases are usually required during the production of MNPs,3-13 which not only complicates the fabrication processes, increases the production cost, but also precludes the production, manipulation and storage of MNPs in ambient conditions. We found that thin layers of graphene are simultaneously formed on the surface of MNPs produced by nano-LaMP, that provide optimum protection against aggregation and oxidation. Unlike other carbon protected MNPs produced by arcdischarge,23 chemical vapor deposition (CVD) and calcination,8,24 the spatial arrangement of MNPs and the gaps between them are precisely controlled in this study, due to the atomically dispersed nature of metal ions in MOF backbone. More importantly, these MNPs are gathered to form 3D architectures that are capable to be patterned under the guidance of laser. EXPERIMENTAL SECTION General Synthetic Procedure of MOFs. Here we use a common Cu containing MOF, HKUST-1,25 as an example to illustrate the operation of nano-LaMP method. Micro HKUST-1 crystals were obtained by mixing Cu(NO3)2·3H2O and benzene1,3,5-tricarboxylate (BTC) in N,N-dimethylformamide (DMF), ethanol and water and incubating at 358 K for 12 h.26 The ob-

tained octahedral shaped HKUST-1 crystals exhibit a threedimensional (3D) porous structure with the pore diameter of ~9 Å (Figure 1A). The average particle size of HKUST-1 crystals used in this study was 20 µm, as observed in their optical and scanning electron microscopy (SEM) images (Figures S1 and S2). The assynthesized crystals were activated by solvent exchange followed by vacuum to remove solvent from the pores. The phase purity of this MOF was confirmed by powder X-ray diffraction (PXRD), the pattern of which matched well with the simulated pattern based on the single crystal structure of HKUST-1. BrunauerEmmett-Teller (BET) surface area of this MOF sample was 1580 m2 g-1, obtained by the N2 adsorption isotherm measured at 77 K, which is consistent with previous reports.25,26 We also use the solvothermal method to synthesise MOFs containing other metal ions. Specifically, MIL-100, ZIF-12, Ni-BTC-bipy, Zn-MOF-74, Cd-MOF-74, CPM-5, Pb-TCPP, and CAU-7,27-34 containing nonnoble metal ions of Fe, Co, Ni, Zn, Cd, In, Pb, and Bi, respectively, are synthesized and activated to prepare the corresponding MOF precursors for nano-LaMP method. The nano-LaMP method. The nano-LaMP method involves two straightforward steps, placement of MOF crystals in a laser



processing zone, and subsequent laser scribing (Figures 1B and S3). In the preparation for nano-LaMP, HKUST-1 crystals were evenly and closely packed in between two glass slides in air. Specifically, in the packing process, MOF particles were gradually filled in a circular mold surrounded by a metal foil, where this metal foil is sandwiched in between two glass slides (Figures 1B and 1G). Metallic Cu was produced by direct laser scribing on to the solid MOF powders, which convert the MOFs to form Cu nanoparticles covered by thin protective graphene outer layers (Figure 1C). These Cu nanoparticles were deposited as a thin film of continuous 3D architecture on the top glass (Figure 1D). The line width of the laser beam can be set between 55 to 380 µm according to the focus length. RESULT AND DISCUSSION The deposited Cu nanoparticle 3D architecture on glass formed by nano-LaMP method exhibit metallic luster under reflected light (Figures 1E, 1F and S5, S6), while they look dark green under transmitted light, which is consistent with the presence of a broad peak around 550 nm in its UV-Vis transmission spectrum (Figure S6). In precious studies, metals were either observed as byproduct in the pursuit of porous carbon converted from MOFs,35 or produced under inert or reductive atmosphere, otherwise metal oxides emerged.22,36 Unfortunately, none of these works demonstrated the capability to fabricate patterns of MNPs. Here, non-noble MNPs are generated by laser as the main product (>70 % by weight) and the entire process is operated in air without extra protective environment (Figure S15). High temporal and spatial accuracy provided by laser, as well as the capability to fabricate patterns are unmatched by direct heating. In order to illustrate the precision of nano-LaMP method, various patterns with fine details were directly written on glasses, such as conductive circuit and Chinese traditional phoenix paper-cut pattern (Figures 1E and 1F), where clear cut corners and edges were formed (Figure 1F), as a result of precise spatial and temporal control by the laser. The entire pattern was finished within 50 seconds in a circular area of 12 mm in diameter, demonstrating rapid processing speed suitable for large scale production (Video S1-S4). The morphology of Cu nanoparticle films on glass was studied by SEM. Backscattered electron (BSE) image analysis was used to separate the signal of metal species from that of carbon species by atomic number, which revealed the uniform distribution of Cu nanoparticles with an average particle size of 13 nm and 2 nm gaps (Figures 2D and S7, S8). Secondary electron (SE) image of the cross section showed the thickness of the film was 50 nm, while corresponding BSE image demonstrated the thickness of metal species was approximately 30 nm, corresponding to two layers of Cu nanoparticles (Figures 2C and S9, S10). The bulk phase purity was confirmed by the presence of fingerprint peaks of metallic Cu at 2θ=43.3°, 50.4° and 74.1° in the PXRD pattern, and the absence of peaks from CuO or Cu2O (Figure 2I). The phase purity in microscopic scale was demonstrated by the selected area electron diffraction (SAED) pattern of the nanoparticle film examined under transmission electron microscopy (TEM), where diffraction circles corresponding to 111, 200, 220 and 311 facets of metallic Cu were clearly observed (Figure 2F). The oxidation state of Cu was studied by X-ray photoelectron spectroscopy (XPS). Detailed analysis of the Cu 2p and Cu LMM Auger spectra showed that all Cu species are in zero oxidation state (Figures 2I and 2J).37 The positions and shapes of these peaks are distinctly different from those of the HKSUT-1 sample (Figure S13), indicating the complete reduction of MOFs. High resolution TEM (HR-TEM) showed that each of the Cu nanoparticle was evenly wrapped by a few graphene layers, where characteristic gaps of 0.34 nm between the layers were observed (Figures 2E and S14). The formation of graphene layers on these Cu nanopar-

ticles provides excellent protection against oxidation. These wellprotected Cu nanoparticles are extremely stable in air and humidity, without losing their metallic nature for 6 months (Figures 2I and 2J). The weight loss was 11 % from thermogravimetric analysis (TGA) at 800 °C in air flow, to give a weight percentage of 71 % for Cu nanoparticles in the entire thin film on glass (Figure S15). A series of experiments were performed to investigate the mechanism of nano-LaMP. First, a UV-VIS-NIR spectrum was used to study the light absorption of an HKSUT-1 sample. The molecular components of the MOF, BTC linker and Cu(NO3)2·3H2O, as well as other Cu species were also studied as controls. High light absorptivity was observed in all Cu containing species at wavelength of 1064 nm, 70, 81 and 94 % for HKSUT-1, CuO and Cu(NO3)2·3H2O, respectively, while low laser absorptivity of only 17 % was observed in the BTC linker component (Figure S16). An isoreticluar MOF composed of Zn SBU instead of Cu, HKUST-1(Zn), was also tested and only exhibited a laser absorptivity of 32 % (Figures S16 and S17). All these above showed that the light absorption was taken place at the Cu containing SBUs in MOF (Figure S23). The high light absorptivity of MOFs leads to high energy conversion efficiency, much improved in comparison to that of the traditional heat exchange methods, where the low thermal conductivities of the MOFs become the limit.38 Second, the light absorbed by MOFs was converted to heat, and the temperature of the entire MOF was raised rapidly (Figure S18). The instantaneous temperature upon laser irradiation with the spot size of 55 µm was accurately measured by light irradiation spectrum fitting against Plank’s black body irradiation equation (Figures S21 and S23b). The local temperature increased as the power of the laser increased, 2210, 2290, 2360 and 2470 K for the power of 3.5, 4.0, 4.5 and 5.0 W, respectively, high enough to induce the decomposition of the organic linkers in the MOF. The decomposition of the carbonaceous linker created a local reductive chemical atmosphere, where H2, CO, CH4, C2H2 and C2H4 were detected by gas chromatography (GC) (Figures S23c and S23e). This reductive atmosphere and extremely high temperature at the local position of laser irradiation led to instant reduction of Cu cations in MOF to atomic Cu species, which then gathered to form Cu MNPs with protective graphene layers, before the diffusion of air from surrounding areas that would have oxidized these MNPs. The size of Cu MNPs was precisely controlled by the laser power. As the laser power increased gradually from 1.5 to 4.5 W, more atomic Cu species were generated at the same time, thus the size of the resulting Cu nanoparticles increased gradually from 13 nm to 200 nm (Figure S7). Third, the pores in MOF structure provide pathways for travel of atomic Cu species to reach glass surface, where they were cooled instantly to create Cu MNPs (Figure S23e). Splashes of atomic Cu species were directly observed along the direction of laser beam reaching more than 1 cm height, when the top glass was removed (Figure S23f). The critical role of porosity for the use of MOF in nano-LaMP method was demonstrated by a control experiment utilizing an organic Cu salt. No obvious metal deposition was detected on glass when nonporous copper benzoate was tested (Figure S19 and S20), although high light absorption was observed (Figure S16). This can be attributed to the lack of pathways for the escape of reduced Cu atoms. Similar phenomena were also observed in the test using a physical mixture of Cu(NO3)2·3H2O and BTC as the precursor, further confirming the importance to have extended pore structure in the precursor, a unique feature of MOF, for the production of metals in nanoscale. The experiments above outlined the three critical factors in the mechanism for the creation of Cu MNPs by nano-LaMP method:


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Journal of the American Chemical Society (1) efficient light adsorption by MOFs, (2) generation of local reduction atmosphere with instant heating and cooling, and (3)

Figure 3. Various non-noble MNPs produced by nano-LaMP method in air displayed along with their corresponding MOF crystals. From left to right, crystal structure of MOFs, optical images, SEM images, PXRD patterns and XPS patterns of MNPs. (A) Fe nanoparticles produced from MIL-100. (B) Co nanoparticles for ZIF-12. (C) Ni nanoparticles from Ni-BTC-bipy. (D) Zn nanoparticles from Zn-MOF74. (E) Cd nanoparticles from Cd-MOF-74. (F) In nanoparticles from CPM-5. (G) Pb nanoparticles from Pb-TCPP. (H) Bi nanoparticles from CAU-7. Fe, Co, Ni, Zn, Cd, In, Pb and Bi are labeled in orange, purple, green, blue, light green, light yellow, yellow and light red, respectively. The crystal lattice of each MNP is displayed on the top right corner of the corresponding optical image. The square patterns are 10 mm×10 mm in the optical images. Scale bar is 200 nm in the SEM images. XPS patterns of fresh prepared sample and sample exposed in air for 1 month was labeled in gray and green circles, respectively. Wavelength of the X-ray source is 1.54056 Å.



Figure 4. In comparison to previous physical and chemical methods for the production of MNPs, nano-LaMP method is capable to produce patterns of MNPs with uniform size and gaps in concurrent with the conversion process. (A) Radar chart for the comparison of various methods for the production of MNPs with multivariate capabilities including chemical stability of the produced MNPs, patterning capability, uniformity of the particle and gap size, fabrication speed, and variety of metals. (B) Detection of trace amount of molecule, CVa here, utilizing plasmatic effect generated from the nanogaps between Cu nanoparticles, by simply dropping aqueous solution of CVa on the device. (C) SERS mapping along the line in the device marked in (B). Uniform signals are observed across the entire device. (D) SERS performance of Cu-Ag nanoalloy pattern under different concentration of the CVa molecule in the test solution. porosity that favors the traveling of atomic Cu species (Figure S23). The nano-LaMP method is applicable to a wide range of nonoble metals. In addition to Cu, eight MOFs, CAU-7, CPM-5, ZnMOF-74, Cd-MOF-74, Pb-TCPP, MIL-100, ZIF-12 and Ni-BTCbipy, were used to generate eight different nanoparticles of Bi, In, Zn, Cd, Pb, Fe, Co and Ni, respectively, all in zero oxidation state, and directly produced in air (Figures 3 and S34 to S42). The crystallinities of these MOFs were confirmed by PXRD (Figure S25 to S32). Their porosity was measured by N2 absorption at 77 K, to give surface areas varied from 110 to 1760 m2g-1 (Figure S25 to S32). The laser absorptivity for MOF-74, MIL-100, ZIF-12, NiBTC-bipy are 48~93 % (Figure S33), and the corresponding MNPs can be generated by laser with the power of 3.5 w. The other MOFs, CAU-7, CPM-5, Cd-MOF-74, Pb-TCPP, exhibit relatively low laser absorptivity of 13 % to 28 %, nevertheless, MNPs can be still produced by elevated laser power of 4.5 w (Figures 3 and S33 to S42). These MNPs, with their characteristic crystal lattice, display metallic luster on glass (Figure 3). PXRD and XPS were used to confirmed the phase purity of these MNPs and their oxidation state, respectively (Figures 3 and S43 to S45). Their particle sizes are uniform as revealed by SEM images (Figure 3). Transition metals of Fe, Co and Ni show small uniform particle sizes from 3 to 15 nm accordingly, while uniform particles with larger sizes (20~200 nm vary from different metal) was found in metals from main group. All these MNPs are stable in air and humidity (Figure 3). The utilization of laser irradiation in nano-LaMP allows for fast and efficient on-chip fabrication of devices in nanoscale, where programmable patterns can be directly written on glasses (Figures 2A, S47 and Video S1-S4). The patterning process take

place concurrently with the production of MNPs by nano-LaMP method, while in other chemical or physical method at present, patterning is usually achieved before or after the formation of MNPs (Figure 4A and Table S3).11,39 In addition, nano-LaMP method excels in uniformity of the particle size in comparison to physical method such as laser ablation,14 and outperforms chemical methods, such as such as atomic layer deposition, pyrolysis and reduction by wet-chemistry,3-13,22,40 in the conversion speed (Figure 4A and Table S1). Furthermore, the patterns of MNPs produced by nano-LaMP are extremely stable in air, thus favoring the storage and transportation of corresponding devices. Last but not the least, the NMP patterns are firmly attached to the surface of glass substrate without any chemical or physical pretreatment (Figure S49), ideally suited for rapid and facile device fabrication. The positional accuracy of the patterns was guaranteed by the optics of the nanosecond pulsed laser, where a small spot size of 55 µm was accessible in this study (Figure S47). The conductivity of the patterns constructed by Cu nanoparticles was high, 1.2×104 S m-1, thus demonstrating the quality of the devices (Figures 2C and S48). This was illustrated in the grids fabricated by nanoLaMP in air with the size of 20×20 mm and interval line distance of 300 µm, which was used to light up a LED light at every corner with a bias voltage of 5.0 V (Figure S49). The speed of fabrication was 15 mm2 s-1, thus a nanodevice in 15×15 mm size can be fabricated within 12 seconds consuming only 1.5 watts power (Video S4), making nano-LaMP an economic solution for nanofabrication. A nano-device composed of MNP grid on glass with 15×15 mm in size was fabricated and directly used for molecular detection by surface enhanced Raman scattering (SERS, Figures 4B and S50 to S58), to further illustrate the capability of the nanoLaMP method. This nano-device can be made of pure Cu and Cu-


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Journal of the American Chemical Society Ag alloys, where extremely low detection limit of 10-12 M for cresyl violet acetate (CVa) was observed (Figure 4D), which is comparable to the state-of-the-art SERS devices (Table S4),41-43 but unprecedented homogeneity (Figure 4C). This was achieved by the uniformly narrow nano-gaps between adjacent MNPs across the entire nano-device, as confirmed by the “hot spots” obtained from finite-difference time-domain (FTDT) simulation on the basis of the TEM image (Figures 2F, 2G and S51). The uniformity of the MNPs in the 3D architecture leads to identical signals across the entire chip (Figure 4C), and the 3D architecture of MNPs are stability in air and humidity for 6 months without altering their oxidation state or decrease in performance (Figure S54). CONCLUSION In summary, we demonstrate the one-step production of nine non-noble MNPs and their corresponding patterns in ambient condition using MOF as precursor and laser as energy source. The unique arrangement of metal ion and organic linker in MOFs and the precise spatial control of laser make this technique suited for nano-device fabrication in a low-cost and time-saving way. MNPs are well known to exhibit unique magnetic, optic and electronic properties, the simultaneous patterning of these MNPs by nanoLaMP method will provides an extra dimension for the exploration of NMPs and possibly lead to previous inaccessible properties or functionalities, beyond the plasmatic effect demonstrated here as an simple illustration. The wide choices of MOFs and the flexibility of their corresponding MNP patterning produced by nano-LaMP will stand as a useful tool to explore the fields of catalysis, batteries and electronics.

Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Details of the synthetic procedures of MOFs and the experimental setups of nano-LaMP method, the morphology and structural characterizations of MOFs and metal nanoparticles, mechanism study of nano-LaMP, SERS measurement, performance comparison, and additional references (PDF)

AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected]

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT We thank Y. Wu, X. Xu, Q. Liu, Prof. F. Ke, and Prof. H. Cong for their valuable advices of this research. We also thank the Test Center and the Large-scale Instrument and Equipment of Wuhan University, the Core Research Facilities of College of Chemistry and Molecular Sciences, Shanghai Synchrotron Radiation Facility (for XRNES test), and UC Berkeley-Wuhan University Joint Innovative Center for the assistance in material characterizations. We acknowledge the supports from National key R&D program of China (2018YFB1107700), National Natural Science Foundation of China (21471118, 91545205, and 91622103), National Key Basic Research Program of China (2014CB239203), and Innovation Team of Wuhan University (2042017kf0232).

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