胺功能化的銅催化劑：氫鍵介導(dǎo)的電化學(xué)CO2還原為C2產(chǎn)物以及優(yōu)越的可充電Zn-CO2電池性能

摘要：有機(jī)分子功能化是一種有前景的策略，用于調(diào)控電化學(xué)CO2還原反應(yīng)（eCO2RR）的C2+產(chǎn)物選擇性和活性。然而，我們對(duì)于電化學(xué)CO2還原調(diào)控機(jī)制的分子水平理解仍然不夠清晰。在本文中，我們成功制備了銅納米顆粒，并使用一系列胺類衍生物（如十六胺（HAD）、N-甲基十六胺（N-MHDA）、十六烷基二甲胺（HDDMA）和十六酰胺（PMM））對(duì)其進(jìn)行功能化，以系統(tǒng)地研究胺表面活性劑分子結(jié)構(gòu)對(duì)eCO2RR選擇性和活性的影響。結(jié)果表明，HDA的功能化可以將C2產(chǎn)物和C2H4的法拉第效率（FE）提高至73.5%和46.4%，并且在?0.9 V vs. RHE （可逆氫電極）電位下，C2產(chǎn)物的分電流密度為131.4mA?cm?2。理論研究發(fā)現(xiàn)，HDA通過與CO2和eCO2RR中間體之間的氫鍵相互作用，富集了*CO2、*CO和其他反應(yīng)中間體，降低了CO―CHO耦合反應(yīng)的動(dòng)力學(xué)能壘，從而促進(jìn)了eCO2RR向C2產(chǎn)物的轉(zhuǎn)化。當(dāng)胺基的H原子被甲基取代后，氫鍵相互作用減弱，競(jìng)爭(zhēng)的析氫反應(yīng)加劇。PMM通過Cu―O鍵與Cu表面發(fā)生鍵合，而不是通過Cu―N鍵，導(dǎo)致Cu-PMM更傾向于產(chǎn)乙醇。原位拉曼光譜顯示，在Cu-HDA表面，CO主要吸附在Cu的頂位吸附位點(diǎn)上，與在Cu表面上的橋式吸附不同，這可能是因?yàn)榍罢弑砻鎸?duì)CO的富集引發(fā)了CO的吸附構(gòu)型變化。HDA功能化還提高了Cu催化劑的表面pH?；贑u-HDA組裝的可充電Zn-CO2電池在放電電流密度為16 mA?cm–2時(shí)，最大功率密度為6.48 mW?cm–2，并具有長(zhǎng)達(dá)60 h的良好充放電穩(wěn)定性。本研究的重點(diǎn)在于通過在分子水平上調(diào)節(jié)Cu基材料的CO2RR活性和選擇性，促進(jìn)CO2-C2的轉(zhuǎn)化，這可能為提高C2產(chǎn)物的產(chǎn)率提供新的見解。

關(guān)鍵詞：二氧化碳還原；CO―CHO耦合；有機(jī)分子功能化；原位拉曼；C2產(chǎn)物；Zn-CO2電池

中圖分類號(hào)：O646

Abstract： The electrochemical carbon dioxide reduction reaction（eCO2RR） can convert CO2 into valuable chemicals， achieving a carboncycle. Copper-based catalysts have demonstrated a unique ability toproduce C2+ products in eCO2RR， which is often limited by the scalingrelationship of the reaction intermediates， complex reaction mechanismand competitive H2 evolution. Organic functionalization is a promisingstrategy for regulating the activity and selectivity of eCO2RR toward C2+products. However， the mechanism behind such regulation of eCO2RR，especially at the molecular level， remains elusive. In this study， Cunanoparticles were prepared and functionalized with a set of aminederivatives， including hexadecylamine （HDA）， N-methylhexadecylamine （N-MHDA）， hexadecyldimethylamine （HDDMA），and palmitamide （PMM）. The impact of the molecular structure of the amine surfactants on the selectivity and activitytoward eCO2RR was systematically explored through both experiments and theoretical calculations. X-ray photoelectronspectroscopy and density functional theory calculations revealed that HDA functionalization of the Cu catalyst surfaceresulted in negative charge transfer from amine molecules to Cu. ECO2RR was examined in a 1.0 mol?L?1 KOH aqueouselectrolyte. HDA functionalization of the Cu catalyst achieved the highest Faradaic efficiency （FE） of 73.5% for C2 productsand 46.4% for C2H4， respectively. It also provided the highest C2 partial current density of 131.4 mA?cm?2 at ?0.9 V vs.reversible hydrogen electrode （RHE） among these amine derivatives functionalized Cu catalysts. In contrast， the highestFE and partial current density for C2 products achieved with pristine Cu catalysts were only 27.0% and 50.5 mA?cm?2，respectively. Theoretical studies demonstrated that hydrogen bonding interactions of HDA with CO2 and eCO2RRintermediates enriched CO2， CO， and other intermediates， lowered the kinetic energy barrier of CO―CHO coupling andthereby promoted eCO2RR to C2 products. Replacing the H atoms of the amine group with methyl groups in N-MHDA andHDDMA resulted in dominant hydrogen evolution reaction （HER） in eCO2RR. PMM bonding with the Cu surface througha Cu―O bond， instead of Cu―N bonding as in HDA， N-MHDA and HDDMA， resulted in preferred ethanol production. Insitu Raman spectroscopy indicated CO adsorption on Cu at atop sites for HDA-capped Cu catalysts， instead of bridge siteCO adsorption on clean Cu surfaces， possibly due to the enriched CO in the former case. HDA also increased the localpH relative to pristine Cu catalysts. The Cu-HDA-based rechargeable Zn-CO2 battery exhibited a superior maximum powerdensity of 6.48 mW?cm–2 at a discharge current density of 16 mA?cm–2 and remarkable rechargeable durability for 60 h，outperforming most of the reported catalysts in the literature. This work enhances CO2-C2 conversion by tuning theeCO2RR activity and selectivity of Cu-based materials， unravels the reaction mechanism at the molecular level， andprovides new insights for promoting C2 products in eCO2RR through surface functionalization with organic molecules.

Key Words： CO2 reduction; CO―CHO coupling; Organic functionalization; In situ Raman; C2 product;Zn-CO2 battery

1 Introduction

eCO2RR） offers an opportunity to convert CO2 into valuablechemicals and fuels using renewable energies， providing a costeffectiveand environmentally friendly approach to addressingclimate change induced by fossil fuel-based industries 1–3. It hasgarnered considerable attention for its potential in renewableenergy conversion and storage， contributing to a carbon-neutralcycle 4–7. However， the highly complex mechanism of eCO2RR，involving multiple electron and proton transfers， leads to slowreaction kinetics and diverse reaction products 8–10. Additionally，eCO2RR also faces competition from the hydrogen evolutionreaction （HER）， which hinders CO2 conversion efficiency andproduct selectivity 11–14. Therefore， it is crucial to developefficient and selective catalysts for eCO2RR and understand thefundamental mechanisms to fully exploit the potential of CO2 asa renewable resource.

Copper （Cu）-based catalysts have generated significantinterest due to their ability to convert CO2 into hydrocarbons andoxygenates， such as ethylene， ethanol， and propanol 13，15，16.Numerous strategies have been adopted to improve the selectivity of C2+ products for Cu-based catalysts， such assurface doping 17，18， defect engineering 19，20， crystal facetregulation 21，22， alloying with other metals 7，18， modulating fieldeffect 23，24 and organic functionalization 25，26. Among thesestrategies， functionalization of Cu catalysts with organics canmediate the adsorption of reaction intermediates by regulatingthe environment of the catalyst surface 27， offering a means tomodulate the selectivity of eCO2RR 26，28. Moreover， thehydrophobicity conferred by organic molecules， which can beregulated by the alkyl chain length， inhibits the HER competitionand benefits in the sealing and accumulation of gas-phasereactants， such as CO2 and CO， thus favoring the eCO2RR to C2products 29，30. Therefore， surface functionalization of metalcatalysts with organics holds significant prospects towardseCO2RR.

Amino derivatives， which can interact with CO2 throughLewis acid-base pairs and bond with eCO2RR intermediatesthrough hydrogen bonding interactions， have been used for CO2capture 31，32 and regulation of activity and selectivity of eCO2RRtowards C2 products 33. In previous studies， thick polyanilinefilm was coated on copper surfaces， significantly improving the selectivity of C2+ products on polycrystalline copper 34. In suchcases， the impact of the bonding interaction between such aminesurfactants with Cu substrate on the activity and selectivity ofeCO2RR was largely ignored. Additionally， most of the aminefunctional groups are far away from the Cu surface and theeCO2RR intermediates on the Cu surface. Thus， the underlyingmechanism for selective production of C2 products at themolecular level remains elusive.

Herein， copper nanoparticles （Cu NPs） were functionalizedwith hexadecylamine （HDA）， N-methylhexadecylamine （NMHDA），hexadecyldimethylamine （HDDMA）， and palmitamide（PMM）， respectively， to systematically explore the impact of theperturbation of the molecular structure of the amine surfactantson the selectivity and activity of eCO2RR towards C2 products.DFT calculations and in situ Raman spectroscopy wereperformed to unravel the eCO2RR mechanism and the structureactivityrelationship at the molecular level.

2 Results and discussion

The synthetic process and surface functionalization of coppernanoparticles （Cu NPs） are depicted in Fig. 1a and elaborated inthe Experimental section （Supporting Information）. Themolecular structures of HDA， PMM， N-MHDA， and HDMA canbe found in Fig. S1 （Supporting Information）. The morphologyof Cu-HDA was characterized using transmission electronmicroscopy （TEM）. As shown in Fig. 1b–d， Cu-HDA exhibitsclear nanoparticle morphology with a size of 61.1 ± 2.3 nm， and the lattice fringe with a lattice spacing of 0.208 nm can bedistinctly observed， corresponding to the （111） plane of metallicCu. Fig. S2 displays the X-ray diffraction （XRD） pattern withpeaks located at 43.3°， 50.4°， and 74.1°， clearly indicatingdiffraction from （111）， （200）， and （220） planes of Cu （PDF 04-0836）. After functionalization with HDA， the diffraction peaksof Cu NPs remain unchanged.

X-ray photoelectron spectroscopy （XPS） was employed toinvestigate the surface composition and chemical state of CuNPs before and after surface functionalization with HDA. In thehigh-resolution Cu 2p XPS spectrum of Cu NPs （Fig. 1e）， thetwo peaks observed at 932.1 and 951.9 eV originate from Cu2p3/2 and Cu 2p1/2 of Cu0/+1 35， while the peaks at 933.9 and 953.7eV are assigned to Cu 2p3/2 and Cu 2p1/2 of Cu2+. The peaks ataround 941.5 and 943.5 eV represent satellites peaks of Cu2+.Following functionalization with HDA， a negative shift of 0.2eV is observed for Cu 2p peaks， indicating electron transfer fromHDA to Cu NPs. As illustrated in the Cu Auger LMM spectra（Fig. 1f）， the peaks at 568.0 and 568.9 eV can be attributed toCu0 and Cu2+ as the main oxidation states， respectively. Both theXPS and Auger LMM spectra of Cu reveal that surfacefunctionalization with HDA leads to an increased content of Cu0relative to Cu2+. Furthermore， the presence of N is confirmed bythe N 1s peak （Fig. 1g）， confirming the successfulimmobilization of HDA on Cu. The binding energy of N 1s is399.7 eV， slightly higher than that of pristine amine （398.8 eV）due to the bonding interaction with Cu 36. Similar results are observed for Cu-PMM （Fig. S3a–c）.

The electrochemical performance of eCO2RR on theprepared catalysts was assessed through constant potentialelectrolysis in a flow cell reactor employing a 1.0 mol?L?1 KOHelectrolyte， as illustrated in Fig. 2 and detailed in Tables S1–S3（Supporting Information）. It is evident that HDAfunctionalization can effectively suppress the HER whilepromoting ethylene production in eCO2RR. The Faradaicefficiency （FE） of C2 products on Cu-HDA increases to 73.5%at ?0.9 V vs. reversible hydrogen electrode （RHE）， with FEs of46.4% for C2H4， 21.0% for C2H5OH， and 6.1% for CH3COOH，respectively. Interestingly， the Cu-PMM electrode exhibits FEof 49.6% for C2 products， which is mainly C2H5OH， with FE of28.1% at ?1.0 V vs. RHE. Both HDA and PMMfunctionalization display a positive effect in promoting theformation of C2 products， resulting in increased total currentdensity， partial current density， and FE of C2 products （Fig. 2d–f）. The total and partial current densities for C2 products reach179.5 and 131.4 mA?cm?2 at ?0.9 V vs. RHE. Tafel slopes forC2H4 and C2H5OH on Cu NPs， Cu-HDA， and Cu-PMM areshown in Fig. 2g，h. In C2H4 production， Cu-HDA exhibits aTafel slope of 743.7 mV?dec?1， significantly lower than that ofCu NPs and Cu-PMM， indicating a fast kinetic for C2H4formation in eCO2RR. Regarding ethanol production， Cu-PMMdemonstrates the lowest Tafel slope of 784.7 mV?dec?1，signifying a preference for ethanol production with PMMdecoration. Cu-HDA maintains stability for over 12 h at ?0.9 Vvs. RHE in 1.0 mol?L?1 KOH （Fig. 2i）， and the originalmorphology of Cu-HDA remains well-preserved after eCO2RRelectrolysis， as shown in Fig. S4， indicating its high stabilityunder the harsh electrochemical condition during eCO2RR.

It is speculated that the hydrogen bonding interactionbetween eCO2RR intermediates and hydrogen atoms in aminegroups may stabilize the reaction intermediates andconsequently regulate products selectivity. Thus， replacinghydrogen atoms of the amine group in HDA may suppresseCO2RR towards C2 products. As shown in Fig. S5a，b anddetailed in Tables S4， S5， Cu NPs were coated with N-MHDAand HDDMA， where one and two hydrogen atoms in aminegroups were replaced by methyl groups， respectively. Theelimination of hydrogen bonding interaction between aminesurfactants and eCO2RR intermediates results in only HER，underscoring the significance of hydrogen bonding in mediatingeCO2RR. Carbon monoxide is considered a significant intermediate of C2 products in eCO2RR. As demonstrated in Fig.S6 and detailed in Tables S6， S7， the FE of C2 products ineCORR is slightly higher than that in eCO2RR， where COconcentration is much higher in CORR than in eCO2RR，indicating that CO coverage on Cu-HDA in eCO2RR is close tooptimal for C―C coupling already. Additionally， the increasedFE for C2H4 further corroborates that HDA functionalization isbeneficial for C2H4 formation.

To investigate the interfacial hydrophilic characteristics，contact angle measurements were conducted on Cu and thesefunctionalized surfaces. Cu-HDA and Cu-PMM electrodesexhibits contact angles of 125.5° and 120.2°， respectively， whichare more hydrophobic than Cu NPs （102.5°）. Thishydrophobicity can be beneficial in suppressing the HER ineCO2RR （Fig. S7）.

To assess the intrinsic eCO2RR performance of the aminefunctionalizedCu catalysts， the electrochemically active surfacearea （ECSA） was evaluated by underpotential deposition of Pb（Pb UPD） using cyclic voltammetry （Fig. S8 and Table S8）.Compared to Cu NPs， the ECSA of Cu-HDA and Cu-PMMelectrodes decreased by 10% due to the coverage of organicligands. However， the current density of amine-coated Cucatalysts exhibits enhanced performance compared to pristineCu catalysts， indicating that the amine coating enhances thecatalytic activity of eCO2RR. As shown in Fig. S9 and detailedin Tables S9–S12， the FEC2 was significantly influenced by theHDA loading， achieving the maximum at a loading of 0.01mmol.

DFT calculations were conducted to explore the modulatedeCO2RR mechanism by amine surfactants at the molecular level.Propylamine was employed to equivalently simulate the HDAmolecule on the Cu （111） surface to maintain high computationalefficiency without changing the main characteristics ofsurfactants （Figs. S10–S16 and Tables S13， S14）. As shown inFig. 3a， the formation energy of *COOH from CO2 on Cu （111）-HDA is 1.10 eV， which is lower than that on the bare Cu （111）surface （1.25 eV）. This suggests that the formation of *COOHon Cu （111）-HDA is thermodynamically favored due tohydrogen bonding with amine， which may improve CO coverageon the Cu surface. CO adsorption （Fig. 3b） on Cu is enhanced by HDA due to hydrogen bonding. Both the increased CO coverageand CO adsorption are conducive to the subsequent C ― Ccoupling reaction.

The C―C coupling for the formation of C2 products canproceed through either the CO―CO or CO―CHO couplingpathway. The formation energy for the CO―CO intermediate onCu （111）-HDA is 1.43 eV， while it is 1.61 eV （Fig. S17a） on Cu（111）. These values are much higher than that of CO―CHO（Fig. 3b）， indicating a preference for the C ― C couplingmechanism via CO―CHO. To further explore the impact ofHDA on the coupling of CO―CHO， the transition states werealso investigated and are shown in Fig. 3b. The energy barrierfor CO―CHO coupling on Cu （111）-HDA （0.87 eV） is 0.23 eVlower than on Cu （111） （1.10 eV）， suggesting that surfacefunctionalization with HDA kinetically promotes CO―CHOcoupling on Cu for the formation of C2 products.

According to previous reports， ethylene and ethanol share acommon *CHCOH intermediate， which can be reduced to *CCHand *CHCHOH， the intermediates of C2H4 and C2H5OH，respectively 37. As shown in Fig. 3c， the lower free energy of theintermediates for C2H4 formation compared to Cu （111） suggeststhat C2H4 production is favorable on Cu （111）-HDA.Additionally， in Fig. S17b， the lower free energy of *CCH2 （0.12eV） compared to *CH3CHOH （0.17 eV）， which are theintermediates of C2H4 and C2H5OH on Cu （111）-HDA，respectively， suggesting that C2H4 formation is energeticallyfavored on Cu （111）-HDA. The formation energy of*CH3CHOH is also lower than that on Cu （111） （0.39 eV）， asshown in Fig. S17c， which enhances C2H5OH formation.Furthermore， the projected density of states （PDOS） for E ? Ef =?6.9 eV of *CO-adsorbed Cu （111）-HDA indicates stronger COadsorption compared to Cu （111） （E ? Ef = ?7.1 eV） and furtherbenefits the CO―CHO coupling reaction （Fig. S17d–e） 38. Thed-bands of metal hybridize with the σ-orbital of intermediates toform d―σ bonds. The shift of PDOS towards the Fermi levelindicates decreased electron occupation of the anti-bondingorbitals， thus strengthening the adsorption of CO on metalcatalysts 15.

The interaction between HDA and Cu occurs through N―Cubonds， and the hydrogen atoms of ―NH2 in HDA interact with*CO2 and key oxygenated intermediates （*COOH， *CO， *CHO，and *OCCHO）， contributing to enhanced CO coverage andCO―CHO coupling to improve C2 production （Fig. 3d–m）. Incontrast， PMM adsorbs on Cu through Cu―O bonds， and nohydrogen bonding between the hydrogen atom in the aminegroup and eCO2RR intermediates was observed in DFTcalculations. Only the nitrogen of ―NH2 forms hydrogen bondswith the key intermediate of ethanol （*CHCHOH）， thusstabilizing the ethanol intermediates and improving ethanolselectivity. This is consistent with the electrochemicalcharacterization results （Fig. S18a–f）. Furthermore， Badercharge analysis （Fig. S18a，b） indicates electron transfer fromHDA to Cu. At the same time， charge transfer from the Cusurface to *CO and *CHO also facilitates CO―CHO couplingon Cu （111）-HDA （Fig. S19c，d） 39，40. Theoretical calculationresults reveal that HDA on the Cu surface exhibits enhancedinteraction with CO2 and eCO2RR intermediates throughhydrogen bonding， improving CO coverage and CO―CHOcoupling， thus promoting the formation of C2 products.Additionally， the electron-donating property of HDA withintermediates also plays a vital role in regulating the selectivityof eCO2RR products.

In situ Raman spectroscopy was employed to further identifythe reaction intermediates and explore the reaction mechanismof HDA-mediated eCO2RR. Fig. 4a–c presents the potentialdependentin situ Raman spectra of eCO2RR on Cu NPs， Cu-PMM， and Cu-HDA acquired at the potential window between?0.8 and ?1.2 V （vs. RHE） and open circuit potential （OCP）. ForCu NPs （Fig. 4a）， there is a weak vibration of CO adsorption onthe bridge sites （COb） and the characteristic vibration of*COCHO （2660 cm?1）， which is generally regarded as a keyintermediate involved in the dimerization process and starts toappear at ?1.1 V （vs. RHE） 19. As shown in Fig. 4b， PMMfunctionalizedCu exhibits a more intense signal of *COCHOand COb， and the characteristic vibration appears at a morepositive potential （?0.9 V vs. RHE）， suggesting acceleratedCO?CHO coupling and enhanced C2 production. For the Cu-HDA electrode， the signal at 2080 cm?1 is attributed to adsorbedCO at atop sites （COa） （Fig. 4c）. According to a previous report，COa dominates when CO coverage is high， which is beneficialfor C―C coupling 41 and enhances the selectivity of C2 productson Cu-HDA. The directly observed broad vibration peak at 2890 cm?1 can be attributed to the CHx group of C2H4， which isconsistent with the C2 products distribution in theelectrochemical characterization of eCO2RR 42，43.

Additionally， the peaks at 1060 and 1350 cm?1 at open-circuitpotential （OCP） and the peak at 1600 cm?1 at the appliedpotentials were clearly observed， which are associated with thestretching of CO3 2?， HCO3? and H2O on the catalyst surface 26，44，45.The vibration intensity of HCO3? was barely observed， and onlyan intense vibration peak from CO3 2? was observed on Cu-HDA.In contrast， only an intense peak of HCO3? was observed for Cuand Cu-PMM， indicating a much increased local pH for Cu-HDA， thus promoting the production of C2 products 46，47.Moreover， the intensity of the Cu―OH vibration peak at 530cm?1 is basically stable for Cu-HDA and Cu-PMM， which alsoshows the effect of amino groups on stabilizing surface pH 48.These in situ Raman spectroscopy results reveal that HDAfunctionalizationleads to higher COa coverage and the increasedstable local pH， which accelerates the formation of C2 productsvia CO―CHO dimerization.

The schematic of the aqueous rechargeable Zn-CO2electrochemical cell was carried out employing 1.0 mol?L?1 KOH and 6.0 mol?L?1 KOH with 0.2 mol?L?1 Zn （CH3COO）2 asthe cathodic and anodic electrolyte， respectively （Fig. 5a）. Thedischarge polarization curve and corresponding power density ofCu-HDA exhibit a maximum power density of 6.48 mW?cm?2 ata discharge current density of 16.0 mA?cm?2， as shown in Fig.5b， which is much superior to most reported rechargeable Zn-CO2 batteries （Fig. 5c 49–57 and Table S15）. The correspondinghigh C2H4 and C2H5OH production displayed in Fig. 5d suggestthe dominance of CO2-to-C2 products conversion during thebattery discharge. Furthermore， the discharge-charge cyclabilitycan continuously operate for 60 h under 5 mA?cm?2， identifyinga remarkable rechargeable durability of the Cu-HDA-based Zn-CO2 battery， as displayed in Fig. 5e. The superior performanceto Cu NPs （Fig. S20） for rechargeable Zn-CO2 batterieshighlights the significance of HDA-functionalization foreCO2RR.

3 Conclusions

In this study， Cu NPs were successfully prepared and surfacefunctionalized.Cu-HDA exhibited an FEC2 of 73.5% andprovided a high C2 partial current density of 131.4 mA?cm?2 at ?0.9 V vs. RHE. Theoretical investigations revealed that HDAfunctionalization not only improved surface CO coverage andreduced the reaction energy barrier for CO―CHO coupling， butalso promoted C2H4 production. Additionally， the interfacialelectronic effect benefited the CO―CHO coupling mechanism，and hydrogen bonds between key intermediates and ―NH2were identified at the molecular level by precisely tuning of themolecular structure of the surface-functionalized amino groups，thus improving the selectivity for C2 products. In situ Ramanspectroscopy provided evidence of the increased COa coverageand higher local pH on Cu-HDA， which enhances the C2products production. The Cu-HDA-based rechargeable Zn-CO2battery exhibited superior maximum power density andremarkable rechargeable durability.

Author Contributions： Conceptualization， Dong Xiang andXiongwu Kang; Methodology， Dong Xiang; Software， KunzhenLi; Validation， Kanghua Miao， Kunzhen Li and Dong Xiang;Formal Analysis， Dong Xiang and Xiongwu Kang;Investigation， Dong Xiang; Resources， Xiongwu Kang， RanLong and Yujie Xiong; Data Curation， Dong Xiang; Writing –Original Draft Preparation， Dong Xiang; Writing – Review amp;Editing， Xiongwu Kang; Visualization， Dong Xiang;Supervision， Xiongwu Kang; Project Administration， XiongwuKang; Funding Acquisition， Xiongwu Kang.

Supporting Information： available free of charge via theinternet at http：//www.whxb.pku.edu.cn.

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