關(guān)鍵詞：給體；受體；水分解；CTF；路易斯堿性

1 Introduction

The utilization of solar energy in photocatalytic water splitting（PWS） presents a sustainable and eco-friendly method forhydrogen production 1–4. Nevertheless， traditional inorganicsemiconductor photocatalysts frequently encounter substantialcharge recombination and photocorrosion problems duringcontinuous photocatalytic reaction conditions， thereby greatlyhindering the efficiency and durability of PWS 5–9. Thephotocatalytic oxidation of organic compounds coupling withhydrogen production offer a viable solution for elevatinghydrogen production performance due to the rapid chargeseparation and sufficient utilization of electron-hole pairs 10–13.Moreover， various modification approaches， such asconstructing S-scheme heterojunctions 14， organic-inorganichybrid composites 15， reversing electron transfer 16，17， facetengineering 18， donor-acceptor modulation 19， built-in electricfield design 20， d-electron structure adjustment 21， localpolarization treatment 22， solid solutions 23， bimetallics 24， twodimentional（2D）/2D composites 25， highly crystalline materials 26，and dual cocatalysts 27，28， have all improved hydrogenproduction to some extent. However， photocatalytic hydrogenproduction still falls significantly short of industrial benchmarksdue to severe charge recombination and a high barrier to wateroxidation. Consequently， it is essential to develop novelphotocatalysts and shed light on PWS mechanisms 29. Incontrast， crystalline triazine-based covalent organic frameworks（CTFs） exhibit significant advantages over traditional inorganicsemiconductors in terms of their high surface areas， exceptionallight harvesting， accelerated charge separation， and robuststability， thereby rendering them more favorable for PWS 30–33.However， CTFs primarily consist of non-polar ringsinterconnected by benzene and triazine rings， rendering CTFsinherently hydrophobic 34，35. Moreover， these rings primarilyconsist of non-metallic elements such as carbon， nitrogen， andhydrogen， which exhibit limited affinity towards H2O moleculesdue to their weak van der Waals interactions 36–39. Thisdeficiency in bonding hampers the adequate adsorption andactivation of H2O， thereby negatively impacting H2O splittingand redox processes in CTFs 40，41. Consequently， it is imperativeto enhance the H2O adsorption and activation capabilities ofCTFs to improve the PWS efficiency.

The NH2 group is a significant hydrophilic moiety， thusanchoring on NH2 groups provides a feasible approach toaugment the affinity of CTFs for H2O 42. The nitrogen atom inthe NH2 group possesses a lone pair of electrons， enabling it toengage in hydrogen bonding and enhance its interaction withH2O molecules. The benzene ring of CTFs can be modified withan NH2 group to form CTF-NH2， thereby enhancing the affinityof CTFs towards H2O. However， the transformation ofintermediates of PWS for CTF-NH2 becomes difficult due to thestrong Lewis alkalinity of the NH2 group caused by the electrondonatedbenzene rings 43–46. The Lewis basicity of the aminegroups primarily depends on the electron density of NH2.Consequently， adjusting the electron density of NH2 in CTF-NH2through donor and acceptor groups represents a viable strategyto ameliorate the conversion of intermediate products 47–51.Nevertheless， the existing research on enhancing intermediatetransformation in CTFs through donor and acceptor groupmodifications is inadequate. Further investigations are requiredto elucidate the mechanisms underlying the impact of thesemodifications on the intermediate transformation of PWSprocesses.

In this study， the NH2 group of CTF-NH2 was modified withan electron-donating ethyl group （C2H5） and an electronwithdrawing5-fluoroethyl group （C2F5）， resulting in C2H5-CTFNH2and C2F5-CTF-NH2. These modifications were aimed atfinely adjusting the electron density and Lewis basicity of theCTF-NH2， to investigate the effects of the Lewis basicity of NH2on the efficiency of PWS. X-ray diffraction （XRD）， infraredspectroscopy （IR）， and Raman spectroscopy were employed tosimulate and analyze the structural composition of three types ofCTF-NH2. Additionally， ultraviolet-visible （UV-vis） lightabsorption spectra and X-ray absorption spectroscopy （XAS）were simulated to demonstrate the impact of various functionalgroup modifications on CTF-NH2. Furthermore， the electricalstructure， work function， and dipole moment were calculated toinvestigate the light absorption， charge separation， and redoxcapability of CTF-NH2. Subsequently， the Gibbs free energy ofhydrogen and oxygen production was computed to examine theimpact of donor （C2H5） and acceptor （C2F5） groups on thesurface reaction process of PWS. Finally， a mechanisminvolving donor-acceptor-modified CTF-NH2 for PWS wasproposed.

2 Computational details

Density Functional Theory （DFT） analyses were conductedusing the Vienna ab initio Simulation Package （VASP）， applyingthe projector augmented-wave （PAW） method for precision. ThePerdew， Burke， and Ernzerhof （PBE） model within thegeneralized gradient approximation （GGA） was selected toeffectively depict the exchange-correlation dynamics. A 2 × 2 ×1 K-point grid in the Brillouin zone with a raised energy barrierof 520 eV was used to ensure thorough surface examination.Optimization processes continued rigorously until the energyand mechanical forces reached minuscule levels of 5 × 10?5 eVand 0.02 eV???1 （1 ? = 0.1 nm）， respectively. A substantialvacuum boundary of 15 ? was incorporated to segregate theperiodic surface arrays， minimizing external influences. Theadvanced DFT-D3 methodology with Grimme’s zero dampingconfiguration was employed for the Van der Waals （vdW）interactions. The Gibbs free energy equation was redefined asΔG = ΔE + ΔEZPE ? TΔS， where ΔE indicates electronic energyshifts， ΔEZPE denotes adjustments in zero-point energy， and ΔSencapsulates the entropy variations adjusted by temperature. TheVASPKIT tool was instrumental in assessing zero-point energiesand examining vibrational frequencies along with entropymetrics for molecules in a gaseous state， placing a focus on theirdynamic behavior 52. Spectroscopic inquiries， including bothvibrational and high-energy state evaluations， utilized the latestCP2K-2023.2 system， applying the PBE functional to ensureaccurate representation of the systems under study. Theexamination of electronic structures was handled throughunrestricted Kohn-Sham DFT under the Gaussian and planewaves （GPW） architecture， integrating Goedecker-Teter-Hutter（GTH） pseudopotentials with a comprehensive TZV2PMOLOPT-GTH basis set across all elements. Adjusted settingsincluded a higher plane wave cutoff at 420 Ry， a stringent selfconsistentfield （SCF） convergence threshold of 1 × 10?5 hartree，and force convergence criteria tightened to 5 × 10?4 Bohr perhartree. Detailed analyses and spectral studies of excited stateswere facilitated using the Multiwfn software 53.

3 Results and discussion

CTF-NH2 is comprised of a 2D lattice structured byalternating triazine rings and aniline units （Fig. 1a）. By graftingethyl （C2H5） and 5-fluoroethyl （C2F5） groups onto aniline， C2H5-CTF-NH2 and C2F5-CTF-NH2 are obtained （Fig. 1b，c）. Afterstructural refinement， the pore diameters of CTF-NH2， C2H5-CTF-NH2， and C2F5-CTF-NH2 are 11.0， 10.1， and 9.9 ?respectively （Fig. 1a–c）. These modifications marginallydecrease the pores of CTF-NH2. However， since C2H5 and C2F5align perpendicularly to the aniline plane， the reduction in poresize is minimal， preserving a substantial specific surface area forthe PWS. Additionally， the introduction of C2H5 and C2F5induces a slight distortion in the CTF-NH2 framework， therebylowering the energy of the system. Furthermore， C2H5 and C2F5generate considerable steric hindrance around CTF-NH2， whichminimizes interactions between layers and facilitates theformation of monolayers in laboratory conditions. The bondlength between the nitrogen atom of the NH2 group in CTF-NH2and the carbon atom of the benzene ring initially measures 1.358?. After the introduction of the C2H5 group， this bond extends to1.366 ?， whereas the introduction of C2F5 reduces it to 1.354 ?，illustrating that the introduction of C2H5 and C2F5 exertsdifferent influence on NH2 groups. XRD simulation results showthat the XRD patterns of CTF-NH2， C2H5-CTF-NH2， and C2F5-CTF-NH2 are nearly identical （Fig. 1d）. The main peak ispositioned at a small angle （less than 10°）， with three strongpeaks at 9.15°， 7.00°， and 5.89° respectively. This can beattributed to the minimal influence of C2H5 and C2F5 on thelattice parameters and space groups of CTF-NH2. However， theintroduction of these functional groups can affect the atomic andelectronic structure of the surface of CTF-NH2. IR spectrasimulation results show that there are characteristic absorptionpeaks of the triazine ring in the infrared spectra of the crystals ofCTF-NH2， C2H5-CTF-NH2， and C2F5-CTF-NH2. In CTF-NH2，the peak corresponding to the stretching vibration mode of theC―N bond is at 1364 cm?1， and the characteristic peak for the C＝N stretching vibration is at 1576 cm?1 （Fig. 1e）. In C2H5-CTFNH2and C2F5-CTF-NH2， there is a slight shift in the peakscorresponding to the C―N and C＝N bonds， indicating that theintroduction of C2H5 and C2F5 affects the triazine rings structure.Additionally， in CTF-NH2， the characteristic peak of N―H is at3413 cm?1. Similarly， due to the influence of C2H5 and C2F5， theN―H stretching vibration peak in C2H5-CTF-NH2 shifts to 3458cm?1， and in C2F5-CTF-NH2 to 3453 cm?1. All three CTFsexhibit a strong in-plane bending vibration characteristic peak ofC―H at 1491 cm–1. Moreover， C2F5-CTF-NH2 has a uniquecharacteristic peak at 1097 cm?1， attributed to the C―F bondstretching vibration of C2F5. To further investigate the crystalstructure of CTFs， Raman spectroscopy was simulated. Theresults show that as a backbone component of CTF-NH2， anilineexhibits four strong absorption peaks due to benzene ringstretching vibrations at 1435， 1540， 1612， and 1672 cm?1 （Fig.1f）. Similarly， in the crystals of C2H5-CTF-NH2 and C2F5-CTFNH2，these peaks shift due to the influence of the C2H5 and C2F5groups attached to the aniline. Additionally， CTF-NH2 has astrong peak at 1009 cm?1， attributed to the out-of-plane bendingvibration of the C―H bond on the aromatic ring. For C2H5-CTFNH2and C2F5-CTF-NH2， the absorption peaks of the C―H bonddecrease to 1003 and 1005 cm?1， respectively. This can beascribed to the relaxation of the internal structure of CTF-NH2caused by the modifications of C2H5 and C2F5.

To examine the optical properties of CTFs， electronicexcitation spectra were simulated. To ensure coverage of theUV-vis light range， the lowest 50 excited states were analyzed.Each vertical line represents the energy of an excited state， withdifferent colors corresponding to different CTFs materials （Fig.2a）. For CTF-NH2， the first excited state S1 predominantlyinvolves an electron excitation from the HOMO to the LUMOorbital， contributing 65.3% to S1. This excited state correspondsto an excitation wavelength of 465 nm and an energy of 2.67 eV.Upon the introduction of the electron donor C2H5 and theelectron acceptor C2F5， S1 remains primarily contributed by theHOMO to LUMO electron excitation， with proportions of 78.2%and 79.0%， respectively. However， the introduction of theelectron donor C2H5 leads to an increase in the excitationwavelength of S1 to 476 nm， while the excitation energydecreases to 2.60 eV. Conversely， the introduction of theelectron acceptor C2F5 results in a decrease in the excitationwavelength of S1 to 433 nm， with a corresponding increase inexcitation energy to 2.86 eV. Gaussian broadening of theseparated excited state energies produces the UV-Vis absorptionspectrum. Changes in the absorption edge of the absorptionspectrum also reveal that the introduction of C2H5 reduces theband gap of CTF-NH2， while C2F5 increases it. XAS simulationsare utilized to identify the coordination environment andelectronic states of CTF-NH2 crystals （Fig. 2b）. To investigatethe effects of C2H5 and C2F5 groups on the NH2 groups at theactive sites， the excited states of the N element （393–404 eV）electrons in the 1s orbitals are studied. The N atom in CTF-NH2exhibits an electron transition from the 1s to anti-bonding πorbitals （1s → π*）， corresponding to a peak at 395.65 eV. ForC2H5-CTF-NH2， this peak shifts to higher binding energy at395.75 eV， while for C2F5-CTF-NH2， it moves to lower bindingenergy at 395.56 eV. This shift is due to the electron-donatingnature of the C2H5 group and the electron-withdrawing nature ofthe C2F5 group， resulting in the electron density of the NH2groups in the three CTFs in the order C2H5-CTF-NH2 gt; CTFNH2gt; C2F5-CTF-NH2. Additionally， CTF-NH2 shows an N-Helectron transition from 1s to σ* orbitals at 397.68 eV， whileC2H5-CTF-NH2 and C2F5-CTF-NH2 show corresponding peaksshifting to lower binding energies at 397.66 and 397.58 eV，respectively， primarily due to an increase in N―H bond length.Similarly， the N―C bond length of 1.354 ? of C2F5-CTF-NH2is significantly shorter than that of 1.358 ? of CTF-NH2，increasing the N-C （1s → σ*） transition absorption peak from398.80 to 399.23 eV.

The Fermi levels of the three CTFs crystals are situated withinthe bandgap， closely aligned with the valence band maximum（VBM）， consistent with typical semiconductor properties （Fig.3a–c）. Modifications with C2H5 and C2F5 groups do not changethe type of semiconductor in CTF-NH2 and they all remain directbandgap semiconductors. CTF-NH2 has a bandgap of 1.79 eV.The addition of C2H5 decreases the bandgap of C2H5-CTF-NH2to 1.70 eV， while the introduction of C2F5 increases the bandgapof C2F5-CTF-NH2 to 1.93 eV. These changes in the bandgapalign with trends observed in UV-Vis absorption spectra. DOSresults manifest the VBM is mainly composed of N 2p orbitals，and the CB minimum （CBM） predominantly involves C 2porbitals （Fig. 3d–f）. Analysis of band structure and DOSindicates that C2H5 and C2F5 modifications do not alter theconduction band （CB） and valence band （VB） compositions ofCTFs.

The band structures and DOS for the three CTFs exhibit theorbital compositions of the VBM and CBM， yet the specificatoms contributing are not explicitly delineated. Twodimensionaltop-down perspectives of the VBM and CBM levelsfor CTF-NH2 illustrate that the VBM predominantly stems fromN atoms on triazine rings， while the CBM chiefly involves Catoms on aniline units （Fig. 4a，d）. This observation implies thattriazine rings act as electron acceptors and aniline units serve aselectron donors in CTF-NH2. Upon modification of CTF-NH2with C2H5， the C atoms on C2H5 do not participate in the CBM，nor does aniline contribute to the VBM （Fig. 4b，e）. The influenceof C2H5 and C2F5 on the CBM of NH2-CTF is marginal. C2H5exerts a minor impact on the CBM， while C2F5 has nearly noeffect on the CBM （Fig. 4c，f）. The findings suggest that thepresence of the electron donor C2H5 and acceptor C2F5minimally affects the VBM and CBM， consistent with the DOSanalysis.

The potential and electric fields within CTFs are elucidatedthrough the computation of work functions and dipole moments.As CTF-NH2 is a 2D material， the work function of the CTFNH2（001） crystal face was calculated to be 5.0 eV （Fig. 5a）. Theintroduction of C2H5， an electron donor， raises the Fermi level，subsequently reducing the work function. Thus， with themodification by C2H5， the work function of C2H5-CTF-NH2decreases to 4.8 eV （Fig. 5b）. Conversely， C2F5 acts as anelectron acceptor， causing the Fermi level of CTF-NH2 to shiftdownward. Therefore， with the C2F5 modification， the workfunction of C2F5-CTF-NH2 increases to 5.7 eV （Fig. 5c）. For 2Dlayered CTFs， the intrinsic electric fields within the plane andbetween layers are beneficial for the migration and separation ofphotogenerated carriers. To illustrate the impact of C2H5 andC2F5 modifications on the intrinsic electric fields of CTF-NH2，the dipole moments in various coordinate directions werecalculated for CTF-NH2， C2H5-CTF-NH2， and C2F5-CTF-NH2（Fig. 5d）. CTF-NH2 exhibits dipole moments primarily in the Xand Y coordinate directions， with a smaller dipole moment in theZ direction due to its ideal 2D layered structure. With the C2H5modification， the dipole moment in the X direction for C2H5-CTF-NH2 remains nearly consistent with that of CTF-NH2.However， in the Y direction， the dipole moment for C2H5-CTFNH2is 10.7 e??， double that of CTF-NH2 （5.0 e??）. This increaseis attributed to the electron-rich layer formed on the surface ofCTF-NH2 due to the introduction of C2H5， leading to an unevencharge distribution. Additionally， since the main chain of C2H5is perpendicular to the CTF-NH2 plane， there is a minor dipolemoment of 0.35 e?? in the Z direction for C2H5-CTF-NH2.Similarly， the electron acceptor C2F5 creates a highly unevencharge distribution on the surface of CTF-NH2， particularly inthe Y direction， resulting in a significant dipole moment of 38.7e?? in the Y direction for C2F5-CTF-NH2. This also results in astronger dipole moment in the Z direction. Thus， the introductionof C2H5 and C2F5 leads to an increase in dipole moments withinthe plane （X and Y directions） and between layers （Z direction），thereby inducing stronger intrinsic electric fields， which arefavorable for charge separation. The total dipole moments ineach coordinate direction reveal that the introduction of C2F5contributes the most significant increase， nearly doubling thetotal dipole moment of CTF-NH2. To provide a more intuitiveexamination of the impact of introducing the electron donorC2H5 and the electron acceptor C2F5 on the surface electrostaticpotential of CTF-NH2， 2D top-view maps of the surfaceelectrostatic potentials for different CTFs were plotted （Fig. 5e–g）. Areas of the material surface depicted in red indicate negativepotential， while blue areas denote positive potential. After theintroduction of C2H5， parts of the C2H5 surface appear blue，suggesting that C2H5 loses electrons and acts as an electrondonor （Fig. 5e，f）. Concurrently， the red color near the N atomsof the aniline groups deepens， indicating that C2H5 induces amore negative potential at NH2， thus enhancing its Lewisbasicity. Upon introducing C2F5， parts of the C2F5 surface showdeep red， indicating that C2F5 gains electrons and functions as anelectron acceptor （Fig. 5g）. Simultaneously， the red color nearthe N atoms of the aniline groups becomes lighter， suggestingthat C2F5 causes the potential at NH2 to become more positive，thereby reducing its Lewis basicity.

To investigate the impact of C2H5 and C2F5 modifications onthe PWS mechanisms of CTF-NH2， the analysis is segmentedinto hydrogen evolution reaction （HER） and the oxygenevolution reaction （OER） components （Fig. 6a–c）. In the HER，hydrogen spontaneously adsorbs on the nitrogen sites of thetriazine rings in CTF， suggesting these sites as the active centersfor hydrogen production （Fig. 6d）. The adsorption free energychanges for hydrogen across the three CTF variants are negative，indicating a thermodynamic favorability of hydrogen adsorptionat these nitrogen sites. Specifically， the electron-donating C2H5group intensifies hydrogen adsorption， whereas the electronacceptingC2F5 group weakens it. Given that hydrogendesorption is the rate-determining step in HER， the energybarrier for HER in C2H5-CTF-NH2 increases to 0.94 eV from0.80 eV in native CTF-NH2， while it decreases to 0.47 eV inC2F5-CTF-NH2 （Fig. 6a）. Regarding OER， which unfolds in foursteps： initially， an H2O molecule adsorbs onto the CTFs surfaceand undergoes dehydrogenation to yield an adsorbed hydroxylgroup （* + H2O ? H+ + h+ = *OH）. This is followed by furtherdehydrogenation of the hydroxyl group to form an adsorbedoxygen atom （*OH ? H+ + h+ = *O）. Subsequently， the oxygenatom reacts with OH– to produce an adsorbed perhydroxylradical （*O + OH– + h+ = *OOH）. Finally， the perhydroxylradical undergoes dehydrogenation and releases as an O2molecule （*OOH ? H+ + h+ = * + O2）. All fundamental OERsteps take place at the NH2 groups on the CTFs， indicating thatNH2 is the active site for oxygen production （Fig. 6d）. The freeenergy changes （ΔG） for these elementary steps are positive，showing that each step in the OER consumes energy. The thirdstep serves as the rate-limiting phase， with barriers of 2.42， 2.46，and 2.12 eV for CTF-NH2， C2H5-CTF-NH2 and C2F5-CTF-NH2，respectively （Fig. 6b）. The introduction of C2H5 leads to overlystrong *O adsorption and conversion obstacle， significantlyraising the energy barrier. Conversely， C2F5 impairs *Oadsorption， thereby reducing the reaction barrier. To evaluate theoverpotential of the OER， the overpotentials at an externalvoltage of 1.23 V were determined to be 1.19， 1.23， and 0.89 Vfor CTF-NH2， C2H5-CTF-NH2 and C2F5-CTF-NH2， respectively（Fig. 6c）.

To elucidate the impact of C2H5 and C2F5 modifications on thebarrier of the rate-determining step in OER， charge densitydifference and Bader charge analyses were performed on theintermediate state *O of three CTF surfaces. The resultsillustrated that the isolated oxygen atom adsorbed on the CTFsurfaces is depicted as yellow， while the CTFs are represented asblue， indicating that the isolated oxygen atom acquires electronsfrom the amine groups on the CTF surfaces （Fig. 7a–c）. Thequantity of electrons transferred from the amine to *O in CTFNH2，C2H5-CTF-NH2， and C2F5-CTF-NH2 are 0.65e， 0.66e， and0.61e， respectively. The introduction of the electron-donor C2H5resulted in an augmented transfer of electrons from the amine to*O， while the electron-acceptor C2F5 modification reduced theelectron transfer. The electron-donor C2H5 amplified theelectron count on *O， thereby enhancing *O adsorption andelevating the transformation difficulty， leading to a heightenedbarrier. Conversely， the electron-acceptor C2F5 diminished theelectron count on *O， attenuating its adsorption but facilitatingits transformation， thus reducing the OER barrier. To furtherprobe the bonding interactions between *O and CTFs， the COHPbetween the adsorbed oxygen atom and the adsorption sitenitrogen atom was computed. The N―O bond lengths in CTFNH2，C2H5-CTF-NH2， and C2F5-CTF-NH2 are 1.346， 1.342， and1.348 ?， respectively （Fig. 7d–f）. These findings suggest thatC2H5 prompts a reduction of the N―O bond length， while C2F5induces an elongation of the bond length. Furthermore， theintegrated COHP （ICOHP） values for CTF-NH2， C2H5-CTFNH2，and C2F5-CTF-NH2 are ?11.83， ?11.88， and ?11.75，respectively， demonstrating that C2H5 enhances the strength ofthe N-O bond， while C2F5 diminishes its strength. The resultscorrespond well with the Bader charge analysis. Further， it wasdetermined that the ICOHP in all three CTFs is primarilycontributed by N 2s―O 2px， N 2px―O 2s， and N 2px―O 2pxinteractions， with the σ-bond interaction of N 2px―O 2px makingthe predominant contribution to the N―O bond. Additionally，C2H5 and C2F5 did not alter the principal contributingcomponents of the N―O bond but solely affected thecontribution values of these components.

4 Conclusion

In conclusion， NH2-modified covalent triazine frameworks（CTF-NH2） with electron-donating ethyl （C2H5） and electronwithdrawing5-fluoroethyl （C2F5） groups were designed. Thestructural analysis showed that C2H5 and C2F5 had minimalimpacts on the XRD， IR， and Raman spectra of CTF-NH2.However， these groups significantly modulated the electrondensity on the amine groups of CTF-NH2， affecting their Lewisbasicity and the redox processes at the CTF-NH2 surface.Moreover， C2H5 and C2F5 also influenced the bandgap， lightabsorption， redox ability， work function， and dipole moments ofCTF-NH2. Compared to C2H5， C2F5 enhanced the redoxcapability of CTF-NH2， accelerated charge separation， reducedthe Lewis basicity of the amine groups， and lowered the energybarriers for the HER and OER processes. Further Bader chargeanalysis revealed that the electron-withdrawing C2F5 decreasedelectron transfer from the benzene ring to the amine group，thereby weakening its Lewis basicity. The reduction in Lewisbasicity led to weaker adsorption of HER and OERintermediates， consequently lowering the energy barriers inPWS. This work provides a reference for modifying the Lewisbasicity of CTFs with electron-donating and electron-acceptinggroups to elevate the efficiency of PWS.

Author Contribution： Conceptualization， Methodology，Validation， Formal Analysis， Investigation， Resources， DataCuration， Writing， Original Draft Preparation， Z.L.; Software，Visualization， Z.W.; Review amp; Editing， Supervision， H. L andQ.L.; Project Administration， Funding Acquisition， Z.L. andZ.W.