調(diào)控ZnIn2S4/Bi2O3 S型異質(zhì)結(jié)的電子結(jié)構(gòu)和潤(rùn)濕性增強(qiáng)光催化析氫

摘要：通過(guò)光催化水裂解制氫來(lái)生產(chǎn)可再生燃料具有巨大的潛力。然而，緩慢的析氫動(dòng)力學(xué)和較差的水吸附對(duì)光催化劑構(gòu)成了重大挑戰(zhàn)。在這項(xiàng)研究中，我們開(kāi)發(fā)了一種簡(jiǎn)單的水熱法，用于從金屬有機(jī)框架（MOF）中合成Bi2O3 （BO），并將其負(fù)載到花狀ZnIn2S4 （ZIS）上。該方法顯著增強(qiáng)了水吸附和表面催化反應(yīng)，從而顯著提高了光催化活性。以三乙醇胺（TEOA）作為犧牲劑，在BO上負(fù)載15% （質(zhì)量分?jǐn)?shù)） ZIS時(shí)，析氫速率達(dá)到了1610 μmol?h?1?g?1，是純BO的6.34倍。此外，利用密度泛函理論（DFT）和從頭算分子動(dòng)力學(xué)（AIMD）計(jì)算，我們確定了ZIS/BO S型異質(zhì)結(jié)界面上的反應(yīng)，包括水吸附和催化反應(yīng)的活性位點(diǎn)。這項(xiàng)工作將為開(kāi)發(fā)具有特定電子性能和潤(rùn)濕性的高性能復(fù)合光催化材料提供有價(jià)值的見(jiàn)解。

關(guān)鍵詞：S型；析氫；潤(rùn)濕性；光催化；電子結(jié)構(gòu)

中圖分類號(hào)：O643

Abstract： The production of renewable fuels through water splitting viaphotocatalytic hydrogen production holds significant promise.Nonetheless， the sluggish kinetics of hydrogen evolution and theinadequate water adsorption on photocatalysts present notablechallenges. In this study， we have devised a straightforward hydrothermalmethod to synthesize Bi2O3 （BO） derived from metal‐organicframeworks （MOFs）， loaded with flower-like ZnIn2S4 （ZIS）. Thisapproach substantially enhances water adsorption and surface catalyticreactions， resulting in a remarkable enhancement of photocatalyticactivity. By employing triethanolamine （TEOA） as a sacrificial agent， thehydrogen evolution rate achieved with 15% （mass fraction） ZIS loadingon BO reached an impressive value of 1610 μmol?h?1?g?1， marking a 6.34-fold increase compared to that observed for bareBO. Furthermore， through density functional theory （DFT） and ab initio molecular dynamics （AIMD） calculations， we haveidentified the reactions occurring at the ZIS/BO S-scheme heterojunction interface， including the identification of activesites for water adsorption and catalytic reactions. This study provides valuable insights into the development of highperformancecomposite photocatalytic materials with tailored electronic properties and wettability.

Key Words： S-scheme; Hydrogen evolution; Wettability; Photocatalysis; Electronic structure

1 Introduction

With the intensifying global energy crisis and worseningenvironmental pollution， there is an urgent need to explorerenewable， environmentally friendly， and more efficient energysources. Hydrogen energy is widely recognized as an optimalalternative for the 21st century due to its widespread availability，high energy content upon combustion， and zero emissions.Photocatalytic water splitting has received significant attentionin recent decades as a means to produce hydrogen. However， theproduction of high-value hydrogen through photocatalytic watersplitting presents substantial challenges 1–7.

There is growing concern regarding the development ofphotocatalysts with exceptional efficiency for hydrogengeneration 8–10. Most single photocatalysts exhibit limitedefficiency due to the rapid recombination of electron-hole pairs，resulting in low hydrogen production activity 11?13. Historically，platinum （Pt） and other precious metals have been consideredsuperior catalysts for hydrogen evolution due to their inherenthigh activity. However， their industrial application is hinderedby their exorbitant cost and limited availability of resources. Toaddress these limitations， various strategies have been devised，including heteroatom doping， electronic structure modulation，nanostructuring， dye sensitization， and heterojunctionconstruction 14–26. Among these strategies， heterojunctionengineering is considered one of the most effective and practicalapproaches as it provides an enlarged specific surface area andan abundance of high-quality active sites. This facilitates thetransfer of photo-excited charge carriers and reduces thediffusion length for both ions and electrons 27–29. The use of Sschemeheterojunctions among different heterostructuresenhances the catalyst's light absorption capacity and provides arobust redox capacity， enabling efficient separation ofphotogenerated electrons and holes. Consequently， this approacheffectively addresses the challenges encountered inphotocatalytic hydrogen production technology 30–36. Therefore，the utilization of S-scheme heterojunctions offers a distinctiveadvantage in advancing photocatalysts with exceptionalefficiency for photocatalytic hydrogen production 37–39.

Recent research has explored emerging areas such asfemtosecond transient absorption （fs-TA） spectroscopy， transientsurface photovoltage （TPV）， and in situ illumination Kelvinprobe force microscopy （KPFM） techniques to demonstrate thesuccessful spatial separation and transfer of photoinducedcarriers through the S-scheme 40–42. Additionally， heterojunctionstructuredmaterials commonly exhibit the quantum confinementeffect 43，44， resulting in an increased electronic bandgap. Thisphenomenon enhances the materials’ redox capabilities forphotocatalytic reactions and improves the quality and quantityof photo-induced charge carriers to some extent. Consequently，the design of efficient， non-noble metal heterojunctions forphotocatalytic hydrogen evolution is essential and highlydesirable.

Metal-organic frameworks （MOFs） represent a class of porouscrystalline materials comprising metal nodes linked by organiclinkers. They hold great promise for catalytic applications due totheir versatile and customizable structures， adjustable nanoporesor nanochannels in terms of size and shape， as well as substantialsurface areas. MOFs are employed as catalysts for water splittingeither directly or as precursors for nano-catalysts. For instance，Peng et al. developed a novel MoS2/O-ZIS photocatalyst，leveraging an MOF structure， which enhances hydrogenevolution activity 45. This study underscores the effectiveness ofZIS as a catalyst for photocatalytic hydrogen evolution.

However， the process of water adsorption and activation on the photocatalyst plays a pivotal role in determining theefficiency of heterogeneous catalytic reactions. This process issignificantly influenced by the morphology and surfacecondition of the photocatalyst 46–48. To improve the efficiency ofhydrogen evolution， our focus is on enhancing adsorptioncapacity and catalytic activity through property modifications orprecise control over semiconductor coupling. Thesemodifications directly contribute to an increase in both thequantity and arrangement of active sites 49. Lin has designed twonovel conjugated porous polymers （CPPs） based on pentadienefor photocatalytic hydrogen production 50. Compared to thehydrophobic octyl-functionalized Tr-F8， the highly wettableamino side chain Tr-F3N exhibits superior hydrogen evolutionreaction （HER） performance. Theoretical simulations haverevealed that the presence of amino groups can optimize themolecular-level interaction between photocatalysts and H2Omolecules， leading to improved charge transfer efficiency.Consequently， introducing ZnIn2S4 into the MOF structure tocreate a heterojunction is employed to modulate the surfaceproperties of the catalyst， thereby enhancing its hydrogenevolution rate. This strategy offers a promising approach forefficient photocatalytic hydrogen evolution.

Building upon this concept， we present the development ofphotocatalysts based on MOF-derived Bi2O3 （BO） loaded withflower-like ZnIn2S4 （ZIS） structures， synthesized through ahydrothermal method. The resulting BO loaded ZIS flower-likestructure significantly enhances the separation rates of electronholepairs， thereby reducing their recombination. Consequently，the hydrogen production rate achieved with BO loaded with15% （mass fraction） ZIS reaches an impressive value of 1610μmol?h?1?g?1， representing a remarkable approximately 6.34-fold increase compared to that of BO alone. Contact anglemeasurements and density functional theory （DFT） calculationssupport the notion that the construction of a ZIS/BOheterojunction enhances the hydrophilicity of the BOphotocatalyst， thereby improving the efficiency ofheterogeneous catalytic reactions and enabling high-efficiencyhydrogen evolution. This synergistic approach， which involvesmanipulating electronic properties and surface characteristics，holds the potential to inspire innovative designs and controlledfabrication of various heterojunction catalytic materials basedon MOFs for applications in the energy and environmentalsectors.

2 Experimental section

2.1 Experimental materials and instruments

Bismuth nitrate pentahydrate （BiNO3?5H2O， analytical grade），1，3，5-benzentriccarboxylic acid （C9H6O6， analytical grade）， zincchloride， indium chloride hydrate （InCl3?4H2O， analyticalgrade）， thioacetamide （TAA， analytical grade）， absolute ethanol，and N，N-dimethylformamide （DMF， analytical grade） were allprocured from Simopharm Chemical Reagent Co.， Ltd.， China，and were used without any further purification.

The equipment utilized in this study included an electronicscale （BSA224S， Saitolis Scientific Instruments Co.， Ltd.，China）， a drying oven （DHG-9053A， Shanghai YihengTechnology Co.， Ltd.， China）， a water bath magnetic stirrer（HWCL-1， Zhengzhou Great Wall Science， Industry and TradeCo.， Ltd.， China）， a box-type oven （KSL-1200X-J， T， HefeiKejing Material Technology Co.， Ltd.， China）， and a mufflefurnace （KSL-1200X-J， Hefei Kejing Material Technology Co.，Ltd.， China）.

2.2 Preparation of photocatalysts

2.2.1 Synthesis of MOF derived BO

The Bi-MOF （CAU-17） precursor was synthesized using amodified version of a previously reported method 51. In thisprocedure， 0.45 g of Bi（NO3）3?5H2O and 2.25 g of C9H6O6 weredissolved in a solution consisting of 180 mL of a mixturecontaining DMF and methanol （in a 4 ： 1 ratio）. The resultingmixture was stirred for 30 min and then transferred into anautoclave， where it was heated to 120 °C and maintained at thistemperature for 24 h in an oven. After natural cooling， the whiteprecipitate obtained was subjected to centrifugation and washedthree times with DMF and methanol. Finally， it was driedovernight at 60 °C to obtain the Bi-MOF （CAU-17） precursor.This precursor was further annealed in an air environment at550 °C for 2 h， with a heating rate of 5 °C?min?1. The resultingproduct was yellow BO nanomaterials.

2.2.2 Synthesis of ZIS

The synthesis of ZIS was carried out following a previouslyreported procedure 52. In detail， a solution was prepared bydissolving 0.136 g of ZnCl2， 0.586 g of InCl3?4H2O， and 0.301 gof thioacetamide （TAA） in 60 mL of deionized water. Afterstirring for 30 min， the mixture was transferred to an autoclaveand heated to 120 °C for 24 h in an oven. Upon natural cooling，the resulting powder exhibited a vibrant yellow color andunderwent three rounds of water washing before being driedovernight at 60 °C.

2.2.3 Synthesis of ZIS/BO

The ZIS/BO composite was synthesized using a hydrothermalmethod similar to that used for ZIS. However， before the reactionin the oven， a specific quantity of ZIS was introduced into theBO precursor and subjected to ultrasonic treatment at ambienttemperature. The products were labeled based on the weightratio of ZIS in the BO precursor， with the followingdesignations： pure BO， 2.5%ZIS/BO， 5%ZIS/BO， 10%ZIS/BO，15%ZIS/BO， and 20%ZIS/BO.

2.3 Characterization

The crystal structure of the powder was determined using anX-ray diffractometer （MiniFlex6， Japan）. Scanning electronmicroscopy （SEM） （S-4800， Japan） and transmission electronmicroscopy （TEM） （JEM-2100F， Japan） were employed toinvestigate the morphologies and microstructure. The opticalproperties were recorded using a UV-Vis spectrometer （UV-2600）. Raman spectra were acquired using a Thermo DXRRaman spectrometer （Thermo Fisher Scientific， USA）. X-ray photoelectron spectroscopy （XPS） measurements were carriedout using a Thermo ESCALAB 250Xi （Thermo FisherScientific， USA）. The C 1s binding energy at 284.8 eV was usedas a reference for calibration. Thermogravimetric analysis （TG）was performed using a STA449C Synchronous ThermalAnalyzer （Netzsch， Germany）. The measurements wereconducted from ambient temperature up to 1000 °C with aheating rate of 5 °C?min?1. Pore characteristics and surface areawere assessed using the Autosorb-iQ nitrogen （N2） adsorptionequipment， manufactured in the United States.Photoluminescence （PL） spectra were recorded using the RF-6000 FL spectrometer， with an excitation wavelength of 365 nm.The hydrophilicity of the catalyst was evaluated by measuringthe contact angle using a contact angle measuring instrument（XG-CAMB3， China）.

2.4 Photocatalytic H2 evolution

The photocatalytic H2 evolution reaction was conducted in aquartz reactor， with the temperature maintained at 293 K usingcyclical cooling water. Specifically， a 100 mL aqueous solutioncontaining 0.02 g of dispersed photocatalyst and triethanolamine（TEOA） was subjected to ultrasonication for 30 min. The reactorunderwent a 30-min purge with Ar to eliminate air and dissolvedO2. Subsequently， the reactor was irradiated for 200 min using a300 W Xe lamp， with the temperature held constant at 293 Kthrough periodic cooling water circulation. The hydrogenproduced during the reaction was analyzed using an automaticon-line vacuum photocatalytic system （MC-SPB10， BeijingMerry Change Technology Co.， Ltd.） and an online gaschromatograph （GC， Agilent 7890B， USA）.

2.5 Photoelectrochemical measurements

Photocurrent measurements were conducted using theCHI660E electrochemical workstation （Shanghai ChenhuaInstrument Co.， Ltd.， China） equipped with a conventional threeelectrodesystem. Pt wires were employed as the counterelectrode， while Ag/AgCl served as the reference electrode. Theworking electrode was prepared by creating a slurry consistingof 5 mg of samples， 100 μL of absolute ethanol， and 10 μL of5% Nafion solution. This mixture was used to coat an F-dopedTin-O （FTO） glass substrate with an effective area of 1 cm2 usingthe dip-coating technique. The FTO glass substrates were driedusing an infrared lamp. A Xe lamp （250 W） served as the lightsource， and a 0.5 mol?L?1 Na2SO4 solution was used as theelectrolyte. The apparent quantum yield （AQY） was determinedusing the same experimental setup， subjecting it tomonochromatic light irradiation at wavelengths of 420， 450， 500，550， and 600 nm. The AQY value was calculated using formula（1）：

AQY（%） = 2（nH2/nP） × 100% （1）

where nH2 and np represent the numbers of evolved H2 molecules and incident photons， respectively.

2.6 Theoretical calculations

The Vienna Ab Initio Simulation Package （VASP） wasemployed to perform DFT calculations within the MedeA platform， utilizing the projector augmented plane-wavetechnique 53. The determination of the exchange-correlationpotential was based on the generalized gradient approximationproposed by Perdew， Burke， and Ernzerh. Our investigationfocused on two dominant facets： the BO （?121） facet and the ZIS（102） facet， as identified from X-ray diffraction （XRD） patternsand transmission electron microscopy （TEM） analysis. Theoptimized BO （?121） facet was modeled with dimensions of11.24 ? × 11.24 ? × 11.24 ? （1 ? = 0.1 nm）， while the ZIS （102）facet had dimensions of 6.73 ? × 3.92 ? × 12.79 ?. These facetswere modeled based on a suitable supercell size of （2 × 1 × 1）and （4 × 3 × 1）， respectively. Vacuum layers were adjusted to athickness of 20 ? to eliminate potential interference fromperiodic structures. It’s worth noting that using a 30 ? vacuumlayer resulted in only a 0.1 meV?atom?1 difference compared tothe 20 ? setting. Therefore， we opted for the 20 ? vacuum layerin subsequent calculations. A cutoff energy of 450 eV waschosen for plane wave calculations， and the Kohn-Shamequation was iteratively solved with an energy threshold of 10?5eV. A k-mesh size of 1 × 2 × 1 was used to integrate over theBrillouin zone. The relaxation process continued until theresidual forces on atoms reached a level lower than 0.05 eV???1.Free energy calculations were performed using the followingformula （2）：

ΔGH* = ΔEH* + ΔEZPE ? TΔS （2）

where ΔEH*， ΔEZPE， and ΔS represent the energy associated withhydrogen adsorption on the catalyst， the vibrational zero-pointenergy of the hydrogen molecule in the gas phase during thereaction， entropy， and temperature， respectively 54. It’s importantto mention that the process of water dissociation through theproton model is more straightforward compared to using ahydrogen atom on the catalytic surface. To establish a newmodel 55，56， we chose to use the proton instead of the hydrogenatom. To simulate H+ on the catalytic surface， adjustments weremade to the Nelect-1 option in Incar.

3 Results and discussion

3.1 Characterization of structure and morphology

Scheme 1 illustrates the manufacturing process of ZIS/BOusing varying ratio percentages. Initially， a prism-like structure of CAU-17 precursor was produced through a straightforwardhydrothermal method， wherein Bi（NO3）3?5H2O and 1，3，5-benzentriccarboxylic acid served as the metal ion center andorganic ligand， respectively. The yellow BO powder wasobtained by subjecting the CAU-17 precursor to pyrolysis underan air atmosphere at a temperature of 550 °C.

The morphology characteristics of the as-fabricated samplesare displayed. The rod-like BO （Fig. 1a）， derived from the CAU-17 precursor， are consistent with previous studies 57，58. Uponloading the flower-like ZIS （Fig. 1b） onto the surface， themorphology undergoes a transformation （Fig. 1c）， providingstrong evidence of the successful fabrication of ZIS/BO.Additionally， the energy dispersive spectrometer （EDS） patternof ZIS/BO （Fig. 1f） demonstrates the presence of Bi， O， Zn， In，and S， further confirming the loading of ZIS on the surface ofBO. The structure of ZIS/BO is observable through TEMimages. The flower-like structure of ZIS loaded on the surfaceof BO has a width of approximately 40 nm （Fig. 1d）. Moreover，the high-resolution transmission electron microscopy （HRTEM）image validates the presence of lattice fringes with an interlayerdistance measuring 0.334 and 0.328 nm， respectively. Thesemeasurements correspond to the crystal planes （102） of ZIS and （?121） of BO， as depicted in Figs. 1e and S1. Additionally， Fig.S2 presents the selected area electron diffraction （SAED）pattern， providing additional evidence to support this claim.Furthermore， the detailed structure and compositions wereinvestigated through TEM EDS mapping （Fig. 1g–l）， whichclearly demonstrates the homogeneous distribution of Bi， O， Zn，In， and S elements throughout the sample.

The crystal structures of pure BO， ZIS， and ZIS/BO hybridswere analyzed using a powder X-ray diffractometer. It is evidentthat the BO sample closely matches the standard card for BO（PDF No. JCPDS 41-1449）， and the distinct diffraction peaksobserved in Fig. 2a indicate its excellent crystalline quality. PureZIS exhibits three characteristic peaks at 2θ = 21.361°， 27.580°，and 47.181°， corresponding to （006）， （102）， and （002） diffractionplanes of ZIS （PDF No. JCPDS 65-2023）. Upon introducing ZISonto the surface of BO， the XRD patterns observed in the assynthesizedZIS/BO samples closely resemble those of pure BO.This similarity can be attributed to the relatively low content ofloaded ZIS 59. Furthermore， the partially enlarged XRD data（Fig. 2b） clearly demonstrates a noticeable shift towards lowerangles in the characteristic peaks corresponding to the （?121）plane of BO as the ZIS loading content increases. This observation suggests a robust interaction between these twomonomers and provides evidence for the successful formation ofZIS/BO hybrids 60. In this study， thermal gravimetric anddifferential scanning calorimetry （TG-DSC） analysis wereconducted to examine the thermal transformation of CAU-17into BO. The TG curves （Fig. 2c） suggest that the initial weightloss below 94.5 °C is attributed to the evaporation of residualorganic solvents. Subsequently， a significant weight reductionbetween 94.5 and 405.4 °C， accounting for an overall decreaseof approximately 59%， corresponds to the conversion of CAU-17 into BO. Furthermore， an exothermic peak at 403.8 °Cobserved in the DSC profile corroborates these findings， aspreviously mentioned.

The surface areas （SBET） and pore structure of thephotocatalysts were investigated using Brunner-Emmet-Teller（BET） analysis. The results revealed adsorption-desorptionisotherms and pore distribution patterns， as shown in Fig. 2d（inset）. Both the bare BO and 15% ZIS/BO samples displaycomparable features of type IV adsorption-desorption with typeH3 hysteresis loops， indicating mesoporous characteristics. Thisobservation is further supported by the detailed curves depictingthe distribution of pore sizes 61. Moreover， the specific surfacearea of bare BO （5.1199 m2?g?1） is smaller than that of the 15%ZIS/BO （11.4317 m2?g?1） sample. According to previous studies 62，63， a larger surface area typically offers more activesites， leading to better photocatalytic abilities. Therefore， thehybrids exhibit superior photocatalytic activities compared tobare BO.

X-ray photoelectron spectroscopy （XPS） analysis aimed toinvestigate the effective synthesis and surface chemicalproperties of pristine BO and ZIS/BO. The survey spectrum inFig. 2e confirms the presence of Bi， O， In， and Zn components，indicating the successful production of nanocompositescomprising ZIS/BO. Additionally， Fig. 2f，g present highresolutionXPS spectra for Bi 4f and O 1s， providing furtherinsights into the surface chemical states. In the case of bare BOsamples， the peaks at energy levels of 158.6 and 163.9 eVcorrespond to Bi 4f7/2 and Bi 4f5/2， respectively 64. The O 1sspectra exhibit two distinct peaks around 529.6 and 530.7 eV，indicating distinctive attributes. Introducing ZIS onto the surfaceof BO results in an observable shift towards higher bindingenergies in the high-resolution XPS spectra for Bi 4f and O 1s inZIS/BO nanocomposites， indicating a significant interactionbetween BO and ZIS 65. The Zn 2p spectrum （Fig. 2h） showspeaks at 1021.9 and 1045.2 eV， corresponding to the Zn 2p3/2 andZn 2p1/2 orbitals， respectively 66. Additionally， the In 3d spectrum（Fig. 2i） displays three characteristic peaks at 441.9， 444.6 and452.2 eV， with the peaks at 441.9 and 444.6 eV corresponding to In 3d5/2 and the peak at 452.2 eV corresponding to 3d3/2.Furthermore， Fig. S3 presents the XPS analysis results for pureZIS. In general， the XPS findings provide further evidence of thesuccessful production of ZIS/BO hybrid materials.

3.2 Effect of photocatalytic activity

Reactions for H2 evolution through photocatalysis wereconducted on the fabricated samples， and their efficiency wasevaluated when exposed to visible light （λ ≥ 420 nm） with TEOAas the sacrificial agent. As shown in Fig. 3a， the bare BOdemonstrates a certain level of H2 generation. However， uponintroducing ZIS onto the surface， there is a notable enhancementin the production of H2. Specifically， when the loadingpercentage reaches 15%， the H2 evolution reaches its peak，approximately 6.34 times higher than that of pure BO， indicatingthe enhanced photocatalytic performance of the ZIS/BO hybrids.However， when the loading ratio reaches 20%， the ZIS/BOexhibits a decrease in the rate of hydrogen evolution comparedto 15%. The reason may be that when the amount of ZIS reachesa certain value， the progress of photocatalytic hydrogenproduction is impeded in terms of efficiency. The stability andreusability of the 15% ZIS/BO hybrids were tested by cyclingthe H2 reaction under the same conditions （Fig. 3b）. Nosignificant decrease in the H2 evolution rate is observed duringfive cycles， proving the excellent stability of ZIS/BO hybrids.According to equation （1）， the apparent quantum efficiency ofthe 15% ZIS/BO composite is 10.8%， 7.8%， 7%， 6.5%， and5.9%， respectively， when the light source wavelength is 420，450， 500， 550， and 600 nm， as shown in Fig. 3c.

Electron spin resonance （ESR） spectra of bare BO and 15%ZIS/BO are presented in Fig. 3d. Both bare BO and 15% ZIS/BOshow the existence of oxygen vacancies （OVs）. The increasedpresence of OVs facilitates the enrichment and electron transferto In and O atoms in the hybrid 15% ZIS/BO material. Theoptical properties of the synthesized samples were examinedusing UV-Vis diffuse reflectance spectroscopy （DRS）. Theobtained results are presented in Fig. 3e， indicating that bothpure BO and ZIS/BO samples exhibit remarkable responsivenessacross the UV to visible light range. With the introduction ofZIS， the light response capacity of all ZIS/BO samples issignificantly improved compared to pure BO. Additionally， thereis a noticeable red-shift in the absorption thresholds， possiblyindicating a synergistic interaction between the monomers 67.The enhanced capacity for capturing light would result in thegeneration of a greater number of charge carriers， therebyimproving the effectiveness of photocatalytic applications 68. Asa consequence， the hybrids synthesized demonstrate promisingcapabilities as effective photocatalysts when exposed to visiblelight.

The evaluation of photocatalytic activities involves assessingthe efficiency of inter separation， which are crucial factors. Thisis done through conducting photocurrent response tests andelectrochemical impedance spectroscopy （EIS） analysis. Fig. 3fshows the photocurrent response of as-fabricated photocatalysts.In comparison to the bare BO， the 15% ZIS/BO displays higherphotocurrent intensities， which is further proved by the EISexperiment. The 15% ZIS/BO sample has a smaller arc radiusthan pure BO （Fig. 3g）. The photocurrent response of ZIS isshown in Fig. S4. It is postulated that a direct relationship mayexist between the strength of photocurrent and the effectivenessof charge separation 69. As a result， the 15% ZIS/BO hybridprepared in this study demonstrates enhanced efficiency incharge migration and separation， leading to improvedphotocatalytic activity. Additionally， the consistent findingsfrom both EIS and photocurrent response measurements aresupported by the results of photoluminescence （PL） analysis.The reduced intensity of PL indicates effective separation anddecreased recombination of photoinduced charge carriers 70. Asshown in Fig. 3h， the as-fabricated 15% ZIS/BO sample displayslower PL intensity. The photocatalytic activity is influenced bythe carrier lifetime， which is a crucial factor. The PL emissionlifetimes of 15% ZIS/BO， bare BO， and samples are recorded as0.69， 0.41， and 0.84 ns respectively （Figs. 3i and S5）. It can beobserved that the longer carrier lifetime in the case of the 15%ZIS/BO sample indicates an enhancement in charge carrierseparation efficiency， leading to improved photocatalyticactivity.

3.3 Reaction mechanism based on S-scheme heterojunction

To gain a comprehensive understanding of the charge transferpathway between ZIS and BO at the interface， we employed aKelvin probe instrument to assess the contact potentialdifference （CPD） of the samples both in the dark and underirradiation. Based on DFT simulations， we determined the workfunctions of pure ZIS and BO to be 4.78 and 5.37 eV，respectively （Fig. 4c，f）. Consequently， ZIS and BO possessFermi energy levels （Ef） of ?3.17 and ?3.91 eV， respectively.These findings suggest that BO has a less-negative Ef comparedto ZIS. When ZIS and BO come into close contact， electrons willmigrate from ZIS to BO until reaching an equilibrium state.

The investigation using photo-irradiated Kelvin probe forcemicroscopy （KPFM） further demonstrated the spatial separationof charges in the ZIS/BO material （Fig. 4a，c）. The difference insurface potential between ZIS and BO is approximately 542 mV（Fig. 4b，e）， indicating the presence of an internal electric field（IEF） responsible for driving the movement of photogenerated charges from ZIS to BO. Under light irradiation， the surfacepotential on ZIS decreased （from 925 to 670 mV） （Fig. 4b），while the surface potential on BO increased （from 383 to 447mV） （Fig. 4d）. This suggests the migration of photogeneratedelectrons from BO to ZIS， resulting in an equal overall chargechange in both components. Additionally， due to the dominantpresence of BO in the ZIS/BO composite， it is expected toexhibit a comparatively lower density of accumulated chargecarriers on its surface compared to ZIS. Specifically， BO showsa modest change in surface potential of only 64 mV， whereas ZISshows a significant change of 255 mV. As depicted in Fig. 4b–d，these observed variations in surface potential at the interfacebetween ZIS and BO provide substantial evidence that underlight exposure， the electron donation primarily originates fromthe BO component within the ZIS/BO heterojunction.

To provide additional evidence for the existence of the Sschemeheterojunction in ZIS/BO， we employed the electronspin resonance （ESR） technique. The S-scheme heterojunctioncan effectively trap photo-induced electrons and holes withstrong reduction/oxidation abilities. The ESR technique allowedus to detect reaction-generated radicals， such as ·OH and ·O2?， onBO， ZIS， and ZIS/BO， enabling an estimation of the redoxcapabilities of these photocatalysts. After exposing the samplesto light for 10 min， we detected the presence of DMPO-·OH andDMPO-·O2? using 5，5-imethyl-1-pyrroline N-oxide （DMPO） asthe spin-trapping agent （Figs. S6 and S7）. The results in Fig. S6confirm the presence of highly oxidative ·OH in the aqueoussolution of ZIS/BO after 10 min of light illumination.Furthermore， Fig. S6 indicates the absence of ·OH in the BOaqueous solution. These findings support the observation that thevalence band （VB） edge of BO （+2.88 V vs. normal hydrogenelectrode （NHE）; Fig. 5d and Table S1） exhibits a higher positivepotential compared to the standard reduction potential of E0（·OH/OH?） （+2.80 V vs. NHE）. Conversely， the VB potential ofZIS is significantly less positive， with a value of +1.68 V vs.NHE. Importantly， Fig. S6 displayed enhanced indications ofDMPO-·OH for ZIS/BO compared to those for ZIS. This can beattributed to the improved efficiency of electron/hole separationand transfer in the S-type heterojunction， which is solely due tothe transition from BO to ZIS.

Furthermore， as shown in Fig. S7， it reveals the existence of·O2? in the methanol solution of ZIS and ZIS/BO after 10 minutesof light exposure. This is attributed to the conduction band （CB）edge of ZIS exhibiting a more negative potential （?0.76 V vs.NHE; Fig. 5d） compared to the standard reduction potential（O2/·O2?） （?0.33 V vs. NHE）. However， the reduction ability ofelectrons in the CB of ZIS resulted in minimal detection ofDMPO-·O2? signals in the methanol solution. Furthermore，stronger signals were detected for ZIS/BO compared to ZIS，indicating an elevated charge dissociation and transportefficiency in ZIS. It is important to mention that no ESR signalwas observed in the blank experiments， indicating the nonparamagneticresponse of the DMPO molecule. As a result， the combination of these discoveries provides strong evidence forthe effective establishment of the S-scheme heterojunction inZIS/BO. Fig. 4c，f illustrate that BO has a lower Fermi levelcompared to ZIS conjugated polymer. When BO and ZIS are inproximity， electrons transfer from ZIS to BO until their Fermilevels match. This results in an accumulation of electrons at theinterface of BO and a decrease in electron density at the surfaceof ZIS， causing downward band bending on BO and upwardband bending on ZIS. This results in the establishment of aninternal electric field at the interface， with the direction from ZISto BO. During irradiation， both BO and ZIS experiencephotoexcitation. The electrons generated by light are transferredfrom the conduction band （CB） of BO to the valence band （VB）of ZIS， where they undergo recombination with carriers. As aresult， the valence band of BO retains photogenerated holeswhile the conduction band of ZIS holds onto photogeneratedelectrons. This charge transfer pathway follows an S-schemeroute， which maintains the strong reducing ability of electrons inZIS and the strong oxidizing ability of VB holes in BO. Thisconfiguration provides a powerful driving force for protonreduction under the action of hole sacrificial agent.

3.4 Mechanism study of H2 evolution

To gain a more profound insight into the underlying processesof photocatalysis， we employed the Mott-Schottky （MS）technique and VB-XPS spectra to investigate the Fermi level andthe semiconductor type of pure BO and the synthesized ZIS. Ouranalysis reveals that both pure BO and the as-synthesized ZISare p-type semiconductors （Fig. 5a，b）. Furthermore， the flat bandlevel of bare BO and the as-fabricated ZIS is determined to be?0.13 and ?0.83 eV， respectively. According to prior research，the conduction band potential （ECB） is approximately 0.1 eVbelow or equal to the flat band level 71–74. Consequently， it canbe inferred that the ECB of bare BO and the as-fabricated ZIS areapproximately ?0.03 and ?0.73 eV. As illustrated in Fig. 5c， theenergy bandgap （Eg） of unmodified BO is measured to be 2.91eV， whereas for the ZIS material after fabrication， it is found tobe 2.41 eV. Additionally， the calculated values for the valenceband maximum （EVB） are determined to be 2.88 eV for bare BOand 1.68 eV for the fabricated ZIS samples. The energy bandstructures of unmodified BO and the ZIS fabricated in theiroriginal states are depicted in Fig. 5d. For detailed calculations，please refer to Table S1.

3.5 Theoretical simulation

To deepen our understanding of the impact of the ZIS/BOheterojunction on the efficiency of the HER， we employed DFTcalculations. The structural models of BO and ZIS are depictedin Fig. 6a （please refer to the “Experimental section” for moredetails）. To explore the electronic structure of the ZIS/BOheterojunction， we began by simulating the charge densitydifference （Fig. 6b）. It is clear that there is charge accumulationnear BO and charge depletion around ZIS. This observationindicates the existence of charge interaction within the ZIS/BOheterojunction， which aligns with the findings from XPS andelectron localization function （ELF） analysis （Fig. 6c）. Thepresence of strong localized regions in Fig. 6c suggests theexistence of covalent bonds between In and O， underscoringtheir covalent nature.

To further investigate the intrinsic relationship between theelectronic configuration and the enhanced photocatalytic HERefficiency of the ZIS/BO heterojunction， we delved into the energy of HER intermediates. The ΔGH* value， which representsthe energy change for the adsorption of a hydrogen atom and thesubsequent formation of molecular H2， serves as a crucialparameter to predict and assess the efficiency of HER on thecatalyst surface. We performed calculations to determine theΔGH* values for Bi elements in BO， as well as Zn， In， and Selements in ZIS （Fig. 6d and Table S2）. The outcome of the DFTcalculation suggests that the ΔGH* values for S in ZIS and O inBO are more negative， indicating excessively strong adsorptionof H and unfavorable conditions for both H2 desorption andrelease. In contrast， the ΔGH* value of In in ZIS/BO （Fig. 6d） isclose to the desired ΔGH* = 0 eV， suggesting favorable Hadsorption and subsequent release of H2， thereby supporting thesuperior HER performance of ZIS/BO. Hence， the introductionof ZIS should serve as the primary catalytic site for HER inZIS/BO heterojunctions， aligning well with the experimentallyobserved enhanced photocatalysis in the composites of ZIS andBO.

Furthermore， to further validate the significance of this work，the hydrogen evolution performance of our photocatalysts wascompared with those reported in previous studies （Fig. S8 andTable S3）.

3.6 Wettability of ZIS/BO

Water adsorption plays a crucial role in the process ofphotocatalytic hydrogen production. To gain deeper insights intothe factors influencing water splitting， it is imperative toexamine the adsorption characteristics of water molecules. Thecatalysts’ contact angle was measured， revealing an originalcontact angle of 27.5°， indicating a hydrophilic nature.Interestingly， the contact angle of 15% ZIS/BO （19.5°） isreduced due to the introduction of ZIS （Fig. 7a）， showingenhanced photocatalytic activity dependent on water adsorption.

To explore the underlying mechanism behind the observedacceleration of the HER rate， molecular BO and water moleculesunderwent Molecular Dynamics simulations for molecularanalysis. Three different modeling systems were implemented，consisting of varying weight percentages （1%， 5%， and 15%） ofZIS/BO and pure water （Fig. 7b）. The force field parameters forVan Der Waals forces （VDW） interactions are shown in TableS4. The likelihood of encountering an oxygen atom at a specificdistance from a designated oxygen atom in water was assessedby computing the radial distribution functions （RDF）interactions involving Owater-Owater and Owater-OBO （Fig. 7c）.

The results suggest that the arrangement of water moleculesin the simulation system is impacted by the presence of ZIS. Inparticular， the initial peak magnitude observed in watermolecules within the BO nanostructure exhibits a significantenhancement when ZIS is incorporated into the 15% ZIS/BOsystem. This implies modifications in the water state of thiscatalyst compared to the other two catalysts. The quantitativeanalysis of hydrogen bonding in systems with varying ZIScontents involves calculating the overcount of hydrogen bondsencompassing both Owater―Owater and Owater―OBO bonds. Theaverage count of hydrogen bonds among water molecules consistently decreases， while the increase in ZIS content leads toan augmentation in the number of hydrogen bonds formedbetween water molecules and BO （Fig. 7d）. This suggests thatthe presence of ZIS hinders the strong connections among watermolecules and the BO nanochannels， resulting in a decrease inpotential energy and an increase in water’s affinity forhydrolysis. Consequently， this improvement contributes to anincrease in HER efficiency. This is consistent with thewettability test results of 15% ZIS/BO and BO catalysts. Allthese findings indicate that the introduction of ZIS enhances thewater absorption of the system， resulting in the ZIS/BO Sschemeheterojunction having excellent hydrophilicity andwettability， which is beneficial for photocatalytic water splittingand hydrogen evolution.

4 Conclusions

In summary， a simple hydrothermal technique was employedto effectively synthesize the S-scheme heterojunction ofZIS/BO. The optimized ZIS/BO heterojunction exhibits ahydrogen production rate of 1610 μmol?g?1?h?1 at a ZIS ratio of15%， which is approximately 6.34 times greater compared to BOalone. The findings suggest that the formation of aheterojunction between ZIS and BO improves the separation ofcharge carriers generated by light and facilitates the transfer ofphoto-induced electrons from BO to ZIS. Experimental tests oncontact angle and molecular dynamics analysis have alsoconfirmed that incorporating ZIS enhances the hydrophilicity，thereby improving its performance in hydrogen evolution. Thissynergistic approach involving adjustments in wettability andelectronic properties holds potential for applications in designingand synthesizing various composite materials for energy andenvironmental purposes.

Conflicts of Interest： The authors declare no conflict of interest.

Author Contributions： Conceptualization， Runhua Liaoand Yingtang Zhou; Methodology， Linfeng Xiao; Software，Mengshan Chen; Validation， Wanlu Ren， Shishi Shen and XibaoLi; Formal Analysis， Linfeng Xiao; Investigation， Runhua Liao;Resources， Yingtang Zhou; Data Curation， Linfeng Xiao;Writing， Original Draft Preparation， Linfeng Xiao; Writing，Review amp; Editing， Linfeng Xiao， Runhua Liao and YingtangZhou; Visualization， Mengshan Chen; Supervision， Xibao Li;Project Administration， Yingtang Zhou; Funding Acquisition，Runhua Liao， Yingtang Zhou and Xibao Li.

Acknowledgement： The authors would like to thankShiyanjia Lab （www.shiyanjia.com） for the XPS etc.measurement and equipment manufacturers （SaifanOptoelectronics， etc.）.

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

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浙江省重點(diǎn)研發(fā)項(xiàng)目（2023 C01191）， 國(guó)家自然科學(xué)基金項(xiàng)目（22262024， 51962023， 51468024）， 江西省重點(diǎn)學(xué)科學(xué)術(shù)技術(shù)帶頭人項(xiàng)目（20232BCJ22008），江西自然科學(xué)基金（20232ACB204007， 20202BABL203037）， 景德鎮(zhèn)市科技局項(xiàng)目（20192GYZD008-33）資助