Surface Atomic Arrangement Research Articles

MOF-derived phase-selective synthesis of ln2O3 with appropriate surface atomic arrangement for CO2 photoreduction

Crystal phase engineering emerges as a powerful strategy to enhance photocatalytic activity, yet controlled phase-selective synthesis and phase-dependent performance understanding remain challenging. In this study, we introduce a novel method for synthesizing phase-engineered In2O3 via the pyrolysis of metal–organic frameworks (MOFs). We demonstrate that the functional groups and pyrolysis temperatures of MOFs are critical for phase-selective synthesis. Specifically, pyrolysis of MIL-68(ln)–NH2 at optimal temperatures yields In2O3 with rhombohedral (rh-In2O3), cubic (c-In2O3), and rhombohedral/cubic heterophase (rh/c-In2O3) structures. Our photocatalytic CO2 reduction tests reveal that c-In2O3 outperforms rh-In2O3 and rh/c-In2O3, achieving a CO production rate of 29.19 μmol g-1h−1 with 94.47 % selectivity. Spectroscopic and theoretical analyses show that c-In2O3 has superior charge transfer efficiency and lower reaction energy barriers, particularly for the rate-determining *CO intermediate, which exhibits a lower Gibbs free energy on its surface. This work provides a significant advancement in optimizing photocatalytic CO2 reduction efficiency through precise phase engineering, underscoring the vital role of phase control in enhancing catalytic performance.

Activating d10 electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H2 by surface atomic arrangement

Relationship between the activity for photocatalytic H2O overall splitting (HOS) and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram, and specially the d10 electronic configuration in valley bottom exhibits inert activity, which seriously fetters the development of catalytic materials with great potentials. Herein, In d10 electronic configuration of In2O3 was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band (In ɛ5p) and descended O 2p-band (O ɛ2p) centers as efficient active sites for chemisorption to *OH and *H during forward HOS, respectively, along with a declined In 4d-band center (In ɛ4d) to inhibit its backward reaction. A stable STH efficiency of 2.23% under AM 1.5 G irradiation at 65 °C has been obtained over the activated d10 electronic configuration with a lowered activation energy for H2 evolution, verified by femtosecond transient absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics. These findings devote to activating d10 electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS, which expands the exploration of high-efficiency catalytic materials.

Water-induced surface ordering facilitating the microcutting of ductile metals

Metal cutting is a crucial process in modern manufacturing. Enhancing the machinability of metals can significantly improve their production efficiency and surface integrity. Coating surface-active media (SAM) on the free surface of the metals before cutting is an easy method to improve machinability, which usually pertains to the category of the renowned Rehbinder effect. However, the existing SAM is usually hazardous and complex materials. Besides, the effect of SAM on the local structure of the metal surface remains unclear. In this study, water is employed as a simple yet often overlooked SAM in the microcutting of copper. Using water as SAM also allows the employment of X-ray absorption fine structure spectroscopy (XAFS) to study the local structure of copper with and without water coating. Results show that water coating on the free surface of copper can significantly reduce the cutting force and chip thickness, and improve the surface finish. Interestingly, removing the water coating enables the recovery of the cutting force, demonstrating a reversible effect. Based on the XAFS results and molecular dynamics simulation, a water-induced surface ordering mechanism is proposed to explain the findings from the microcutting experiments. This mechanism suggests that water molecules can induce surface ordering in copper, resulting in reduced surface energy and fracture toughness of copper, thus enhancing machinability. This work provides valuable insights into the comprehension of the Rehbinder effect and shows that picometer-scale modifications of the surface atom arrangement can considerably alter the deformation mode of metals, paving the way for the development of new manufacturing processes.

Oxygen vacancy and boron dual sites enable efficient oxygen activation for emerging contaminant degradation: Boosted exciton dissociation via built-in electric field modulation

Two-dimensional (2D) layered materials are promising photocatalysts for environmental remediation through O2 activation. However, the inherent robust excitonic effects from the confined-layer structure hinder the generation of highly oxidative free radicals from the preferred charge transfer pathway. Taking 2D BiOBr as a prototype, we implemented a superficial surface boronizing method to incorporate oxygen vacancy (OV)-boron (B) dual sites onto the surface. The OV-B dual sites disorder the surface atomic arrangement of BiOBr and induce strong built-in electric field (BEF). This effectively weakens exciton binding energy, boosts exciton dissociation into free charges, and facilities the transfer and separation of free charges, which collectively enables charge transfer to surpass excitonic effects as the dominant O2 activation pathway. Consequently, BiOBr with OV-B dual sites outperforms pristine and mono-OV modified BiOBr in both O2 activation and emerging contaminant degradation. This work offers insightful strategies for modulating 2D photocatalysts to optimize O2 activation towards efficient contaminant removal.

Protein Corona Formation on Cadmium-Bearing Nanoparticles: Important Role of Facet-Dependent Binding of Cysteine-Rich Proteins.

Cadmium-bearing nanoparticles, such as nanoparticulate cadmium selenide (CdSe) and cadmium sulfide (CdS), widely exist in the environment and originate from both natural and anthropogenic sources. Risk assessment of these nanoparticles cannot be accurate without taking into account the properties of the protein corona that is acquired by the nanoparticles upon biouptake. Here, we show that the compositions of the protein corona on CdSe/CdS nanoparticles are regulated collectively by the surface atomic arrangement of the nanoparticles and the abundance and distribution of cysteine moieties of the proteins in contact with the nanoparticles. A proteomic analysis shows that the observed facet-dependent preferential binding of proteins is mostly related to the cysteine contents of the proteins, among commonly recognized protein properties controlling the formation of the protein corona. Theoretical calculations further demonstrate that the atomic arrangement of surface Cd atoms, as dictated by the exposed facets of the nanoparticles, controls the specific binding mode of the S atoms in the disulfide bonds of the proteins. Supplemental protein adsorption experiments confirm that disulfide bonds remain intact during protein adsorption, making the binding of protein molecules sensitive to the abundance and distribution of Cd-binding moieties and possibly molecular rigidity of the proteins. The significant conformational changes of adsorbed proteins evidenced from a circular dichroism spectroscopy analysis suggest that disrupting the structural stability of proteins may be an additional risk factor of Cd-bearing nanoparticles. These findings underline that the unique properties and behaviors of nanoparticles must be fully considered when evaluating the biological effects and health risks of metal pollutants.

Optimization of d-p band centers as efficient active sites for solar energy conversion into H2 by tuning surface atomic arrangement

The lowered reaction energy barrier and accelerated dynamic behavior for photocatalytic H2O overall splitting (HOS) involving oriented chemisorption, activation and conversion of *H and oxyhydrogen intermediates are crucial for solar energy conversion into H2 (STH). Herein, the localized heterojunction (Cd-S-Ni) composed of NiS and CdS via. tuning surface atomic arrangement with S atoms as the shared ligands has been constructed to synchronously elevate and optimize Ni 3d (Ni ε3d) and S 2p (S ε2p) band centers as efficient active sites for chemisorption of oxyhydrogen and *H intermediates with a declined Cd 4d band center (Cd ε4d) to suppress reverse reaction. A sustainable STH of 3.21 % under AM 1.5 G has been completed over Cd-S-Ni with a decreased activation energy for H2 evolution, verified by fs-TAS, in situ DRIFTS and dynamic DFT. These results devote to solving the reaction energy barrier and dynamical bottleneck for HOS by optimizing εd and εp.

Crystal-Phase- and B-Content-Dependent Electrochemical Behavior of Pd─B Nanocrystals toward Oxygen Reduction Reaction.

The manipulation of crystal phases in metal-nonmetal interstitial alloy nanostructures has attracted considerable attention due to the formation of unique electronic structures and surface atomic arrangements, resulting in unprecedented catalytic performances. However, achieving simultaneous control over crystal phase and nonmetal elements in metal-nonmetal interstitial alloy nanostructures has remained a formidable challenge. Here, a novel synthesis approach is presented for Pd─B interstitial alloy nanocrystals (NCs) that allows investigation of the crystal-phase- and B-content-dependent catalytic performance. Through comparison of the oxygen reduction reaction (ORR) properties of Pd─BX interstitial alloy NCs with different crystal phases and B contents, achieved by precise control of reaction temperature and time, the influences of crystal phase and B contents in the Pd─BX interstitial alloy NCs on ORR are precisely investigated. The hexagonal closed packed (hcp) PdB0.5 NCs exhibit superior catalytic activity, with mass activities reaching 2.58 A mg-1, surpassing Pd/C by 10.3 times, attributed to synergistic effects by the hcp crystal phase and relatively high B contents. This study not only provides a novel approach to fabricate interstitial alloy nanostructures with unconventional crystal phases and finely controlled nonmetal elements but also elucidates the importance of crystal phase and nonmetal element content in optimizing electrocatalytic efficiency.

Theoretical study of the effects of surface Cu coordination environment on CO2 hydrogenation to CH3OH

The coordination environment of Cu (the coordination number and arrangement of surface atoms) plays an important role in CO2 hydrogenation to CH3OH. Compared with the extensive studies of the effects of coordination number, the comprehensive effects of coordination number and arrangement of surface atoms were seldom explored in literature. To unravel the effects of surface Cu coordination environment on CO2 hydrogenation to CH3OH, the adsorption and reaction behaviors of H2 and CO2 on Cu(111), (100), (110) and (211) with different coordination numbers and arrangement of surface Cu were systematically calculated by density functional theory (DFT) and kinetic Monte Carlo (kMC) simulation. It was found that the adsorption energies of intermediates in CO2 hydrogenation on Cu surfaces increase with the decrease of coordination number. When the Cu coordination numbers are similar, the charge density on the open surface derived from the different atom arrangement becomes larger and leads to stronger interaction with intermediates than that on the compact one. DFT calculation and kMC simulation indicate that methanol formation pathway follows CO2*→HCOO*→HCOOH*→H2COOH*→H2CO*→CH3O*→CH3OH* on four Cu facets; CO formation is via CO2 direct dissociation on Cu(111), (100) and (110) but COOH* dissociation on (211). The low-coordinated surface Cu with more openness on Cu(211) is the highly active site for CO2 hydrogenation to CH3OH with high turnover of frequency (3.71 × 10−4 s−1) and high selectivity (87.17 %) at 600 K, PCO2 = 7.5 atm and PH2 = 22.5 atm, which is much higher than those on Cu(111), (100) and (110). This work unravels the effects of coordination environment on CO2 hydrogenation at the molecular level and provides an important insight into the design and development of catalysts with high performance in CO2 hydrogenation to CH3OH.

Surface atomic arrangement of primary particles through pre-oxidation to enhance the performance of LiNi0.8Co0.1Mn0.1O2 cathode materials

The primary drawback of Ni-rich LiNixCoyMn1-x-yO2 (NCM, x ≥ 0.8) cathodes lies in their capacity and voltage fading, a phenomenon principally attributed to interfacial instability and intergranular cracks. This study introduces a simple pre-oxidation treatment to modify the grain boundary of LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material as an efficient solution to these issues. Spectroscopic analysis and atomic-level imaging affirm that this pre-oxidation treatment facilitates both the conversion of Ni2+ to Ni3+ and the formation of an ordered NiOOH structure on the surface of precursor primary particles. Consequently, the final NCM811 product displays a distinct layered structure with a reduced degree of Li/Ni disorder. Furthermore, a rock-salt phase surface reconstruction layer is in-situ induced on the surface of NCM811 primary particles during the solid-state lithiation process, providing a protective coating against further degradation of the R3¯m-layered phase beneath it. Therefore, this enhanced NCM811 demonstrates superior structural stability regarding phase transition, cathode-electrolyte interface structure, and morphological integrity. When compared to bare NCM811 and modified NCM811 based on secondary particles, this enhanced NCM811 exhibits greater reversible capacity, superior initial coulombic efficiency, and excellent capacity retention. This study thus offers a promising approach to induce the ordered surface reconstruction of primary cathode particles, forming a conformal protective layer that improves electrochemical stability.

Sub-millisecond pulsed laser engineering of CuOx-decorated Pd nanoparticles for enhanced catalytic CO2 hydrogenation

Catalytic CO2 hydrogenation to fuels and chemicals presents a promising avenue for addressing global warming and advancing toward a net-zero economy. Surface atomic rearrangement of catalysts has attracted growing interest as a means to manipulate catalyst activity and selectivity. Herein, we designed a ternary nanocatalyst comprising CuOx species decorated Pd nanoparticles (NPs) supported on Co oxide (denoted as CPCu) for catalytic CO2 hydrogenation. Sub-millisecond laser treatment (1 mJ per pulse) was used to manipulate the surface atomic arrangements of CPCu the catalyst. The CPCu nanocatalyst showed a significant enhancement in both CH4 production and CO production at 300 °C compared to the Pd/Co catalyst. Notably, the CH4 production using the laser-treated nanocatalyst (denoted as CPCu-L) was 66.6 % higher than the untreated one (CPCu) at 300 °C. Comprehensive catalyst characterizations revealed that CuOx species promoted CO2 activation, while neighboring Pd domains effectively dissociated H2 molecules, leading to enhanced CH4 production. This study demonstrates the potential of sub-millisecond laser treatment for tailoring catalyst surfaces, offering a promising strategy to design more active and selective catalysts for CO2 hydrogenation.

Interfacial Second-Harmonic Generation via Superposition of Symmetries in a Double-Resonance-Enhanced Plasmonic Nanocavity.

Second-harmonic generation (SHG) has rapidly advanced with the miniaturization of on-chip devices and has found many applications, including optical frequency conversion, nonlinear imaging, and quantum technology. However, owing to the obvious phase-matching constraints involved in nonlinear optical interactions in bulk crystals and the decrease in the length and strength of nonlinear interactions in nanophotonic and surface/interface systems, improving the SHG efficiency and manipulating its optical properties at the nanoscale are challenging tasks. Herein, a monocrystalline silver microplate and nanocube-coupled nanocavity with double-resonance plasmonic modes and an ultrasmall gap were constructed, resulting in efficiently enhanced SHG. In particular, the SHG from the silver microplate (111) is polarization-dependent, and the anisotropy of the SHG in the plasmonic nanocavity can be further controlled via the superposition of symmetries at the interface and plasmonic waveguide-cavity modes. The interfacial SHG provides technology for developing lattice surface atomic arrangement and nanostructure rapid characterization, nonlinear light sources, and on-chip nonlinear nanophotonic devices.

Sulfidation-Induced Surface Local Electronic and Atomic Structures in a Silver Catalyst Enables Silicon Photocathode for Selective and Efficient Photoelectrochemical CO2 Reduction.

Converting CO2 to value-added chemicals through a photoelectrochemical (PEC) system is a creative approach toward renewable energy utilization and storage. However, the rational design of appropriate catalysts while being effectively integrated with semiconductor photoelectrodes remains a considerable challenge for achieving single-carbon products with high efficiency. Herein, we demonstrate a novel sulfidation-induced strategy for in situ grown sulfide-derived Ag nanowires on a Si photocathode (denoted as SD-Ag/Si) based on the standard crystalline Si solar cells. Such an exquisite design of the SD-Ag/Si photocathode not only provides a large electrochemically active surface area but also endows abundant active sites of Ag2S/Ag interfaces and high-index Ag facets for PEC CO production. The optimized SD-Ag/Si photocathode displays an ideal CO Faradic efficiency of 95.2% and an onset potential of +0.26 V versus the reversible hydrogen electrode, ascribed to the sulfidation-induced synergistic effect of the surface atomic arrangement and electronic structure in Ag catalysts that promote charge transfer, facilitate CO2 adsorption and activation, and suppress hydrogen evolution reaction. This sulfidation-induced strategy represents a scalable approach for designing high-performance catalysts for electrochemical and PEC devices with efficient CO2 utilization.

Facet-dependent in-situ formation of oxygen vacancy and plasmonic Bi in BiOBr nanosheets and resultant influence on the generation and separation of charge carriers

The development of advanced photoactive materials has aroused widespread interest, but is severely plagued by the inherent narrow photo-responsive range and rapid recombination of electrons and holes. In this study, the unconventional BiOBr nanosheets decorated with Bi0 and oxygen vacancies (OVs) are successfully synthesized through a facial one-pot hydrothermal method, followed by heat treatment. Cetyltrimethylammonium bromide and mannitol contribute to the selective exposure of (001) and (010) facets, respectively. The absence of the outermost Br atoms facilitates the simultaneous generation of OVs and Bi0 on the surface during heating, forming the Schottky junction. The synergy of SPR in the Bi0 metal, OVs and Schottky junction can effectively enhance the light absorption and charge separation. This work proposes and verifies a feasible approach to construct defects in-situ by regulating the crystal facets and manipulating the surface atomic arrangement and coordination.

General synthesis and atomic arrangement identification of ordered Bi-Pd intermetallics with tunable electrocatalytic CO2 reduction selectivity.

Intermetallic compounds (IMCs) with fixed chemical composition and ordered crystallographic arrangement are highly desirable platforms for elucidating the precise correlation between structures and performances in catalysis. However, diffusing a metal atom into a lattice of another metal to form a controllably regular metal occupancy remains a huge challenge. Herein, we develop a general and tractable solvothermal method to synthesize the Bi-Pd IMCs family, including Bi2Pd, BiPd, Bi3Pd5, Bi2Pd5, Bi3Pd8 and BiPd3. By employing electrocatalytic CO2 reduction as a model reaction, we deeply elucidated the interplay between Bi-Pd IMCs and key intermediates. Specific surface atomic arrangements endow Bi-Pd IMCs different relative surface binding affinities and adsorption configuration for *OCHO, *COOH and *H intermediate, thus exhibiting substantially selective generation of formate (Bi2Pd), CO (BiPd3) and H2 (Bi2Pd5). This work provides a comprehensive understanding of the specific structure-performance correlation of IMCs, which serves as a valuable paradigm for precisely modulating catalyst material structures.

Facet-dependent peroxymonosulfate activity and mechanism of CuO for degradation of organic pollutants

CuO is currently used as an effective activator for peroxymonosulfate (PMS), which exhibits complex radical, nonradical, or both activation pathways. However, there exists a knowledge gap concerning the relationship between CuO exposed facets and the PMS activation pathway, which should require further investigation. This study employed a simple and facile hydrothermal method to controllably prepare CuO samples with exposed {010} and {001} facets (referred to as CuO-010 and CuO-001, respectively). The main aim was to further study the facet-dependent PMS activation mechanism. The experimental results showed that the CuO-001 exhibited significantly higher activation efficiency than the CuO-010 due to the different surface atomic arrangement. Furthermore, scavenging experiments and EPR analyses revealed that CuO-010 exhibited both radical (SO4•− and •OH) and non-radical (1O2) pathways, synergistically degraded tetracycline (TC) and 4-nitrophenol (4-NP). Conversely, the CuO-001 displayed non-radical (1O2) and Cu(Ⅲ) intermediates, collaborating to oxidize the degradation of TC and 4-NP. More importantly, the generated 1O2 species and Cu(Ⅲ) intermediates exhibited a preference for reacting with amino or phenolic compounds containing electron-rich functional groups. Moreover, the CuO-001 also showed excellent resistance to anion interference, stability, and compatibility of a wide pH range. The outcomes of this study provide new insights into the comprehensiveness facet-dependent activation of PMS and the design of efficient metal oxide catalysts using the facet strategy for effective degradation of amino/phenolic pollutants in wastewater.

Unraveling the origin of facet-dependent photocatalytic H2O2 production over anatase TiO2

A typical photocatalytic H2O2 production reaction primarily comprises three processes: photoabsorption, electron–hole separation and transfer, and surface oxygen reduction reaction. Previous researches have focused on revealing the origin of the facet effect in photocatalysis. However, a comprehensive understanding of the structure–activity relationship for facet effect at atomic scale remains limited. Herein, we provide fundamental insights into photocatalytic H2O2 production performance of three types of TiO2 with predominantly exposed (101), (100), or (001) facets. The TiO2 nanosheets with exposed (001) facet exhibit the highest H2O2 yield rate of 649.2 μmol g-1 h-1, which is 29.2 and 5.2 times higher than those of TiO2 with (101) facet and (100) facet, respectively. Band alignment, charge carrier behavior, and surface reaction are studied systematically and correlated with unique surface atom arrangement. Even with narrowed light-response range, short charge carrier lifetime, inferior charge separation, and inconspicuous specific surface area, the (001) facet exposed TiO2 still performs best. The experimental results and density functional theory (DFT) calculations reveal that the under-coordinated Ti atoms on (001) surface serve as active sites and have strong interaction with oxygen molecule, while the Ti atoms on (101) and (100) surface can hardly adsorb and activate oxygen molecule. Hence, we suggest that the significantly lowered barrier for oxygen molecule adsorption and activation results from intrinsic surface sites rather than band-alignment, and the charge carrier behavior plays the principal role in this case. This work may provide semiquantitative insights into the origin of facet effect in photocatalysis.

Crystal-Phase Engineering in Heterogeneous Catalysis.

The performance of a chemical reaction is critically dependent on the electronic and/or geometric structures of a material in heterogeneous catalysis. Over the past century, the Sabatier principle has already provided a conceptual framework for optimal catalyst design by adjusting the electronic structure of the catalytic material via a change in composition. Beyond composition, it is essential to recognize that the geometric atomic structures of a catalyst, encompassing terraces, edges, steps, kinks, and corners, have a substantial impact on the activity and selectivity of a chemical reaction. Crystal-phase engineering has the capacity to bring about substantial alterations in the electronic and geometric configurations of a catalyst, enabling control over coordination numbers, morphological features, and the arrangement of surface atoms. Modulating the crystallographic phase is therefore an important strategy for improving the stability, activity, and selectivity of catalytic materials. Nonetheless, a complete understanding of how the performance depends on the crystal phase of a catalyst remains elusive, primarily due to the absence of a molecular-level view of active sites across various crystal phases. In this review, we primarily focus on assessing the dependence of catalytic performance on crystal phases to elucidate the challenges and complexities inherent in heterogeneous catalysis, ultimately aiming for improved catalyst design.

Unlock the Visible-Light Photocatalytic OWS by Surface Disorder-Engineered Bi-Based Composite Oxides through Phosphorization.

It has been proven that the introduction of disorder in the surface layers can narrow the energy band gap of semiconductors. Disordering the surface's atomic arrangement is primarily achieved through hydrogenation reduction. In this work, we propose a new approach to achieve visible-light absorption through surface phosphorization, simultaneously raising the energy band structure. In particular, the surface phosphorization of BixY1-xVO4 was successfully prepared by annealing them with a small amount of NaH2PO2 under a N2 atmosphere. After this treatment, the obtained BixY1-xVO4 showed distinct absorption in visible light. The surface phosphorization treatment not only improves the photocatalytic activity of BixY1-xVO4 but also enables visible-light photocatalytic overall water splitting. Furthermore, we demonstrate that this surface phosphorization method is universal for Bi-based composite oxides.

Phase engineering of Pt-Mn intermetallics for durable oxygen reduction reaction electrocatalysis

Controlling the crystal phase of intermetallic has been demonstrated as a promising strategy for enhancing oxygen reduction reaction (ORR) performance. However, the controlled synthesis of intermetallic with specific crystal phases remains a formidable challenge. Herein, structure ordered Pt-Mn intermetallics with face-centered cubic Pt3Mn (fcc-Pt3Mn/C) and face-centered tetragonal PtMn (fct-PtMn/C) are synthesized via an impregnation-reduction method. Benefiting from the rational control of crystal phase, fct-PtMn/C with optimal surface atomic arrangement and binding environment exhibits higher activity than fcc-Pt3Mn/C and Pt/C. Moreover, fct-PtMn/C exhibits a superior mass activity retention rate of 90.3 % after 50,000 potential cycles from 0.6 to 1.0 V compared to significantly lower rate of 56.0 % and 34.8 % for fcc-Pt3Mn/C and Pt/C, respectively. Structural analysis reveals that fct-PtMn/C maintains its crystal phase, particle size, and morphology exceptionally well during the durability test, demonstrating its outstanding structural stability. Theoretical calculations indicate that phase engineering can lower the reaction energy barrier, weaken the adsorption energy of reaction intermediates on fct-PtMn/C, and thus enhance the ORR performance.

Mechanism analysis of surface structure-regulated Cu2O in photocatalytic antibacterial process

The effects of exposing crystal planes and vacancy defect engineering can induce unique surface atom arrangements that strongly influence the physicochemical properties of semiconductor materials. This paper used Cu2O with different surface structures as a research model. A liquid-phase method was chosen for surface structure regulation to prepare Cu2O semiconductors (Vo-(111)Cu2O, Vo-(100)Cu2O, Vo-(110)Cu2O) with different exposed crystalline surfaces analyze the antibacterial mechanisms of other faceted models in the photodynamic antibacterial process. The bactericidal effect of Vo-(111)Cu2O (40 μg/mL, 100%) was better than that of Vo-(100)Cu2O and Vo-(110)Cu2O. DFT simulations show that the photocatalytic antimicrobial performance of Vo-(111)Cu2O is improved due to surface defect structures caused by unsaturated coordination bonds and suspension bonds on its exposed crystalline surfaces. The suspension bonds act as active centres for trapping electrons, leading to a lower carrier complexation rate on the material surface. The antibacterial mechanism of Vo-(111)Cu2O showed that oxidative sterilization by reactive oxygen species (ROS) was the dominant factor (61.98%) in the antibacterial process. The most potent depolarizing effect on E. coli, the highest copper ion solubilization, and the highest ROS yield. Therefore, ROS oxidative sterilization, copper ion leaching sterilization, and contact damage synergistically affect E. coli from the inside out.