Field Scanning Transmission Electron Microscopy Research Articles

Si/AlN p-n heterojunction interfaced with ultrathin SiO2

Ultra-wide bandgap (UWBG) materials offer significant potential for high-power RF electronics and deep ultraviolet photonics. Among these, AlxGa1−xN stands out due to its tunable bandgap (3.4 eV to 6.2 eV) and excellent material properties. However, achieving efficient p-type doping in high aluminum composition AlGaN remains a challenge. This study presents a novel approach by fabricating a p+Si/n-AlN/n+AlGaN heterojunction using semiconductor grafting. Atomic force microscopy (AFM) revealed smooth surfaces for AlN and the nanomembrane, with roughness values of 1.96 nm and 0.545 nm, respectively. High-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) confirmed a sharp and well-defined Si/AlN interface with minimal defects and strong chemical bonding. X-ray photoelectron spectroscopy (XPS) measurements identified a type-I heterojunction with a valence band offset (ΔEv) of 2.73–2.84 eV and a conduction band offset (ΔEc) of 2.22–2.11 eV. The pn diode devices exhibited linear current–voltage (I-V) characteristics, an ideality factor of 1.92, and a high rectification ratio of 3.3 × 104, with a turn-on voltage of 3.9 V. Temperature-dependent I-V measurements showed stable operation up to 90 °C. The heterojunction’s high-quality interface and impressive electrical performance underscore its potential for advanced AlGaN-based optoelectronic and electronic applications.

Straightforward Synthesis Methodology for Obtaining Excellent ORR Electrocatalysts From Biomass Residues Through a One Pot‐High Temperature Treatment Approach

AbstractMaterials prepared from biomass residues are potential candidates to substitute the Pt‐based commercial electrocatalysts in oxygen reduction reaction (ORR). Although some investigations have reported activity and durability comparable to Pt/C using biomass‐derived catalysts based on Fe─N─C sites, it remains a challenge to decrease the environmental impact of the production of these materials. A straightforward procedure is developed to obtain excellentORR electrocatalysts from biomass residues which requires a single high‐temperature treatment. The final washing step is avoided by optimizing the initial amount of Fe precursor (FeC2O4). Besides the formation of iron oxide nanoparticles, a highly dispersed Fe phase is detected by High Angle Annular Dark Field Scanning Transmission Electron Microscopy and Energy Dispersive X‐Ray Spectroscopy (HAADF‐STEM‐XEDS) analysis as well as graphitic carbon structures. The best performance for almond shell‐based electrocatalysts is achieved for the sample containing 4.6 wt. % of Fe. The procedure developed is also applied to oceanic posidonia and eucalyptus residues, also showing excellent ORR behavior. The best sample is studied in a primary Zn‐air battery (ZAB) obtaining a maximum power density of 59 mW cm−2 and 755 mAh gZn−1 capacity.

Toward a Procedure for the Template Free Growth of Te Nanowires Across an Insulator by Electrodeposition.

In this work, we present a method for direct, site-selective growth of tellurium nanowires by electrochemical deposition. The Te nanowires were grown laterally between two specially designed nanoband electrodes across a gap, and over a dielectric material, forming a lateral device structure directly. The resulting wires are crystalline and phase pure, as evidenced by Raman spectroscopy, EDS (energy dispersive X-ray spectroscopy), and ADF-STEM (annular dark field scanning transmission electron microscopy). The precise conditions for lateral growth of the nanowires were investigated and the fabrication of an electronic device from the as-deposited material, without the need for any transfer process or further contact fabrication, is demonstrated.

Engineered Core-Shell SiC@SiO2 Nanofibers for Enhanced Electromagnetic Wave Absorption Performance.

To enable SiC material to achieve high electromagnetic wave (EMW) absorption performance, solving its impedance mismatch with EMW is necessary. Therefore, a novel approach is proposed for the precise control of impedance matching by adjusting the shell thickness of SiO2 nanolayers on the surface of SiC nanofibers (NFs). High-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) reveals the atomic scale oxidation process of SiC, providing fresh insights into the oxidation mechanism. By oxidizing to construct a heterogeneous core-shell structure nanofiber (NF) can effectively lock the incident EMW inside the NF through the generated charges gathered at the interface, forming an electronic barrier that prevents the outward propagation of EMWs. The produced SiC@SiO2 NFs-3 exhibits exceptional EMW absorption properties, including an impressive minimum reflection loss (RLmin) of -53.09dB and a broad maximum effective absorption bandwidth (EABmax) of 8.85GHz. These findings not only deepen understanding of the oxidation mechanism of SiC but also offer valuable insights for further enhancing the EMW absorption capabilities of SiC materials, paving the way for their application in advanced EMW technologies.

Obtaining 3D Atomic Reconstructions from Electron Microscopy Images Using a Bayesian Genetic Algorithm: Possibilities, Insights, and Limitations.

The Bayesian genetic algorithm (BGA) is a powerful tool to reconstruct the 3D structure of mono-atomic single-crystalline metallic nanoparticles imaged using annular dark field scanning transmission electron microscopy. The number of atoms in a projected atomic column in the image is used as input to obtain an accurate and atomically precise reconstruction of the nanoparticle, taking prior knowledge and the finite precision of atom counting into account. However, as the number of parameters required to describe a nanoparticle with atomic detail rises quickly with the size of the studied particle, the computational costs of the BGA rise to prohibitively expensive levels. In this study, we investigate these computational costs and propose methods and control parameters for efficient application of the algorithm to nanoparticles of at least up to 10 nm in size.

Characterization of L12-Al3Ce phase and its purification mechanism in the Al-Ce-TiCN alloy

Rare earth element Ce has a positive purifying effect on Fe and Si impurities in pure aluminum. In this study, we unveiled the mechanism of Ce purification of Fe and Si impurities in commercial pure aluminum at the atomic scale via utilizing the properties of TiCN nanoparticles, which exhibit distribution along grain boundaries and impede solute atom diffusion at specific cooling rates. The transition phase L12-Al3Ce was characterized in aluminum, which is considered to be an important transition phase to purified products. Furthermore, High Angle Dark Field Scanning Transmission Electron Microscopy (HADDF-STEM) and 3D Atom Probe Tomography (3D-APT) results showed that Ce could respectively enrich the Fe and Si impurities, resulting in the formation of Al-Ce-Fe and Al-Ce-Si clusters. Density functional theory (DFT) results indicated that Fe and Si atoms can incorporate into L12-Al3Ce crystal, forming more stable structures and therefore giving rise to the formation of Al-Ce-Si and Al-Ce-Fe nanoclusters. This study provides atomic-scale insights into the mechanism of Ce purifying Fe and Si impurities in aluminum.

Boosting catalytic activity of π-π interactions-stabilized PdNPs for water-mediated Suzuki couplings of aryl chlorides

Utilizing unique interactions to enhance the catalytic performance of supported metal catalysts is a crucial strategy in catalyst design, albeit one that presents a significant challenge. This study introduces an original approach involving the use of π-π interactions to stabilize palladium nanoparticles (PdNPs) with a 2Br-substituted imidazolium-based covalent organic framework (COF, IHP-Br-PdNPs) for efficient water-mediated Suzuki reactions involving deactivated aryl chlorides and arylboronic acids at ambient conditions. Through extensive structural characterization employing techniques including Fourier transform infrared spectroscopy (FT-IR), cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS 13C NMR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 adsorption, and X-ray photoelectron spectroscopy (XPS), we demonstrate the immobilization of highly stable and well-dispersed PdNPs was obtained. The designed IHP-Br-PdNPs demonstrate stability for up to 36 months in ambient air and can be efficiently recycled. After 9 catalytic cycles, there was no significant decline in catalytic performance, and the particle size of PdNPs remained constant at approximately 4-8 nm throughout the reactions. The coordination mode between the stabilizer and metal, specifically the π-π interaction between the 2Br-substituted imidazolium moiety and the Pd metal surface, plays a key role in stabilizing various active species and facilitating distinct catalytic pathways. This study provides valuable insights into the development of π-π interactions supported metal catalysts, which enhance stability and catalytic activity in advanced water-mediated synthesis applications.

Accelerating precipitation hardening by natural aging in a 6082 Al-Mg-Si alloy

It is well known that long time natural aging (NA) after quenching from solution treatment will significantly reduce the precipitation hardening kinetics and peak hardness of most 6xxx aluminum alloys during later artificial aging (AA). Here we demonstrate an effective strategy to accelerate precipitation hardening, taking advantage of NA. It is found that by a short time pre-aging (PA) at AA temperature, NA for up to 1 year can reduce the time to peak strength in a 6082 alloy during later AA. A simultaneous increase in yield strength and uniform elongation at peak-aged condition can be achieved as a result of finer and denser age-hardening precipitates than those formed by direct AA treatment. Quantitative characterization of the precipitate microstructure by annular dark field scanning transmission electron microscopy (ADF-STEM) and atom probe tomography (APT) reveals that PA generates a small fraction of fine β″ needle precipitates composed of 6–9 β″-eyes and a substantially high density of GP-zones composed of 3–5 β″-eyes, which are stable at room temperature and can grow easily into β″ upon AA. During NA after PA, more GP-zones with at least 2 β″-eyes form while the larger GP-zones inherited from PA grow further, both of which can act as the precursors of β″ precipitates during later AA.

Highly Selective Conversion of Carbon Dioxide to Methane by Copper Single Atom Electrocatalysts.

Electrocatalytic carbon dioxide reduction into high-value chemicals is one of the important solutions to the greenhouse effect and energy crisis. However, the slow kinetic process of eight electrons requires the development of efficient catalysts to improve the yields. Single atom catalysts (SACs) with high activity and selectivity have become an emerging research frontier in the field of heterogeneous catalysis. Herein, a catalyst comprised of Cu single atoms loaded on carbon substrate (Cu-NC) is developed for highly selective electrocatalytic reduction of CO2 to methane (CH4). The optimal catalyst (Cu-NC-1-4) exhibits a faradaic efficiency (FE) of over 50 % for CH4 within a wide potential window from -1.3 V to -1.8 V (vs. RHE) and the highest FE of CH4 is up to 67.22 % at -1.6 V (vs. RHE). Meanwhile, the product selectivity of CH4 among all the carbon products reaches 93.00 %, and the activity decay can be negligible via the 70-hour-stability-test. The existence of atomic dispersed Cu-N3 sites was verified by high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption near edge structure (XANES). Density functional theory (DFT) calculations show that the effective adsorption of the key intermediate *CO on Cu-N3 sites prompts the generation of CH4.

Silver nanoparticles modified with MoS2 and β-cyclodextrin as SERS substrate for rapid determination of cysteamine hydrochloride in meat products

An efficient Surface-enhanced Raman scattering (SERS) method for the detection of cysteamine hydrochloride (CSH) was developed by synthesizing a composite substrate comprising silver nanoparticles (AgNPs) functionalized with MoS2 and β-cyclodextrin (β-CD). The enhanced Raman signals of CSH by β-CD/MoS2/AgNPs substrate were the contribution of electromagnetic enhancement (EM) as well as chemical enhancement (CM), and the enhancement factor (EF) can reach up to 3.11 × 106 (peak at 633 cm−1). Various instrumental techniques were used to characterize the substrate, such as X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and ultraviolet visible (UV–vis). The binding of β-CD/MoS2/AgNPs and CSH was confirmed by UV–vis and Fourier transform infrared (FT-IR). The optimal experimental conditions were determined by single factor experiments as well as response surface model. The influences of different metal ions and analogous drugs on the detection of CSH were investigated. Under optimum conditions, a good linear correlation (R = 0.9997) was established for CSH in the range of 10.00–1000.00 nmol/L, and the limit of detection (LOD) was as low as 0.78 nmol/L (S/N = 3). The contents of CSH in meat samples were detected. The recovery was 96.6–103.1 %, and the relative standard deviation (RSD) of the measurement was 0.7–3.9 % (n = 7).

Simultaneous 2D Projection and 3D Topographic Imaging of Gas-Dependent Dynamics of Catalytic Nanoparticles.

Catalyst deactivation through pathways such as sintering of nanoparticles and degradation of the support is a critical factor when designing high-performance catalysts. Here, structural changes of supported nanoparticle catalysts are investigated in controlled gas environments (O2, H2O, and H2) at different temperatures by imaging simultaneously the nanoparticle structures in 2D projection and the 3D surface-sensitive topography. Platinum nanoparticles on carbon support as a model system are imaged in an environmental transmission electron microscope (ETEM), with concurrent acquisition of high-angle annular dark field scanning TEM (HAADF-STEM) and secondary electron (SE) images. Particle migration and coalescence occurs and shows gas-dependent kinetics, with nanoparticles moving across and through the support during and after coalescence. The temperature required for motion is lower in O2 than in H2O and H2, explained through the nature of the gas/nanoparticle interactions. In O2 and H2, the carbon support degrades by trench formation along migration pathways, and the particles move continuously, indicating a chemical reaction between gas and support. In H2O gas, motion is more discontinuous and oriented particle attachment occurs, as expected from theoretical predictions. These results suggest that multimodal imaging in ETEM that combines HAADF-STEM and SE data provides comprehensive information regarding catalyst dynamics and degradation mechanisms.

Morphology and crystallography of E-(Al18Cr2Mg3) nano dispersoids in 7475 Al alloy

The morphology and crystallography of E-(Al18Cr2Mg3) nano dispersoids in 7475 Al alloy have been studied by using transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and electron tomography (ET). Seven distinct morphologies have been three-dimensionally distinguished at the nanoscale: (i) triangular plates on {111}Al, (ii) hexagonal plates on {111}Al, (iii) rods parallel to <110>Al, (iv) small tetrahedra with {111}Al facets, (v) small octahedra, (vi) spheres and (vii) irregular shapes. Twinning can contribute to the diverse morphologies of E nano dispersoids. The orientation relationships (ORs) between E nano dispersoids and Al matrix have been systematically investigated by selected area electron diffraction (SAED) patterns, HRTEM and matrix calculation. The results from the matrix calculation indicate the absence of clear ORs between E nano dispersoids and Al matrix in 7475 Al alloy.

A new insight into largely defocused HAADF-STEM imaging and visualization of strain field

A crystalline bilayer specimen with a semi-coherent interface can generate moiré fringes in the high-angle annular-dark field scanning transmission electron microscopy (HAADF-STEM) imaging. Moreover, when the probe is significantly defocused, this specimen can produce largely defocused probe (LDP)-STEM patterns. Although the electron channeling effect serves as the fundamental principles for HAADF-STEM imaging, its connection to the emergence of LDP-STEM patterns remains unclear. The missing link lies in identifying the location of the imaged region. To address this issue, we examined the strain field in three-dimensional space and its interaction with the convergent electron beam, taking the PbZrO3/SrTiO3 (PZO/STO) heterostructure as an example. We discovered a new intensity relationship for LDP-STEM patterns in the PZO/STO heterostructure, which can be well explained by our theory. We also found that, generated by imaging the strain zone, these patterns revealed information that might be obscured in traditional high resolution STEM images, showing a unique advantage in characterizing the strain field. Furthermore, we provided discussions on visualizing the strain field, including the misfit dislocation network and array. Our research offers a novel perspective on the LDP-STEM imaging and clarifies the approach to characterizing the strain field.

Effect of Pre-Deformation on Precipitation in Al–Zn–Mg–Cu Alloy

AbstractIn this work, strengthening effects and evolution of precipitates in a pre-deformed Al–Zn–Mg–Cu alloy during ageing were investigated using Vickers hardness measurements, tensile tests, and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). It was found that all cold rolled conditions had higher mechanical strength than the non-deformed condition for all ageing times and that this effect increases at higher deformation ratios. It was also found that the non-deformed condition has a higher age hardening response than that of the cold rolled conditions. A homogeneous precipitate distribution was observed in the non-deformed condition, while the cold rolled conditions contained non-uniformly distributed precipitates due to the introduced dislocations. This led to larger precipitate sizes and a reduction in the precipitate number densities in the pre-deformed conditions. HAADF-STEM analysis revealed differences in the fraction of different precipitate types between the non-deformed and the cold rolled conditions. η', η2, and disordered η phase were observed in the non-deformed condition, while η', η2 and the newly identified Y phase were observed in the cold rolled conditions. The disordered η phase contained structural units of the η1 phase and was associated with reducing the lattice misfit between this phase and the Al matrix. Formation of the Y phase was related to an accelerated nucleation rate in the regions of high dislocation density. Graphical abstract

Kobellite homologues from the Boliden Au–Cu–(As) deposit, Sweden: jigsaw patterning via nanoscale intergrowths in chessboard structures

Abstract Sulfosalt assemblages in a specimen from the Boliden Au–Cu–(As) deposit in northern Sweden, comprise micrometre to nanometre scale intergrowths of Se-rich izoklakeite and tintinaite with average formulae and calculated homologue number (N) given as: (Cu1.88Fe0.18)2.06(Pb22.92Ag1.47Cd0.01Zn0.01)24.41(Sb13.12Bi8.69)21.8(S50.19Se6.43Te0.12)56.73,N = 3.83, and (Cu1.31Fe0.74)2.05(Pb10.58Ag0.18Cd0.05Zn0.02)10.83(Sb10.2Bi5.23)15.43(S32.22Se2.46)34.7, N = 2.05, respectively. Tintinaite coexists with (Bi, Se)-rich jamesonite. High-angle annular dark field scanning transmission electron microscopy (HAADF STEM) imaging reveals chessboard structures comprising PbS and SnS modules with the number of atoms in the octahedral (M) sites counted as: n1 = 18 and n2 = 8 for tintinaite and n1 = 30 and n2 = 16 for izoklakeite. The homologue number can be calculated using the formula: N = (n1/6)–1 and N = n2/4 for PbS and SnS modules giving NTti = 2 and NIz = 4. A new N = 3 homologue, defined by n = 12 and n = 24 SnS and PbS modules, respectively, is identified as single or double units within areas with intergrowths between kobellite and izoklakeite. HAADF STEM imaging also reveals features attributable to lone electron pair micelles within the Sb-rich kobellite homologues. Atomic-resolution EDS STEM chemical mapping of Pb–Bi–Sb-sulfosalts shows a correlation with crystal structural modularity. The maps also highlight sites in the SnS modules of tintinaite in which Sb &gt; Bi. Coherent nanoscale intergrowths between tintinaite and izoklakeite define jigsaw patterns evolving from chessboard structures and are considered to have formed during co-crystallisation of the two phases. Displacement textures and crosscutting veinlets (a few nm in width) are interpreted as evidence for superimposed syn-metamorphic deformation and are associated with the redistribution of Bi and Se. Imaging and mapping using HAADF STEM techniques is well suited to characterisation of Pb–Sb–Bi-sulfosalt phases, offering largely untapped potential to unravel the evolution of chessboard structures with applications across mineralogy but also extending into allied fields.

Thermal decomposition of oxygen‐containing Ta3N5${\rm {Ta}}_3{\rm {N}}_5$

AbstractTransition metal nitrides, especially tantalum nitrides, are pivotal for applications in extreme environments demanding excellent mechanical properties and thermodynamic stability. Among them, ‐TaN, a high‐pressure polymorph of tantalum nitride with its exceptional bulk modulus (362 GPa) and hardness (31.7 GPa) promises to have many technological uses. Another nitride, , has gained importance as a photocatalyst for water splitting using visible light. The Ta–N phase diagram indicates that the thermal decomposition of pure leads to the formation of ‐TaN. However, usually has some amount of oxygen as an impurity mainly due to its synthesis route. We found that the ‐TaN phase, which is usually observed at high pressures, is formed during the thermal decomposition of oxygen containing . The presence of ‐TaN is verified using several experimental techniques such as X‐ray diffraction, Raman spectra, high‐angle annular dark field scanning transmission electron microscopy (STEM‐HAADF), and electron energy loss spectroscopy (EELS). Elemental distribution analyzed through energy dispersion X‐ray spectroscopy (XEDS) in STEM reveals about 7 at.% of oxygen in ‐TaN. First‐principle calculations are performed to examine the thermodynamic stability of oxygen substituted ‐TaN and pure ‐TaN via formation enthalpies, elastic constants, and phonon dispersion calculations. The computational studies confirm that oxygen in ‐TaN enhances its thermodynamic stability. The calculated electron localization functions establish the bonding characteristics between Ta, N, and O, confirming the same.

Redox-driven surface generation of highly active Pd/PdO interface boosting low-temperature methane combustion

The supported Pd catalyst has been a benchmark for methane elimination. However, the active structures have been long under debate. Here, by the aberration-corrected high angle annular dark field scanning transmission electron microscopy, operando X-ray absorption spectroscopy and quasi in situ X-ray photoelectron spectroscopy, we revealed the two-dimensional metallic Pd bumps on the PdO surface (litchi-like structure) generated by the redox atmosphere under the lean condition as a highly active structure of the Pd/Al2O3 catalyst. The substantially increased Pd/PdO interfaces boost the methane combustion activity higher than the similar catalysts reported previously, and remarkably enhance the reaction rate by 15.5 and 10.7 times that of pure PdO or metallic Pd counterpart under lean condition at 300 °C, respectively. Density-functional theory calculations confirm the synergistic C–C bond activation of methane on the Pd/PdO interfaces. Our work provides new insight into the traditional understanding of the chemical state and particle size effects of the industrial Pd catalysts for methane oxidation.

Microstructural Evolution and Tensile Properties of Al-Si Piston Alloys during Long-Term Thermal Exposure

The present study investigated microstructural evolution and changes in tensile properties of an Al-Si piston alloy subjected to thermal exposures at 250 and 350 °C for 150, 300, and 500 h. Microstructural and nanoscale precipitates were characterized using a combination of high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) images and scanning electron microscopy (SEM). The tensile testing was performed. The results demonstrated that the thermal exposure induced granulation of the δ-Al3CuNi particles, alongside precipitation of the θ-Al2Cu phase particles and AlCu clusters within the matrix. Specifically, an increase in the size and number density of the θ-Al2Cu phase particles was observed with exposure time at 250 °C. Conversely, at 350 °C, the θ-Al2Cu particles exhibited a gradual increase in size with prolonged thermal exposure, coupled with a decrease in their number density. AlCu clusters precipitated solely at a thermal exposure temperature of 350 °C, with precipitation intensifying over time. Moreover, a decrease in the alloy’s tensile strength and an increase in elongation were noted after thermal exposure. Finally, the present study discussed the precipitation mechanisms of θ-Al2Cu particles and AlCu clusters within the grains, suggesting that the AlCu clusters exerted a more effective strengthening effect compared to the θ-Al2Cu particles.

Anodic Electrodeposition of IrO x Nanoparticles from Aqueous Nanodroplets.

Electrodeposition has been used for centuries to create new materials. However, synthetic platforms are still necessary to enrich a variety of nanomaterials that can be electrodeposited. For instance, IrO x is a popular material for the water oxidation reaction, but electrodeposition strategies for the controlled growth of IrO x nanoparticles are lacking. Here, we demonstrate the anodic electrodeposition of IrO x nanoparticles from aqueous nanodroplets. Field emission scanning electron microscopy (FESEM) and scanning transmission electron microscopy (STEM) images confirm the macro- and microstructure of the resulting nanoparticles. IrO x nanoparticles of 43 ± 10 nm in diameter were achieved. X-ray photoelectron spectroscopy (XPS) showed the presence of Ir(III) and Ir(IV) hydrated oxyhydroxide species. The synthesis of IrO x nanoparticles under anodic conditions using water nanodroplets expands the capabilities of our technique and provides a tunable platform for IrO x nanoparticle electrodeposition.

Enhanced Photocatalytic Activity of Surface‐Modified TiO2 with Bimetallic AuPd Nanoalloys for Hydrogen Generation

Herein, commercial titania (TiO2‐P25) is modified with mono‐ and bi‐metallic (Au, Pd, and AuPd) nanoparticles synthesized by chemical reduction method using NaBH4 as a strong reducing agent at room temperature. Bimetallic AuPd nanoalloys homogeneous in size and well dispersed on the TiO2 surface are obtained. The charge‐carrier dynamics, which is a key factor in photocatalysis, is studied by time‐resolved microwave conductivity. The results reveal that surface modification plays a crucial role in charge‐carrier separation, increasing the activity under UV–vis light irradiation. The bimetallic AuPd nanoalloys formation is confirmed by high‐angle annular dark field scanning transmission electron microscopy and corroborated by semiempirical molecular dynamics simulations (Gupta‐LAMMPS). The surface‐modified TiO2 with bimetallic AuPd nanoalloys exhibits higher photocatalytic activity compared to TiO2 modified with their monometallic counterparts. The experimental results are also supported by density functional theory and density functional tight binding calculations, which show that alloying AuPd with low Pd content presents significant synergetic effects for hydrogen generation under UV–vis light from aqueous triethanolamine solutions. Additionally, the AuPd/TiO2 photocatalysts are stable with cycling.