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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Transition-metal doped titanate nanowire photocatalysts boosted by selective ion-exchange induced defect engineering

Defect engineering through elemental doping is an efficient way to boost the performance of semiconductor photocatalysts. For this work, transition-metal (TM) doped titanate nanowires (TNWs) were prepared via ion-exchange over the titanate precursors and demonstrated for the Rhodamine B (RhB) degradation under ultraviolet (UV) light irradiation. The ion-exchange of selective ions (V 5+ , Cr 3+ , Ni 2+ , and Zn 2+ ) with protons from pristine TNWs resulted in the hierarchical meso-porosity of nanowires with large pores of ~5–20 nm by TM doping and small pores of ~3.6–4.5 nm inherited from pristine TNWs, which facilitates the mass transfer while maintaining high surface area and active sites. Meanwhile, the TM intercalation partially reduces the Ti 4+ to Ti 3+ and narrows the optical bandgap, which, together with oxygen vacancies and superoxide radicals from pristine TNWs, enhance the adsorption and photocatalytic degradation performance of RhB. This work helps to elucidate the effects of transition-metal doping and provides a rational strategy towards high performance titanate-based photocatalysts for efficient and sustainable wastewater treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Node Distortions as a Means of Defect Engineering in Zr-Based MOFs

Defect engineering in Zr-based metal–organic frameworks (Zr-MOFs) has focused primarily on missing-linker defects. However, recent studies suggest that node dehydroxylation–which creates distortions and coordinatively unsaturated Zr sites (Zr cus )–may have a more significant impact on properties. The present work uses pair distribution function (PDF) and thermogravimetric analysis coupled with systematic defect manipulation to study the effect of node dehydroxylation and missing-linker defects in UiO-66. By employing rapid heat treatment (RHT) under humid flow, we tracked the transition from high-symmetry [Zr 6 O 4 (OH) 4 ] 12+ to distorted [Zr 6 O 6 ] 12+ nodes. This structural evolution significantly improves As(V) uptake, whereas increasing the number of missing linkers–via chemical treatment or RHT of mixed-ligand frameworks–fails to enhance performance. Crucially, our detection of distorted nodes in as-synthesized UiO-66 also raises the possibility that these defects were silently present in many earlier studies that span various applications, where their role in governing performance may have been inadvertently overlooked. The present study challenges the prevailing “missing-linker” paradigm and establishes cluster dehydroxylation as a defect-engineering strategy to enhance Lewis-acidic performance in Zr-MOFs.

Adsorption↗
DOE OSTI2026

Direct Observation of Ultrafast Defect-Bound and Free Exciton Dynamics in Defect-Engineered WS 2 Monolayers

Defects in two-dimensional transition metal dichalcogenides (TMDCs) broadly affect their optical and electronic properties. Directly capturing the ultrafast processes of exciton trapping and defect-bound exciton formation is crucial for understanding and advancing defect-mediated optoelectronics and quantum technologies. However, the weak transient optical absorption of defect-bound excitons has limited their experimental observation to date. Here, we report the direct observation of the ultrafast dynamics of defect-bound excitons in monolayer WS 2 crystals with a high density of monosulfur vacancies (V S ) and W-site defect complexes (S W V S ) resulting from synthesis by alkali metal halide-assisted chemical vapor deposition. The dynamics of excitons bound to these defects, along with their coherent interactions with free excitons, are elucidated using ultrafast optical spectroscopy. Using above band-edge photoexcitation, we find that both free and defect-bound excitons simultaneously form within 300 fs from hot carrier relaxation. The defect-bound excitons exhibit shorter lifetimes than free excitons, leading to a population difference of the corresponding excitonic states and free exciton trapping within a 1–100 ps window. Band-edge photoexcitation of free and defect-bound exciton states reveals ultrafast interconversion within ∼150 fs (comparable to our temporal resolution), indicating possible coherent coupling between these states. We further demonstrate efficient up-conversion of defect-bound excitons to free excitons with photon energies up to ∼300 meV below the free exciton resonance. In conclusion, these findings provide insights into the ultrafast dynamics of defect-bound excitons in TMDCs and their coupling with free excitons, which are relevant to defect-engineered optoelectronic, quantum photonic, and valleytronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Transformation of Highly Stable Pt Single Sites on Defect Engineered Ceria into Robust Pt Clusters for Vehicle Emission Control

Engineering surface defects on metal oxide supports could help promote the dispersion of active sites and catalytic performance of supported catalysts. Herein, a strategy of ZrO 2 doping was proposed to create rich surface defects on CeO 2 (CZO) and, with these defects, to improve Pt dispersion and enhance its affinity as single sites to the CZO support (Pt/CZO). The strongly anchored Pt single sites on CZO support were initially not efficient for catalytic oxidation of CO/C 3 H 6 . However, after a simple activation by H 2 reduction, the catalytic oxidation performance over Pt/CZO catalyst was significantly boosted and better than Pt/CeO 2 . Pt/CZO catalyst also exhibited much higher thermal stability. The structural evolution of Pt active sites by H 2 treatment was systematically investigated on aged Pt/CZO and Pt/CeO 2 catalysts. With H 2 reduction, ionic Pt single sites were transformed into active Pt clusters. Much smaller Pt clusters were created on CZO (ca. 1.2 nm) than on CeO 2 (ca. 1.8 nm) due to stronger Pt-CeO 2 interaction on aged Pt/CZO. Consequently, more exposed active Pt sites were obtained on the smaller clusters surrounded by more oxygen defects and Ce 3+ species, which directly translated to the higher catalytic oxidation performance of activated Pt/CZO catalyst in vehicle emission control applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Defect engineering of porous aromatic frameworks via end capping improves dioxane removal from water

Amorphous porous organic polymers show promise for energy-efficient adsorptive separations, but it is difficult to understand or improve their performance through intentional structural modification. Herein, we report the synthesis of porous aromatic frameworks (PAFs) with pore structures tailored by the incorporation of a monofunctionalized end-capping monomer that disrupts framework topology. Combining experimental characterization with molecular simulations, we show that this defect engineering strategy yields less densely crosslinked networks, which leads to pore collapse and the presence of unique adsorption sites. These defect-engineered PAFs exhibit enhanced removal of 1,4-dioxane, an important environmental pollutant, from water. Increasing the concentration of end-capping monomers produces PAFs with narrower pore size distributions and improved 1,4-dioxane uptake. These results illustrate that defect engineering can effectively modulate polymer connectivity and porosity for applications in selective adsorptive separations. In conclusion, this technique avoids post-synthetic treatments and presents another approach to tailor amorphous polymeric adsorbents.

36 MATERIALS SCIENCE↗
DOE OSTI2025

UV-Enabled Defect Engineering in Multilayer GaSe and InSe and UV Writing of the Grating Pattern

III–VI post-transition-metal chalcogenides are layered semiconductor materials that exhibit direct band gaps in multilayers. Defect engineering is essential in 2D layered semiconductors for functional devices. Here, in this work, we report defect engineering in multilayer gallium selenide (GaSe) and indium selenide (InSe), where defects generated by ultraviolet (UV, 325 nm) laser irradiation result in an additional photoluminescence (PL) line. The additional PL line is due to defect-bound excitons. Characteristics of the defect emission are similar in GaSe and InSe samples subjected to UV irradiation, air annealing, and hydrostatic pressure. Two-beam UV interference was applied to create grating patterns with a periodic array of low and high densities of defects in GaSe. Density functional theory has identified the defect type in GaSe. The results provide valuable insights into defect generation and UV scribing of photonic circuits in 2D Se-based multilayers for optical integration in a 2D platform.

2D multilayered materials↗
DOE OSTI2025

Recent advances in rational design of defect-engineered photocatalysts toward sustainable NH 3 synthesis as H 2 carrier: From fundamental and development to machine-learning

In this study, we provide a detailed overview of the fundamental mechanisms underpinning photocatalytic N 2 reduction. We also discuss advances in catalyst design for the synthesis of NH 3 . Particular emphasis is placed on the role of surface defect engineering, which includes the creation of surface defects to enhance the performance of semiconducting photocatalysts for efficient N 2 reduction. In addition, the application of a machine learning-based computational modeling approach is discussed as an important driving force for predicting and regulating NH 3 synthesis efficiency based on catalyst features and reaction conditions. Finally, existing challenges and future perspectives for improving the performance of defect-engineered photocatalysts are outlined to contribute to the ongoing discourse on sustainable ammonia generation. This review aims to clarify recent progress in the rational design of defect-containing photocatalysts for the synthesis of NH 3 and encourages innovative approaches to catalyst optimization rather than solely focusing on new materials.

08 HYDROGEN↗
DOE OSTI2024

Atomistic Probing of Defect-Engineered 2H-MoTe 2 Monolayers

Point defects dictate various physical, chemical, and optoelectronic properties of two-dimensional (2D) materials, and therefore, a rudimentary understanding of the formation and spatial distribution of point defects is a key to advancement in 2D material-based nanotechnology. In this work, we performed the demonstration to directly probe the point defects in 2H-MoTe 2 monolayers that are tactically exposed to (i) 200 °C-vacuum-annealing and (ii) 532 nm-laser-illumination; and accordingly, we utilize a deep learning algorithm to classify and quantify the generated point defects. We discovered that tellurium-related defects are mainly generated in both 2H-MoTe 2 samples; but interestingly, 200 °C-vacuum-annealing and 532 nm-laser-illumination modulate a strong n-type and strong p-type 2H-MoTe 2 , respectively. While 200 °C-vacuum-annealing generates tellurium vacancies or tellurium adatoms, 532 nm-laser-illumination prompts oxygen atoms to be adsorbed/chemisorbed at tellurium vacancies, giving rise to the p-type characteristic. This work significantly advances the current understanding of point defect engineering in 2H-MoTe 2 monolayers and other 2D materials, which is critical for developing nanoscale devices with desired functionality.

2H-MoTe 2↗
DOE OSTI2020

Tuning the Wettability of Metal–Organic Frameworks via Defect Engineering for Efficient Oil/Water Separation

Zirconium-based metal–organic frameworks (MOFs) have attracted interest due to their chemical and thermal stabilities and structural tunability. In this article, we demonstrate the tuning of the wettability of a UiO-66 structure via defect-engineering for efficient oil/water separation. UiO-66 crystals with controlled levels of missing-linker defects were synthesized using a modulation approach. As a result, the hydrophilicity of the defect-engineered UiO-66 (d-UiO-66) can be varied. In addition, a thin layer of hydrophilic d-UiO-66 was successfully fabricated on a series of stainless steel meshes (d-UiO-66@mesh), which exhibited excellent superhydrophilic and underwater superoleophobic properties and displayed interesting separation performance for various oil/water mixtures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Defects and Defect Engineering of Two-Dimensional Transition Metal Dichalcogenide (2D TMDC) Materials

As layered materials, transition metal dichalcogenides (TMDCs) are promising two-dimensional (2D) materials. Interestingly, the characteristics of these materials are transformed from bulk to monolayer. The atomically thin TMDC materials can be a good alternative to group III–V and graphene because of their emerging tunable electrical, optical, and magnetic properties. Although 2D monolayers from natural TMDC materials exhibit the purest form, they have intrinsic defects that limit their application. However, the synthesis of TMDC materials using the existing fabrication tools and techniques is also not immune to defects. Additionally, it is difficult to synthesize wafer-scale TMDC materials for a multitude of factors influencing grain growth mechanisms. While defect engineering techniques may reduce the percentage of defects, the available methods have constraints for healing defects at the desired level. Thus, this holistic review of 2D TMDC materials encapsulates the fundamental structure of TMDC materials, including different types of defects, named zero-dimensional (0D), one-dimensional (1D), and two-dimensional (2D). Moreover, the existing defect engineering methods that relate to both formation of and reduction in defects have been discussed. Finally, an attempt has been made to correlate the impact of defects and the properties of these TMDC materials.

2D materials↗
DOE OSTI2021

Tunable Broad Light Emission from 3D “Hollow” Bromide Perovskites through Defect Engineering

We report hybrid halide perovskites consisting of corner-sharing metal halide octahedra and small cuboctahedral cages filled with counter cations have proven to be prominent candidates for many high-performance optoelectronic devices. The stability limits of their three-dimensional perovskite framework are defined by the size range of the cations present in the cages of the structure. In some cases, the stability of the perovskite-type structure can be extended even when the counterions violate the size and shape requirements, as is the case in the so-called "hollow" perovskites. In this work, we engineered a new family of 3D highly defective yet crystalline "hollow" bromide perovskites with general formula (FA) 1-x (en) x (Pb) 1-0.7x (Br) 3-0.4x (FA = formamidinium (FA + ), en = ethylenediammonium (en 2+ ), x = 0-0.44). Pair distribution function analysis shed light on the local structural coherence, revealing a wide distribution of Pb-Pb distances in the crystal structure as a consequence of the Pb/Br-deficient nature and en inclusion in the lattice. By manipulating the number of Pb/Br vacancies, we finely tune the optical properties of the pristine FAPbBr 3 by blue shifting the band gap from 2.20 to 2.60 eV for the x = 0.42 en sample. A most unexpected outcome was that at x > 0.33 en incorporation, the material exhibits strong broad light emission (1% photoluminescence quantum yield (PLQY)) that is maintained after exposure to air for more than a year. This is the first example of strong broad light emission from a 3D hybrid halide perovskite, demonstrating that meticulous defect engineering is an excellent tool for customizing the optical properties of these semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Defect engineering in nickel via electrodeposition following low temperature annealing

Electrodeposited nickel coatings are characterized by high densities of crystalline defects including dislocations, growth twins, and hydrogen bubbles/voids, arising from the non-equilibrium nature of deposition. While these metastable features influence as-deposited properties, their evolution under low temperature annealing remains unexplored. Here, in this study, we demonstrate that low temperature annealing (200 °C) induces significant microstructural rearrangement without grain growth, enabling defect engineering through thermally assisted dislocation motion and twin boundary migration. Notably, we observe faceted twin boundaries and dislocation organization into extended networks, which have been rarely reported under such annealing conditions. These transformations are attributed to hydrogen-assisted defect mobility, facilitated by the release or redistribution of hydrogen trapped during deposition. These structural transformations correlate with a significant enhancement in mechanical properties, including a twofold increase in yield strength and improved ductility. Our findings highlight the role of trapped hydrogen in mediating low-temperature defect mobility and twin boundary evolution, offering a unique pathway for microstructural tuning of metallic coatings through controlled annealing.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Constructing uniform oxygen defect engineering on primary particle level for high-stability lithium-rich cathode materials

Lithium-rich layered cathode materials are considered to be research focus of cathode candidates for next generation lithium-ion batteries due to their high specific capacity and low cost. However, lattice deoxidation associated with elemental migration and internal local shrinkage usually results in deteriorated cyclic performance and notorious voltage attenuation, severely limiting its application. In this paper, we have successfully injected uniform oxygen defects into surface region of Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 primary particles under the high-pressure and weak carbonate environment. Various experimental investigations indicate that the injected robust oxygen defects can not only mitigate detrimental interfacial reactions but also suppress unfavorable lattice variation and particle breakage. More importantly, theoretical calculations unravel the critical roles of oxygen defects in regulating energy band structure for strengthened anionic reversibility. Owing to stabilization effects of unique oxygen defect engineering, the modified Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 cathode has harvested dramatically enhanced electrochemical performance including a high initial coulombic efficiency of 96.6%, an outstanding capacity retention of 91.96% (1C, 200 cycles) and suppressed voltage decay of only 1.62 mV per cycle. Therefore, this facile and effective defect engineering strategy could establish new guidance for promoting practical application of Li-rich Mn-based cathode material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Lithiation-Induced Defect Engineering to Promote Oxygen Evolution Reaction

Exploring efficient electrocatalysts for oxygen evolution reaction (OER) is an urgent need to advance the development of sustainable energy conversion. Though defect engineering is considered an effective strategy to regulate catalyst activity for enhanced OER performance, the controllable synthesis of defective oxides electrocatalysts remains challenging. Here, oxygen defects are introduced into NiCo 2 O 4 nanorods by an electrochemical lithiation strategy. By tuning in situ lithiation potentials, the concentration of oxygen defects and the corresponding catalytic activity can be feasibly regulated. In addition, the relationship between the changes in the defect density and electronic structure and the lithiation cut-off voltages is revealed. The results show that NiCo 2 O 4 nanorods undertook intercalation and two-step conversion reaction, in which the lithiation-induced conversion reaction gives rise to a CoO@NiO-based structure with higher defect density and lower oxidation states. As a result, the defective CoO@NiO-based catalyst exhibits exceptional OER activity with an overpotential of 270 mV at 10 mA cm -2 , which is about 74 mV below the pristine nanomaterials. In conclusion, this research proposes a novel strategy to explore high-performance catalysts with structural stability and defect control.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Controllable oxygen vacancy defect engineering of BiVO 4 porous structures for room temperature NH 3 detection

Controlling structural features of sensing material while judiciously introducing vacancy defect states for revamping the electronic properties of the sample to obtain its superior gas sensing performance, is quite rare. Herein, we report for the first time, the room temperature (RT) ammonia (NH 3 ) detection of peanut-like porous bismuth vanadate (BiVO 4 ) with a stable monoclinic phase. The developed BiVO 4 possess abundant oxygen vacancies and porosity by virtue of calcinations (400–800 ℃). BiVO 4 calcined at 400 ℃ exhibits high selectivity towards NH 3 with a maximum response of 1421 @ 270 ppm at RT, which is 2.5 fold enhanced compared to without calcined BiVO 4 (response of 547 @ 270 ppm NH 3 ). The oxygen defective BiVO 4 appeared highly durable and stable even under high humid conditions (∼60 %). Besides, the porosity of BiVO 4 not only enhances the specific surface area (19.8 m 2 /g) but also results in fast diffusion of NH 3 molecules, leading to a reduction in the decay time (34 s for 90 ppm NH 3 ). The density functional theory (DFT) uncovers that the oxygen vacancy formation in BiVO 4 augments the NH 3 sensing capabilities by enhancing the adsorption energy of NH 3 . This work provides insight into the sensing mechanism of increased response caused by defect engineering and porosity, which will be favourable for fabricating high-performance NH 3 sensors at RT.

DFT analysis↗
DOE OSTI2020

Doping of Cr in Graphene Using Electron Beam Manipulation for Functional Defect Engineering

Chromium atoms in graphene have been proposed to exhibit magnetic moments and spin-selective conducting states depending on the local bonding geometry within the graphene structure, which could lead to interesting applications in spintronics. Despite this interest, there are few direct experimental reports of Cr dopants in graphene even though it is theorized to be stable. Here, we demonstrate the introduction of single Cr dopant atoms into the graphene lattice and onto graphene edges through the controlled use of a focused electron beam in a scanning transmission electron microscope. Here, we show local control of doping locations, and when coupled with targeted in situ milling during scanning of the e-beam, these strategies demonstrate an important component of the fabrication of tailored nanostructured devices in the electron microscope. The approach is validated with first-principles calculations to understand synthesis pathways during fabrication and reveal the energetics and local properties of Cr atoms embedded in graphene; for example, Cr doping can convert graphene into a magnetic and semiconducting material, which suggests Cr-doped graphene can be used as a building block for potential electronic devices and a means to construct them.

36 MATERIALS SCIENCE↗