Engineering PapersSearch

DOE OSTI · 3367235

Controlling Exsolution Dynamics in High‐Entropy Oxides for Highly Active and Selective Acetylene Semi‐Hydrogenation

Yu, Hailing [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division]·Wang, Caiqi [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000198849990)·Siniard, Kevin M. [Univ. of Tennessee, Knoxville, TN (United States)]·Wang, Qingju [Univ. of Tennessee, Knoxville, TN (United States)]·Zhang, Yuanpeng [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division] (ORCID:0000000342243361)·Boscoboinik, J. Anibal [Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)] (ORCID:0000000250907079)·Tong, Xiao [Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)] (ORCID:0000000255679677)·Gomez, Eliseo Perez [Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)]·Yuan, Shuai [Vanderbilt Univ., Nashville, TN (United States)]·Asundi, Arun S. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)]·Mueller, Oliver [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)]·Martins, Murillo Longo [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division]·Cheng, Yongqiang [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division]·Koehler, Michael Richard [Univ. of Tennessee, Knoxville, TN (United States)]·Jiang, De‐en [Vanderbilt Univ., Nashville, TN (United States)] (ORCID:0000000151670731)·Wu, Zili [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000244683240)·Yang, Zhenzhen [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000202334747)·Dai, Sheng [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000280463931)

Abstract

Exsolution-derived catalysts feature robust metal–support interactions that enhance catalytic performance; yet achieving precise control over exsolution dynamics in multicomponent oxides remains challenging. In this study, we demonstrate that exsolution behavior in high-entropy oxides (HEOs) can be rationally tuned through coupled lattice- and valence-engineering to create a highly active and selective catalyst for acetylene semi-hydrogenation. Incorporation of Li + into a rock salt-structured HEO (LiNiMgCuZnCoO x and LiHEO) induces local lattice distortion, generates oxygen vacancies, and partially oxidizes Co sites from Co 2+ to Co 3+ , collectively modulating local charge redistribution. This strategy enables facilitated Cu nanoparticle exsolution and alters the exsolution sequence from Cu 0 > Ni 0 > Co 0 in pristine HEO to Cu 0 > Co 0 > Ni 0 in the LiHEO. The resulting catalyst via controlled exsolution exhibits superior activity and ethylene selectivity, outperforming state-of-the-art transition metal systems. This work establishes entropy-enabled lattice and valence engineering as a facile route to programmable exsolution for enhanced catalysis.

Explore related subjects

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Yu, Hailing [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division], Wang, Caiqi [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000198849990), Siniard, Kevin M. [Univ. of Tennessee, Knoxville, TN (United States)], Wang, Qingju [Univ. of Tennessee, Knoxville, TN (United States)], Zhang, Yuanpeng [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division] (ORCID:0000000342243361), Boscoboinik, J. Anibal [Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)] (ORCID:0000000250907079), Tong, Xiao [Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)] (ORCID:0000000255679677), Gomez, Eliseo Perez [Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)], Yuan, Shuai [Vanderbilt Univ., Nashville, TN (United States)], Asundi, Arun S. [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)], Mueller, Oliver [SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)], Martins, Murillo Longo [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division], Cheng, Yongqiang [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division], Koehler, Michael Richard [Univ. of Tennessee, Knoxville, TN (United States)], Jiang, De‐en [Vanderbilt Univ., Nashville, TN (United States)] (ORCID:0000000151670731), Wu, Zili [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000244683240), Yang, Zhenzhen [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000202334747), Dai, Sheng [Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division] (ORCID:0000000280463931). 2026-05-15. Controlling Exsolution Dynamics in High‐Entropy Oxides for Highly Active and Selective Acetylene Semi‐Hydrogenation. https://doi.org/10.1002/anie.9920205

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related reports

Cyclic moisture reactivation of calcium sorbents for long duration thermochemical energy storage

The transition to a flexible and reliable energy infrastructure, using electro-thermal energy generation technologies such as geothermal, concentrated solar power, and nuclear, usually demands simultaneous advancement of thermal energy storage (TES) to support on-demand electricity generation and industrial applications while mitigating the inherent intermittency of renewable energy sources and power outages from direct energy generation. Among TES technologies, thermochemical energy storage (TCES) based on calcium looping emerges as a compelling high-power energy storage candidate due to its high reaction enthalpy, compatibility with elevated operating temperatures, and abundance of low-cost materials. However, the long-term durability of calcium-based sorbents for TCES is hindered by surface sintering and particle aggregation, leading to performance degradation over repeated thermal cycles. This study explores a moisture hydration-based strategy to regenerate a degraded calcium sorbent and mitigate performance degradation for long duration TCES. The addition of moisture transforms calcium oxide into calcium hydroxide and produces intercalation water layers, associated with a regenerated surface area and reduced calcium oxide crystallite size. Both these effects are beneficial in restoring the sorbents' reactivity for carbonization. Additionally, an optimized hydration-assisted reactivation protocol balances the recovered energy storage capacity with heating penalty required for moisture removal from hydrated samples, resulting in an enhanced energy storage capacity up to 176% compared to benchmark sorbents that undergo cycling without reactivation after 60 cycles. In conclusion, these results highlight the potential of hydration-assisted reactivation to enhance the long-term performance of TCES, providing an effective pathway to advancing electro-thermal storage technologies.

36 MATERIALS SCIENCE