Summary

The article discusses the concept of high-entropy ceramics (HECs) with a specific focus on high-
entropy oxides, particularly (NiMgCuZnCo)O5. These materials have gained attention due to
their remarkable stability and the unique properties bestowed upon them by unconventional
coordination environments of metal cations.

The design of high-entropy phases is primarily guided by Gibbs free energy (ΔG), where the
entropic contribution (TΔS) plays a dominant role. As a result, a diverse family of HECs has
been developed, encompassing various oxide structures, including rocksalts, perovskites, and
spinels, as well as other compounds like sulfides, carbides, and nitrides. However, the
incorporation of multiple elements in HECs, often in significant proportions, poses challenges
such as phase separation or element segregation. Typically, high reaction temperatures are
required to force metal cations to occupy similar sites uniformly and randomly, which can
compromise the materials' structural integrity.

The article argues that the role of mixing enthalpy (ΔHmix) has been underestimated in previous
research. Higher sintering temperatures and configurational entropy (ΔSconfig) have been used
to compensate for the enthalpy contribution, but this approach has limitations. The article
suggests that decreasing ΔHmix is a more effective strategy for creating single-phase high-
entropy ceramics at lower temperatures while maintaining porous and defect-rich structures.

The article then shifts its focus to ABO3-type perovskite oxides, particularly LaMnO3, which is
significant in heterogeneous catalysis due to its tunable composition in the B site. While high-
entropy LaMnO3 perovskite materials have been successfully synthesized, the high calcination
temperatures required have resulted in bulky materials, limiting their potential applications.

In response to this challenge, the article proposes a novel approach to reduce ΔG and prepare
single-phase high-entropy LaMnO3-type perovskite (HE-LMO) materials. Instead of solely
emphasizing TΔS, the article seeks to decrease ΔHmix, thereby enabling the creation of high-
entropy perovskite materials at lower temperatures, maintaining their desired structural
properties for use in various applications

Critique/Analysis

Authors’ introduction of the topic for the audience

The introduction provided in the text outlines the background and context for the research on
high-entropy ceramics (HECs), particularly focusing on high-entropy oxides. Here's a summary
of the key points from the introduction:

1. In 2015, the Rost group introduced a novel type of HECs called entropy-stabilized oxides, with
the example (NiMgCuZnCo)O5.
2. HECs have gained significant attention due to their exceptional stability, surpassing traditional
unary and binary ceramic materials.
3. HECs, characterized by unconventional coordination environments of metal cations, exhibit
unexpected physico-chemical properties.
4. The design of single high-entropy phases is guided by Gibbs free energy (ΔG), where entropic
contribution (TΔS) plays a dominant role. This principle has greatly expanded the family of
HECs, encompassing various oxides, sulfides, carbides, nitrides, and more.
5. However, the challenge with HECs lies in the complex interactions between multiple elements,
which often leads to phase separation or element segregation, requiring high reaction
temperatures to achieve a uniform structure.
6. Scientists have traditionally focused on the role of entropic contributions and high reaction
temperatures, paying insufficient attention to the mixing enthalpy (ΔHmix).
7. The article suggests that decreasing ΔHmix may enable the formation of single-phase HECs at
lower temperatures while maintaining the desired structural characteristics.
8. ABO3-type perovskite oxides, such as La-based perovskites, have been widely studied for their
tunable composition in the B site, which enhances their performance in heterogeneous catalysis.
9. While high-entropy LaMnO3 perovskite materials have been synthesized successfully, the high
calcination temperatures required result in bulky materials, limiting their applications.
10. The key concept of the presented work is to reduce the ΔH value to a similar magnitude of TΔS,
enabling the synthesis of high-entropy LaMnO3-type perovskite nanoparticles at milder sintering
temperatures.
11. The article discusses a novel strategy for constructing high-entropy LaMnO3-type perovskite
(HE-LMO) with a high surface area and enhanced catalytic performance for CO oxidation.
12. The article highlights the importance of oxygen vacancies and their role in catalytic activity and
stability, presenting computational insights and experimental evidence to support these claims.

This introduction sets the stage for the research presented in the article, emphasizing the need to
explore new approaches to create high-entropy ceramics with unique properties and applications
in catalysis.

Presentation of literature review in the article

The article discusses the development of high-entropy ceramics (HECs), focusing on
LaNi0.2Mn0.2Cu0.2Fe0.2Co0.2O3−δ (HE-LMO), a high-entropy LaMnO3-type perovskite
oxide. HECs, such as entropy-stabilized oxides, have gained significant attention due to their
stability and unique physico-chemical properties resulting from the unusual coordination
environments of metal cations. The design of single high-entropy phases is guided by Gibbs free
energy (ΔG), with entropic contribution (TΔS) playing a crucial role.

The study outlines a novel approach to lower ΔH (mixing enthalpy) to facilitate the synthesis of
HE-LMO at lower temperatures. By producing high-entropy hydroxides with high internal
energy, ΔH mix was reduced to a negative value, allowing for the formation of a single
perovskite phase at a milder sintering temperature. This innovative method yielded HE-LMO
nanoparticles with a high surface area, which demonstrated superior catalytic performance and
stability in CO oxidation.
 The research combines experimental characterization techniques, such as XRD, SEM, and XPS,
with computational approaches, including DFT calculations, to provide insights into the
properties and reactivity of HE-LMO. The results indicate that the abundance of oxygen
vacancies plays a significant role in enhancing catalytic activity. Furthermore, the study
highlights the potential of high-entropy ceramics in catalysis, especially in the presence of
moisture, thanks to their stable structures.

This work provides a promising strategy for the design and synthesis of high-entropy ceramics
with improved properties, emphasizing the importance of lowering mixing enthalpy to facilitate
their formation at lower temperatures.
Emphasize on the importance of undergoing this article

The article emphasizes the importance of understanding and controlling the

thermodynamic aspects of high-entropy ceramics (HECs), specifically entropy-stabilized
oxides, and highlights how this knowledge can lead to the development of advanced
materials with unique properties. Here are some key points that highlight the
importance of this article:

1. High-Entropy Ceramics (HECs): The article introduces HECs, particularly entropy-

stabilized oxides, which are composed of multiple elements in roughly equal
proportions. These materials have been of great interest due to their exceptional
stability and unique physico-chemical properties.
2. Challenges in HEC Synthesis: It points out the challenges in synthesizing HECs, such as
phase separation or element segregation due to the differences in atomic radii and the
high mixing enthalpy. This often requires high reaction temperatures, which can
negatively impact the materials' properties, like pore structure and defect content.
3. Emphasis on ΔHmix: The article highlights that scientists have often overlooked the
role of mixing enthalpy (ΔHmix) when designing HECs. While high temperatures were
used to compensate for high ΔHmix, it has adverse effects on the materials. The authors
argue for decreasing ΔHmix, which could lead to lower sintering temperatures and
better material properties.
4. Specific Focus on LaMnO3-type Perovskite Oxides: The study focuses on LaMnO3-
type perovskite oxides and their tunable compositions for applications in heterogeneous
catalysis. LaMnO3 perovskites have demonstrated excellent redox properties, but their
high calcination temperatures have been a limitation.
5. Novel Approach: The central concept of the study is to reduce the ΔH value to a similar
magnitude as TΔS, allowing the synthesis of high-entropy LaMnO3-type perovskites
(HE-LMO) at lower sintering temperatures. This approach is intended to maintain the
porous and defect-rich structure of the material.
6. Synthesis Method: The article describes a redox reaction strategy to synthesize high-
entropy LaMnO3-type perovskite nanoparticles with high surface areas. This method
 involves the creation of high-entropy hydroxides as precursors, with a focus on
decreasing ΔHmix.
7. Characterization and Properties: The article discusses the characterization of the
synthesized high-entropy LaMnO3 materials, including their crystalline structure,
morphology, surface area, oxygen defects, and the presence of oxygen vacancies. These
materials are shown to possess improved properties and enhanced catalytic
performance, particularly in CO oxidation.
8. Theoretical and Computational Insights: Density functional theory (DFT) calculations
are used to understand the thermodynamics and catalytic mechanisms. The presence of
oxygen vacancies around transition metals is highlighted as a key factor contributing to
the catalytic activity.
9. Stability in Moist Conditions: The study also demonstrates the stability of Redox-HE-
LMO in the presence of moisture, which can be crucial for real-world catalytic
applications.

In summary, this article underscores the significance of understanding and manipulating

thermodynamic factors, specifically ΔHmix, in the design and synthesis of high-entropy
ceramics, with a particular focus on LaMnO3-type perovskites. The outcome of this
research is the development of high-entropy materials with improved properties for
catalytic applications, and it proposes a novel approach for achieving this.