Linear Scaling Relations Research Articles

Designs of Tandem Catalysts and Cascade Catalytic Systems for CO2 Upgrading

AbstractUpgrading CO2 into multi‐carbon (C2+) compounds through the CO2 reduction reaction (CO2RR) offers a practical approach to mitigate atmospheric CO2 while simultaneously producing high value chemicals. The reaction pathways for C2+ production involve multi‐step proton‐coupled electron transfer (PCET) and C−C coupling processes. By increasing the surface coverage of adsorbed protons (*Had) and *CO intermediates, the reaction kinetics of PCET and C−C coupling can be accelerated, thereby promoting C2+ production. However, *Had and *CO are competitively adsorbed intermediates on monocomponent catalysts, making it difficult to break the linear scaling relationship between the adsorption energies of the *Had/*CO intermediate. Recently, tandem catalysts consisting of multicomponents have been developed to improve the surface coverage of *Had or *CO by enhancing water dissociation or CO2‐to‐CO production on auxiliary sites. In this context, we provide a comprehensive overview of the design principles of tandem catalysts based on reaction pathways for C2+ products. Moreover, the development of cascade CO2RR catalytic systems that integrate CO2RR with downstream catalysis has expanded the range of potential CO2 upgrading products. Therefore, we also discuss recent advancements in cascade CO2RR catalytic systems, highlighting the challenges and perspectives in these systems.

Designs of Tandem Catalysts and Cascade Catalytic Systems for CO2 Upgrading.

Upgrading CO2 into multi-carbon (C2+) compounds through the CO2 reduction reaction (CO2RR) offers a practical approach to mitigate atmospheric CO2 while simultaneously producing high value chemicals. The reaction pathways for C2+ production involve multi-step proton-coupled electron transfer (PCET) and C-C coupling processes. By increasing the surface coverage of adsorbed protons (*Had) and *CO intermediates, the reaction kinetics of PCET and C-C coupling can be accelerated, thereby promoting C2+ production. However, *Had and *CO are competitively adsorbed intermediates on monocomponent catalysts, making it difficult to break the linear scaling relationship between the adsorption energies of the *Had/*CO intermediate. Recently, tandem catalysts consisting of multicomponents have been developed to improve the surface coverage of *Had or *CO by enhancing water dissociation or CO2-to-CO production on auxiliary sites. In this context, we provide a comprehensive overview of the design principles of tandem catalysts based on reaction pathways for C2+ products. Moreover, the development of cascade CO2RR catalytic systems that integrate CO2RR with downstream catalysis has expanded the range of potential CO2 upgrading products. Therefore, we also discuss recent advancements in cascade CO2RR catalytic systems, highlighting the challenges and perspectives in these systems.

Dynamic Metal-Ligand Coordination Boosts CO2 Electroreduction.

The interfacial structure of heterogeneous catalysts determines the reaction rate by adjusting the adsorption behavior of reaction intermediates. Unfortunately, the catalytic performance of conventionally static active sites has always been limited by the adsorbate linear scaling relationship. Herein, we develop a triazole-modified Ag crystal (Ag crystal-triazole) with dynamic and reversible interfacial structures to break such a relationship for boosting the catalytic activity of CO2 electroreduction into CO. On the basis of surface science measurements and theoretical calculations, we demonstrated the dynamic transformation between adsorbed triazole and adsorbed triazolyl on the Ag(111) facet induced by metal-ligand conjugation. During CO2 electroreduction, Ag crystal-triazole with the dynamically reversible transformation of ligands exhibited a faradic efficiency for CO of 98% with a partial current density for CO as high as -802.5 mA cm-2. The dynamic metal-ligand coordination not only reduced the activation barriers of CO2 protonation but also switched the rate-determining step from CO2 protonation to the breakage of C-OH in the adsorbed COOH intermediate. This work provided an atomic-level insight into the interfacial engineering of the heterogeneous catalysts toward highly efficient CO2 electroreduction.

Yolk‐Shell Structured Zinc‐Cobalt‐Ruthenium Alloy Oxide Assembled with Ultra‐Small Nanoparticles: A Superior Cascade Catalyst toward Oxygen Evolution Reaction

AbstractStructure engineering has proven to be an effective strategy for improving the catalytic performance and reducing the cost of ruthenium oxide‐based catalysts toward oxygen evolution reactions (OER). Herein, a polyhedron‐shaped yolk‐shell structure composed of zinc‐cobalt‐ruthenium ternary metal alloy oxide (ZnCo‐RuO2/C) is prepared, by taking advantage of the Kirkendall effect. The yolk‐shell frame and the ensembled metal oxide nanoparticles are 116.9 ± 25.9 nm and 3.1 ± 0.7 nm in diameter, respectively. The porous yolk‐shell structure of ZnCo‐RuO2/C exposes abundant active sites and facilitates mass transfer for OER. Theoretical calculations indicate that ZnCo‐RuO2 may break the linear scaling relationship for the OER intermediates and dramatically reduces the energy barrier of the potential determining step, which may be one of the factors that are responsible for the enhanced OER performance of ZnCo‐RuO2/C. In 1 m KOH aqueous electrolyte, ZnCo‐RuO2/C delivers an overpotential of only 180 mV at 10 mA cm−2 and a Tafel slope of 63 mV dec−1, superior to that of single metal‐doped, pristine and commercial RuO2. As an anode catalyst of zinc‐air batteries, ZnCo‐RuO2/C exhibits improved power density and durability relative to commercial RuO2, very promising for practical application.

Consistency of the regional response to global warming levels from CMIP5 and CORDEX projections

Assessing the regional responses to different Global Warming Levels (GWLs; e.g. + 1.5, 2, 3 and 4 ºC) is one of the most important challenges in climate change sciences since the Paris Agreement goal of keeping global temperature increase well below 2 °C with respect to the pre-industrial period. Regional responses to global warming were typically analyzed using global projections from Global Climate Models (GCMs) and, more recently, using higher resolution Regional Climate Models (RCMs) over limited regions. For instance, the IPCC AR6 WGI Atlas provides results of the regional response to different GWLs for several climate variables from both GCMs and RCMs. These results are calculated under the assumption that the regional signal to global warming is consistent between the GCMs and the nested RCMs. In the present study we investigate the above assumption by evaluating the consistency of regional responses to global warming from global (CMIP5) and regional (CORDEX) projections. The dataset aggregated over the new IPCC reference regions, available from the IPCC AR6 WGI Atlas repository, is analyzed here for temperature and precipitation. The existing relationships between the regional climate change signals and global warming are compared for both CMIP5 and CORDEX. Our results show significant linear scaling relationships between regional changes and global warming for most of the regions. CORDEX and CMIP5 show remarkably similar scaling relationships and similar robustness in the emergence of the climate change signal for most of the regions. These results support the use of regional climate models in the context of global warming level studies.

A study of the temperature effect on the spray characteristics in the cone-jet mode of electrohydrodynamic atomization (EHDA) with viscous liquids

In this work, the near-field spray characteristics of electrohydrodynamic atomization (EHDA) for viscous liquids (ethanol, G20, G40, G50, G66, and glycerol) under various temperatures T (T is from 293 to 343 K), electric Bond numbers BoE (BoE is from 0 to 3.5) and dimensionless flow rate Q* (Q* is from 11 to 400) have been investigated by employing a high-speed imaging technique. The transition of the spray modes, variations of the spray angle θ1, semi-angle of Taylor cone θ2, and spraying droplet size (the Sauter mean diameter D32 and the probability density function) in the cone-jet mode have been studied experimentally. The results indicate that the stable cone-jet mode disappeared regardless of increasing BoE for working fluids with relatively higher viscosity (G50, G66, and glycerol). Nevertheless, the temperature elevation promotes the appearance of the stable cone-jet mode, e.g., G66 fluid could form the stable cone-jet as liquid temperature increases to 343 K. Moreover, the temperature plays a significant role in improving the spray angle and the semi-angle of the Taylor cone, as well as droplet size distributions. Specifically, in the case of G40 fluid, the spray angle increased from about 20.8°–23.9° at room temperature (293 K) to around 34.1°–37° at 343 K. Meanwhile, the droplet size distributions were shifting from 9.73–35.49 μm at 293 K to 4.39–23.84 μm at 343 K. The increase in temperature causes a dramatic viscosity reduction in highly viscous fluids, and the viscous dissipation during the atomization reduced substantially. As a result, more kinetic energy was retained to overcome the surface energy and thus improve the quality of the spray. In addition, the dimensionless droplet size D* in the stable cone-jet mode shows a linear scaling relationship with Q*. By introducing an Arrhenius-type equation to account for the temperature effect, a model to predict dimensionless droplet size D* under various dimensionless flow rates Q* and liquid temperatures T has been proposed. The model is in good agreement with the experimental data under the stable cone-jet mode in the EHDA for viscous fluids at a range of temperatures.

Modulation of *CHxO Adsorption to Facilitate Electrocatalytic Reduction of CO2 to CH4 over Cu-Based Catalysts

Copper (Cu) can efficiently catalyze the electrochemical CO2 reduction reaction (CO2RR) to produce value-added fuels and chemicals, among which methane (CH4) has drawn attention due to its high mass energy density. However, the linear scaling relationship between the adsorption energies of *CO and *CHxO on Cu restricts the selectivity toward CH4. Alloying a secondary metal in Cu provides a new freedom to break the linear scaling relationship, thus regulating the product distribution. This paper describes a controllable electrodeposition approach to alloying Cu with oxophilic metal (M) to steer the reaction pathway toward CH4. The optimized La5Cu95 electrocatalyst exhibits a CH4 Faradaic efficiency of 64.5%, with the partial current density of 193.5 mA cm-2. The introduction of oxophilic La could lower the energy barrier for *CO hydrogenation to *CHxO by strengthening the M-O bond, which would also promote the breakage of the C-O bond in *CH3O for the formation of CH4. This work provides a new avenue for the design of Cu-based electrocatalysts to achieve high selectivity in CO2RR through the modulation of the adsorption behaviors of key intermediates.

Adsorbate Bond Number Dependency for σ- and π-bonds in Linear Scaling Relationships

Despite the exigent role of heterogeneous catalysts, designing them in a bottom-up fashion remains a challenge. Linear scaling relationships are, thus far, perhaps the most auspicious first-principles design methodology relating adsorbate strength to catalyst activity. Yet, the successful application of scaling relations as a general design strategy, or even rationally breaking them, is still often limited to simple reactions such as σ-bond cleavage for monodentate adsorbates, and the relationships are nearly always established on close-packed surfaces. Here, it is discussed that for σ- and π-bonds, the metal–adsorbate system has opposite energetic dependency in the offset, which is directly related to the corresponding two classes of structure sensitivity that have empirically been observed in the literature for decades. The discussed observations imply that some currently invoked theories explaining the physical and chemical principles that dominate linear scaling relationships in both inter-adsorbate and BEP linear scaling relationships perhaps do not sufficiently explain them. The discussion is aimed at broadening the applicability of this rational design principle.

Breaking the Linear Scaling Relationship of the Reverse Water–Gas–Shift Reaction via Construction of Dual-Atom Pt–Ni Pairs

Oxide-supported single-atom catalysts hold great potential for reverse water–gas–shift (RWGS) reactions. Nevertheless, it remains challenging to break the linear scaling relationships between the adsorption and desorption capability of catalysts. Herein, we report the design of ZrO2-anchored dual-atom Pt–Ni pairs for the RWGS reaction. The dual-atom material delivers a CO selectivity as high as 99.8% and a space-time yield of 157.2 μmolCO gcat–1 s–1 at atmospheric pressure. Theoretical calculations reveal that the dual-atom Pt–Ni pairs could direct the dual electronic transfer paths (dxz and dyz) to the 2π* orbitals of CO2 in the RWGS reaction, which achieve strong hybridization between them to enable efficient activation of CO2. Moreover, the delocalized charge in dual-atom Pt–Ni may lead to a facile desorption of the CO product.

Oxidation of metallic Cu by supercritical CO2 and control synthesis of amorphous nano-metal catalysts for CO2 electroreduction

Amorphous nano-metal catalysts often exhibit appealing catalytic properties, because the intrinsic linear scaling relationship can be broken. However, accurate control synthesis of amorphous nano-metal catalysts with desired size and morphology is a challenge. In this work, we discover that Cu(0) could be oxidized to amorphous CuxO species by supercritical CO2. The formation process of the amorphous CuxO is elucidated with the aid of machine learning. Based on this finding, a method to prepare Cu nanoparticles with an amorphous shell is proposed by supercritical CO2 treatment followed by electroreduction. The unique feature of this method is that the size of the particles with amorphous shell can be easily controlled because their size depends on that of the original crystal Cu nanoparticles. Moreover, the thickness of the amorphous shell can be easily controlled by CO2 pressure and/or treatment time. The obtained amorphous Cu shell exhibits high selectivity for C2+ products with the Faradaic efficiency of 84% and current density of 320 mA cm−2. Especially, the FE of C2+ oxygenates can reach up to 65.3 %, which is different obviously from the crystalline Cu catalysts.

Amine Groups in the Second Sphere of Iron Porphyrins Allow for Higher and Selective 4e-/4H+ Oxygen Reduction Rates at Lower Overpotentials.

Iron porphyrins with one or four tertiary amine groups in their second sphere are used to investigate the electrochemical O2 reduction reaction (ORR) in organic (homogeneous) and aqueous (heterogeneous) conditions. Both of these complexes show selective 4e-/4H+ reduction of oxygen to water at rates that are 2-3 orders of magnitude higher than those of iron tetraphenylporphyrin lacking these amines in the second sphere. In organic solvents, these amines get protonated, which leads to the lowering of overpotentials, and the rate of the ORR is enhanced almost 75,000 times relative to rates expected from the established scaling relationship for the ORR by iron porphyrins. In the aqueous medium, the same trend of higher ORR rates at a lower overpotential is observed. In situ resonance Raman data under heterogeneous aqueous conditions show that the presence of one amine group in the second sphere leads to a cleavage of the O-O bond in a FeIII-OOH intermediate as the rate-determining step (rds). The presence of four such amine groups enhances the rate of O-O bond cleavage such that this intermediate is no longer observed during the ORR; rather, the proton-coupled reduction of the FeIII-O2- intermediate with a H/D isotope effect of 10.6 is the rds. These data clearly demonstrate changes in the rds of the electrochemical ORR depending on the nature of second-sphere residues and explain their deviation from linear scaling relationships.

Trends in CO2 Reduction on Transition Metal Dichalcogenide Edges

Electrocatalytic CO2 reduction is a promising solution to close the anthropogenic carbon cycle. However, linear scaling relations among reaction intermediates of the CO2 reduction reaction (CO2RR) and the competing hydrogen evolution reaction (HER) limits the Faradaic efficiencies and selectivities of traditional transition metal catalysts. The two-dimensional transition metal dichalcogenides (TMDCs) is a promising class of catalysts for the reaction. Selected transition metal dichalcogenides have been shown experimentally to effectively reduce CO2 and in some cases produce “beyond CO” products. The majority of theoretical investigations have focused on MoS2 and WS2, materials that have been widely studied for various applications, e.g desulfurization, HER, Li metal batteries and optical devices. In this computational study, we go beyond Mo and W and study the edge configurations, adsorption properties and aqueous stability of a range of TMDC materials in the 2H phase. We show that the most stable edge configuration is highly dependent on the specific composition of the material, while adsorption properties of H, CO, and COOH vary significantly with edge configuration. We furthermore find that, while a linear scaling among H and CO adsorbates is observed within each group of the sulfides, selenides, and tellurides, respectively, the scaling is shifted toward weaker H bonding and stronger CO bonding going from sulfides to selenides to tellurides. A similar trend is observed for CO/COOH for some edge configurations. The results indicate that the transition metal ditellurides are a promising class of materials with the potential of reducing CO2 further than CO while limiting HER.

Mitigating Coke Formations for Dry Reforming of Methane on Dual-Site Catalysts: A Microkinetic Modeling Study

Dry reforming of methane (DRM) utilizes carbon dioxide (CO2) and methane (CH4) for syngas production. However, carbon accumulation leads to quick catalyst deactivation. In this study, we developed microkinetic models to describe dual-site catalyst systems to promote catalytic reactivity and suppress coke formation. These dual-site systems serve as idealized bifunctional catalyst models with well-defined active sites targeting different types of chemistries in one reaction network. According to density functional theory (DFT) calculations, the Co and Co–Mo2N interfacial sites in the Co–Mo ternary nitride (i.e., Co3Mo3N) show distinct reactivities toward CH4 decomposition and CHx oxidation, respectively. DFT calculations suggested that DRM intermediates (e.g., OH, CHO) do not always follow unified linear scaling relationships. Hence, a breakthrough was achieved from the limitations of the intrinsic linear correlations embedded in species adsorptions and activations. We employed microkinetic modeling to quantify the enhancement in syngas productions related to bifunctionality. Moreover, we confirmed that Co3Mo3N is the most effective in mitigating coke formation by facilitating the oxidation and transportation of carbonaceous species (e.g., C, CH) from the initial active sites to sustain a high reactivity. This work has shed light on rational catalyst designs to achieve high reactivity and long-term stability, especially for reactions such as DRM.

A Kinetic Control Strategy for One‐Pot Synthesis of Efficient Bimetallic Metal‐Organic Framework/Layered Double Hydroxide Heterojunction Oxygen Evolution Electrocatalysts

AbstractHeterojunction materials are promising candidates for oxygen evolution reaction (OER) electrocatalysts to break the linear scaling relationship and lower the reaction barrier. However, the application of heterojunction materials is always hindered by the complicated multistep synthetic procedures which bring cost, complexity, and reproducibility issues. Herein, a strategy of kinetic controlled synthesis is developed to achieve the one‐pot formation of bimetallic metal‐organic framework (MOF)/layered double hydroxide (LDH) heterojunction electrodes as highly efficient OER electrocatalysts. The heterojunction electrodes present hierarchical structures with highly porous NiFe‐LDH nanosheet networks vertically grown on the surface of NiFe‐MOF‐74 microprisms, promoting fast mass transport and high exposure of active sites. The strong interactions at the MOF/LDH heterojunction interfaces contribute to the outstanding OER activity surpassing the state‐of‐art RuO2 OER catalysts. The MOF/LDH heterojunction electrode exhibits an ultralow overpotential of only 159.7 mV to reach the current density of 10 mA cm−2, and yields large current densities at small overpotential (100 mA cm−2 at 230.2 mV and 1000 mA cm−2 at 284.3 mV) with long‐term durability. This study presents an innovative approach to construct heterojunction materials with simple one‐step synthesis, offering a promising pathway for high‐efficiency electrocatalyst development.

Tailoring the coordination environment of double-atom catalysts to boost electrocatalytic nitrogen reduction: a first-principles study.

Tailoring the coordination environment is an effective strategy to modulate the electronic structure and catalytic activity of atomically dispersed transition-metal (TM) catalysts, which has been widely investigated for single-atom catalysts but received less attention for emerging double-atom catalysts (DACs). Herein, based on first-principles calculations, taking the commonly studied N-coordinated graphene-based DACs as references, we explored the effect of coordination engineering on the catalytic behaviors of DACs towards the electrocatalytic nitrogen reduction reaction (NRR), which is realized through replacing one N atom by the B or O atom to form B, N or O, N co-coordinated DACs. We found that B, N or O, N co-coordination could significantly strengthen N2 adsorption and alter the N2 adsorption pattern of the TM dimer active center, which greatly facilitates N2 activation. Moreover, on the studied DACs, the linear scaling relationship between the binding strengths of key intermediates can be attenuated. Consequently, the O, N co-coordinated Mn2 DACs, exhibiting an ultralow limiting potential of -0.27 V, climb to the peak of the activity volcano. In addition, the experimental feasibility of this DAC system was also identified. Overall, benefiting from the coordination engineering effect, the chemical activity and catalytic performance of the DACs for NRR can be significantly boosted. This phenomena can be understood from the adjusted electronic structure of the TM dimer active center due to the changes of its coordination microenvironment, which significantly affects the binding strength (pattern) of key intermediates and changes the reaction pathways, leading to enhanced NRR activity and selectivity. This work highlights the importance of coordination engineering in developing DACs for the electrocatalytic NRR and other important reactions.

Universal properties of metal-supported oxide films from linear scaling relationships: elucidation of mechanistic origins of strong metal-support interactions.

The properties of ultrathin (1-2 monolayer) (hydroxy)oxide films on transition metal substrates have been extensively studied as models of the celebrated Strong Metal-Support Interaction (SMSI) and related phenomena. However, results from these analyses have been largely system specific, and limited insights into the general principles that govern film/substrate interactions exist. Here, using Density Functional Theory (DFT) calculations, we analyze the stability of ZnO x H y films on transition metal surfaces and show that the formation energies of these films are related to the binding energies of isolated Zn and O atoms via linear scaling relationships (SRs). Such relationships have previously been identified for adsorbates on metal surfaces and have been rationalized in terms of bond order conservation (BOC) principles. However, for thin (hydroxy)oxide films, SRs are not governed by standard BOC relationships, and a generalized bonding model is required to explain the slopes of these SRs. We introduce such a model for the ZnO x H y films and confirm that it also describes the behavior of reducible transition metal oxide films, such as TiO x H y , on metal substrates. We demonstrate how the SRs may be combined with grand canonical phase diagrams to predict film stability under conditions relevant to heterogeneous catalytic reactions, and we apply these insights to estimate which transition metals are likely to exhibit SMSI behavior under realistic environmental conditions. Finally, we discuss how SMSI overlayer formation for irreducible oxides, such as ZnO, is linked to hydroxylation and is mechanistically distinct from the overlayer formation for reducible oxides such as TiO2.

Identification of linear scaling relationships in polysulfide conversion on α-In2Se3-supported single-atom catalysts.

Developing highly active single-atom catalysts (SACs) for suppressing the shuttle effect and enhancing the kinetics of polysulfide conversion is regarded as an important approach to improve the performance of Li-S batteries. However, the adsorption behaviors of polysulfides and the catalytic properties of host materials remain obscure due to the lack of mechanistic understanding of the structure-performance relationship. Here, we identify that the adsorption energies of polysulfides on 3d transition-metal atoms supported by two-dimensional α-In2Se3 with downward polarization (TM@In2Se3) are highly correlated with the d-band centers of the TM atoms. Introduction of the TM atoms on the α-In2Se3 surface improves the electrical conductivity and meanwhile, significantly enhances the adsorption strength of polysulfides and suppresses the shuttle effect. A mechanistic study of polysulfide conversion on TM@In2Se3 shows that the Li2S2 dissociation is the potential-determining step with low activation energies, indicating that TM@In2Se3 can accelerate the kinetics of polysulfide conversion. Electronic structure analysis shows that the kinetics of the potential-determining step on TM@In2Se3 is related to the TM-S interaction in Li2S2-adsorbed TM@In2Se3. A linear scaling relationship between activation energy and the integrated crystal orbital Hamilton population of TM-S in the potential-determining step on TM@In2Se3 is identified. Based on the evaluation of stability, conductivity and activity, we concluded that Ti@In2Se3, V@In2Se3, and Fe@In2Se3 are the promising cathode materials for Li-S batteries. Our findings provide a fundamental understanding of the intrinsic link between the electronic structure and catalytic activity for polysulfide conversion and pave a way for the rational design of SAC-based cathodes for Li-S batteries.

Breaking linear scaling relationships with transition metal carbides

Transition metal carbides (TMCs) are proposed as catalysts and supports for small metal particles to replace expensive late transition metals as heterogeneous catalysts.

Single-Site Metal-Organic Framework and Copper Foil Tandem Catalyst for Highly Selective CO2 Electroreduction to C2 H4.

Tandem catalysis is a promising way to break the limitation of linear scaling relationship for enhancing efficiency, and the desired tandem catalysts for electrochemical CO2 reduction reaction (CO2 RR) are urgent to be developed. Here, a tandem electrocatalyst created by combining Cu foil (CF) with a single-site Cu(II) metal-organic framework (MOF), named as Cu-MOF-CF, to realize improved electrochemical CO2 RR performance, is reported. The Cu-MOF-CF shows suppression of CH4 , great increase in C2 H4 selectivity (48.6%), and partial current density of C2 H4 at -1.11V versus reversible hydrogen electrode. The outstanding performance of Cu-MOF-CF for CO2 RR results from the improved microenvironment of the Cu active sites that inhibits CH4 production, more CO intermediate produced by single-site Cu-MOF in situ for CF, and the enlarged active surface area by porous Cu-MOF. This work provides a strategy to combine MOFs with copper-based electrocatalysts to establish high-efficiency electrocatalytic CO2 RR.

Spatial Modulation and Thermal-Induced Spin Phase Transition on the Negative Thermal Expansion of ScF3 with Metal Dopants

Negative thermal expansion (NTE) is an intriguing physical property of solids, which is often related to the lattice, phonons, charges, and spin. However, most of the studies are mainly focused on the phonons, and the spin-related mechanism in open framework compounds remains unclear owing to the lack of more experimental pieces of evidence. Here, based on the first-principles calculations combined with the quasi-harmonic approximation, we carried out studies of the NTE properties of ScF3 with metal dopants to reveal the roles in NTE of both the spatial effects and spin states. For most of the dopants, the NTE coefficient decreases with the decrease of ionic radius, obeying a linear scaling relationship. Interestingly, for magnetic impurities with a spin phase transition from a high spin state to a low spin state, we show that they will exhibit a Jahn–Teller distortion behavior and enhance the longitudinal vibration mode. In turn, the longitudinal vibration mode has a large positive Grüneisen parameter, which can offset the NTE obviously. This work not only proposes a new insight into the NTE mechanism about impurities in ScF3 but also provides an approach to tailor the NTE properties for fluorides with magnetic impurities as well as oxides.