Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation

Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation Shunfang Li, Feixiang Zhang, Panshuo Wang, Yandi Zhu, Jinlei Shi, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4937470/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 12 Feb, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract In modern chemistry, the development of highly efficient room-temperature catalysts is of great significance and remains a long-standing challenge in various typical reactions. Here, we theoretically demonstrate that the two-dimensional (2D) multiferroic, Cr(half-fluoropyrazine) [Cr(h-fpyz) 2 ], is a promising single-atom catalyst (SAC) operating at room-temperature for CO oxidation. The rate-limiting barrier is merely 0.33 eV, leading to a reaction rate (i.e., 2.86×10 6 s −1 ) of five orders of magnitude higher than its monoferroic derivative [Cr(pyz) 2 ], due to the synergetic effects of two aspects. First, the more flexible ligand rotations in Cr(h-fpyz) 2 facilitate the activation of O 2 molecule, simultaneously enhancing the charge transfer and spin-accommodation process. Second, on Cr(h-fpyz) 2 , O 2 adsorption induces a distinctly lower local positive electric field, reducing the electrostatic repulsion of the polar CO molecule. These findings may also pave the way for establishing highly efficient SAC platforms based on 2D multiferroics where multidegree of freedom (e.g. spin, polarity) synergistically matter. Physical sciences/Physics/Condensed-matter physics/Ferroelectrics and multiferroics Physical sciences/Chemistry/Catalysis/Catalytic mechanisms Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction With the rapid advancement of modern industry and the intensifying energy crises, the development of highly efficient catalysts has become critically important for a range of complex chemical reactions. However, most catalysts encounter complex stability issues, and their practical applications are also generally constrained by the relatively high operating temperature 1, 2 . The U.S. Department of Energy (US-DOE) has set the goal of achieving 90% conversion of all criteria pollutants at 150°C－“the 150°C challenge” 3 . Nevertheless, such a temperature is still approximately 100°C lower than current state-of-the-art commercial automotive catalysts. In general, charge 4 , spin 5 , orbital 6 , and polarity 7 can simultaneously play significant roles in chemical processes. Correspondingly, if a catalytic platform possesses well-matched degrees of freedom, such as spin and polarity, with those of the reactants, high-performance selective catalysis can be achieved 8-10 . Recent reports have demonstrated that high spin states of the catalysts can significantly enhance various chemical processes 8-10 , which can be effectively explained by Wigner’s spin selection rule 9, 11-15 . Moreover, recent advances have confirmed that electric field 16, 17 and ferroelectricity can play a crucial role in enhancing the catalytic activities, such as CO 2 electrocatalytic reduction 18 and photocatalytic water splitting 19 . This enhancement is primarily due to the significantly improved charge transfer facilitated by ferroelectric materials 20 . Therefore, developing highly efficient room-temperature catalysts leveraging the synergetic effects of the aforementioned degrees of freedom is both anticipated and warranted. Multiferroics, which simultaneously encompass ferroelectric, ferromagnetic, and ferroelastic orders, have attracted significant attention from researchers due to their promising applications in various fields 21-23 . These applications include nonvolatile multistate data storage, magnetoelectric sensors, multifunctional and electrically controlled spin wave devices 24, 25 . Moreover, due to the tunable orders and the synergies of different degrees of freedom, such as charge, spin, and orbital integrated within a single phase, it is reasonable to expect that multiferroics could serve as highly efficient room-temperature catalytic candidates. Very recently, a new type of two-dimensional (2D) multiferroic material, i.e. , a 2D metal-organic framework room-temperature multiferroicity (RT-MF), specifically Cr(h-fpyz) 2 (h-fpyz = half-fluoropyrazine) 26 has been predicted, with stable ferroelectricitis and ferrimagnetic phase up to around 400 and 600 K, respectively. This unique 2D material can be rationally designed by introducing relatively large ferroelectricity (4.8 μ C/cm 2 ) through fluorination 27 in Cr(pyz) 2 , while retaining the ferromagnetic coupling (3.61 μ B/Cr) between the evenly dispersed metal ions. Essentially, this 2D RT-MF structure can be understood as a derivative of the experimentally fabricated bulk metal-organic ferrimagnetic layered material 28 , exhibiting a high Curie critical temperature of up to 515 K and significant coercivity (7500 Oersted) at room-temperature. Moreover, from geometric perspective, the present 2D RT-MF Cr(h-fpyz) 2 structure, featuring evenly dispersed Cr species in single-atomic form stabilized by surrounding organic ligands, represents a promising candidate for high-loading single-atomic catalyst (SAC). SAC represents an important enabling concept 29 and has been intensively exploited in the broad field of chemical catalysis, such as CO 2 reduction 30 , CO oxidation 31, 32 , O 2 reduction 33 , N 2 reduction 34 , hydrogen evolution reaction 35 , and oxygen evolution reaction 36 . Furthermore, by probing the interactions between the single-atom reactive sites and the reactants, multiple potential physical mechanisms have been established from various perspectives. For example, insights from the aspects of geometric flexibility 37, 38 , charge transfer 39, 40 , orbital hybridizations 41, 42 , and spin selection 43, 44 have been proposed. However, in these related investigations, the materials used as SAC platforms typically exhibit only one type of ferroic order, such as ferromagnetism 45, 46 , or ferroelectricity 47, 48 . To date, despite extensive research on the distinctive physical properties of both 2D multiferroic materials 49-51 , and the catalysis of numerous SAC systems 6, 29 , the synergetic effect of these aspects on the room-temperature catalytic performance of 2D RT-MF SAC structures, such as Cr(h-fpyz) 2 , remains significantly underexplored. Here, employing state-of-the-art first-principles calculations and model analysis, taking spin-triplet O 2 activation and polar molecule CO oxidation as a prototypical example, we demonstrate that the present 2D RM-MF Cr(h-fpyz) 2 can serve as a highly efficient SAC candidate operating at room-temperature. The calculated rate-limiting energy barrier is approximately 0.33 eV, resulting in a reaction rate of 2.86×10 6 s −1 . This rate is five orders of magnitude higher than its monoferroic derivative [Cr(pyz) 2 ] counterpart, due to the synergetic effects of magnetism and ferroelectricity. Specifically, the flexible rotation of the organic ligand in the multiferroic Cr(h-fpyz) 2 functions as a controllable knob, enhancing the charge transfer and spin accommodation during the activation of spin-triplet O 2 molecule, while simultaneously lowering the local normal positive electric field. This synergetic mechanism results in the polar CO molecule experiencing relatively low repulsive electrostatic interactions and a significantly reduced reaction barrier, making the 2D RM-MF Cr(h-fpyz) 2 a promising candidate for a room-temperature SAC system. Beyond their various applications due to the exotic physical properties, the present findings significantly broaden the potential applications of 2D multiferroics in the crucial field of chemical catalysis. Moreover, this work may direct new avenue towards developing highly efficient SAC platforms for various other important chemical processes where multiple degrees of freedom, such as spin and polarity, synergistically matter. Results Geometric and electronic structures of the 2D RM-MF Cr(h-fpyz) 2 . First, we briefly reexamined the optimized geometric structure of the 2D Cr(h-fpyz) 2 26 metal-organic framework, simulated within a unit cell comprising four Cr metal atoms and eight h-fpyz organic ligands. Here, four of the latter are connected to the central Cr atoms in a clockwise manner (Fig. 1a). Our extensive spin-polarized density-functional theory (DFT) calculations confirmed that in the 2D Cr(h-fpyz) 2 structure, Cr ions exhibit a preference for ferromagnetic order over antiferromagnetic order by about 0.25 eV/f.u., consistent with prior research findings 26 . Moreover, the calculated magnetic moment (MM) of each four-coordinated Cr ion is about 3.68 μ B, which is antiparallel to that of its four adjacent h-fpyz ligand molecules, each possessing a MM of 0.84 μ B. Thus, the ground state of 2D Cr(h-fpyz) 2 is ferrimagnetic, with a total MM of approximately 8.0 μ B per primitive unit cell. Furthermore, it has been identified that the 2D Cr(h-fpyz) 2 system exhibits an antiferroelectric (AFE) state, due to the antiparallel arrangements of the eight h-fpyz ligand molecles in the primitive cell (Fig. 1b). Fig. 1c shows the side view of Cr(h-fpyz) 2 . The spin-polarized band structure and density of states (DOS) (Fig. 1d) demonstrate a direct energy band gap of approximately 0.55 eV, which aligns with previous DFT calculations 26 . Activation of spin-triplet O 2 on 2D Cr(h-fpyz) 2. Subsequently, we investigate the adsorption and activation of spin-triplet O 2 on 2D Cr(h-fpyz) 2 , which is the key step for CO oxidation. It is revealed that the O 2 molecule preferentially adsorbs on the Cr I site, with an adsorption energy ( E ads ) of 1.10 eV. This adsorption is accompanied by a significant increase in the O-O bond length from 1.24 to 1.44 Å (Fig. 1e). Here, we define E ads = － [E(O 2 － Cr(h-fpyz) 2 ) － E(O 2 ) － E(Cr(h-fpyz) 2 )]. On Cr II and Cr III , the calculated E ads are relatively low, 0.68 and 0.36 eV, respectively. These distinct adsorption behaviors at the three different sites can be attributed to the contrasting local geometric environments of the antiferroelectric state in the 2D RM-MF Cr(h-fpyz) 2 structure. Specifically, on Cr I , Cr II , and Cr III , the adsorbed O 2 is surrounded by four H atoms, two H and two F atoms, and four F atoms of the four organic ligands, respectively (Supplementary S1). In other words, the incoming O 2 molecule may experience disparate local electric field (LEF) nearby (~ 3 Å) above the Cr I and Cr III atoms, as demonstrated (Figs. 2a, d). This directly influences the charge transfer, as discussed shortly, and accounts for the distinct activities of these two types of Cr single-atom reactive sites. These findings strongly indicate that the catalysis of ferroelectric materials 25-28 can be effectively modulated by the ferroelectric polarization direction down to the single-atom scale, specifically in SAC systems. Note that, here the spin-orbit coupling (SOC) effect has a negligible influence on O 2 adsorption and activation. Therefore, the subsequent calculations were performed without considering SOC. Second, we conduct Bader charge analysis to examine the charge transfer (Δρ = ρ(O 2 -Cr(h-fpyz) 2 ) － ρ(O 2 ) － ρ(Cr(h-fpyz) 2 )) between the incoming O 2 and the Cr(h-fpyz) 2 catalytic substrate. Here, ρ(O 2 ) and ρ(Cr(h-fpyz) 2 ) represent the calculated charge obtained from the isolated ground-state O 2 molecule and the 2D Cr(h-fpyz) 2 substrate, respectively. To gain a clearer understanding of the charge transfer, we conducted a Bader charge analysis on the 2D Cr(h-fpyz) 2 substrate (Supplementary Fig. 2). Briefly, in this pristine 2D RM-MF, both nitrogen (N) and fluorine (F) atoms accommodate charge transferred predominantly from their neighboring chromium (Cr) atoms, amounting to approximately 1.3 |e|, as well as from carbon (C) atoms. Here, C atoms can be classified into two types, which are coordinated by H and F atoms, termed C H and C F , respectively. The nearest neighboring C H and C F of Cr I (Cr II ) donate about 0.46 (0.36) and 1.09 (0.99) |e|, respectively. Note that, when the incoming O 2 molecule is positioned more than 10 Å above the designated Cr I active site, as termed the initial state (IS), negligible charge transfer is observed between O 2 and the substrate (Supplementary Fig. 3). Upon O 2 adsorption on the reactive Cr I (Cr III ) hosting site, approximately 1.02 (0.79) |e| is transferred from the substrate to O 2 respectively (Fig. 2b, e). Such a distinct charge transfer between Cr I and Cr III accounts for their contrasting catalytic behaviors in CO oxidation, as discussed later. In this process, the reactive Cr I (Cr III ) atom, along with the remaining C, H, and F (C, N, and F) atoms donate electrons by approximately 0.23, 0.69, 0.31, and 0.06 |e| (0.21, 0.39, 0.16, and 0.08 |e|), respectively. Furthermore, Cr II and Cr III (C I and Cr II ) which positioned approximately 7.02 and 9.92 Å (9.92 and 7.02 Å) away from Cr I (Cr III ), respectively contribute negligible charge transfer to the adsorbed O 2 . It is noteworthy that, although the Cr I reactive site is directly linked by the N atom of the h-fpyz ligand, the second nearest neighboring C atoms of Cr I , in another word, the nearest neighboring C atoms of Cr II , dominate the charge transfer to the adsorbed O 2 (Supplementary Fig. 4). Additionally, due to the significantly lower electronegativity of H than that of F, the nearby H atoms donate significantly more charge to the adsorbed O 2 species than F atoms. This further rationalizes the contrasting E ads of the O 2 on Cr I , Cr II , and Cr III sites. In contrast to charge transfer, the reactive Cr I atom, along with the substrate N, and C atoms, play a crucial synergetic role in accommodating the spin transferred from the adsorbed O 2 molecule. This facilitates its spin triplet-to-singlet activation of the O 2 molecule, which is the key step for CO oxidation. Similar to the definition of charge transfer Δρ, here we define the magnetic moment transfer as ΔM = M(O 2 − Cr(h-fpyz) 2 ) − M(O 2 ) − M(Cr(h-fpyz) 2 ).The initial state (IS) primarily reflects the intrinsic magnetic moment of the incoming spin-triplet O 2 molecule and the substrate (Supplementary Fig. 3b), with negligible interactions between them. Upon O 2 adsorption, the total magnetic moment of the optimized O 2 -Cr(h-fpyz) 2 complex remains at 8 μ B (spin quantum number S O 2 -Cr(h-fpyz) 2 = 4). That is, the spin−spin coupling between the spin-triplet O 2 molecule ( S O 2 = 1) and the Cr(h-fpyz) 2 catalyst ( S Cr(h-fpyz) 2 = 4) follows the channel of “1 + 4 = 4”, which is a spin-allowed reaction according to Wigner’s spin selection rule 9, 11-15 . Such a classic rule restricts that the total spin quantum number S O 2 -Cr(h-fpyz) 2 in the spin-allowed reaction should satisfy S O 2 -Cr(h-fpyz) 2 = | S Cr(h-fpyz) 2 − S O 2 |, | S Cr(h-fpyz) 2 − S O 2 |+1, ..., | S Cr(h-fpyz) 2 + S O 2 |, where S Cr(h-fpyz) 2 and S O 2 are the spin quantum numbers of the substrate Cr(h-fpyz) 2 and an isolated ground state O 2 molecule, respectively. However, the local spin moment of the optimized O 2 -Cr(h-fpyz) 2 complex with O 2 adsorbed on Cr I (Cr III ) reactive stie changes intriguingly, as shown in Fig. 2c (f). Specifically, the magnetic moment of the adsorbed O 2 on Cr I (Cr III ) is reduced from 2.0 μ B to nearly zero, i.e., - 0.24 ( - 0.02) μ B, indicating that the O 2 molecule has transitioned from a spin triplet state to singlet. Correspondingly, the magnetic moment of the Cr I (Cr III ) atom is reduced from 3.68 (3.69) to 3.01 (3.08) μ B, with a reduction of 0.67 (0.61) μ B. Somewhat unexpectedly, the nearby non-metal atoms, such as C and N, in the vicinity of the reactive Cr I (Cr III ) atom primarily accommodate the magnetic moments by 0.83 (0.60) μ B. However, the relatively distant transitional metal atoms, Cr II and Cr III (Cr I and Cr II ) only accommodate about 0.02(0.03) µ B upon O 2 adsorption and activation. These results demonstrate a significant synergetic spin communication mechanism among the O 2 molecules, the substrate p -block C/N atoms, and the d -block Cr reactive site in activation of spin-triplet O 2 . Collectively, comparing the cases of O 2 adsorption on Cr I and Cr III , it is evident that the reactivity of the Cr atom increases with the synergy of charge transfer and spin communication involving the p -block C/N atoms. According to Wigner’s spin selection rule, catalytic system in a low spin state ( S =0) typically exhibits high inertness towards spin-triplet O 2 13, 14 . This observation convincingly demonstrates the crucial role of the magnetic order of the 2D RM-MF Cr(h-fpyz) 2 in facilitating the activation of ground state O 2 molecule. CO oxidation on 2D Cr(h-fpyz) 2. Now, we continue to examine the minimum energy pathway (MEP) of CO oxidation on 2D Cr(h-fpyz) 2 (step i, Fig. 3) via interacting with the adsorbed O 2 molecule (step ii, Fig. 3). Note that, here we have also verified the CO adsorption on the pristine Cr(h-fpyz) 2 , and the optimized E ads (CO) is merely about 0.37 eV, which is much lower than that of E ads (O 2 )=1.10 eV. Therefore, for the present system, CO oxidation should prefer the E-R reaction mechanism with O 2 preferentially adsorbed. It is observed that, the adsorbed O 2 molecule is readily attacked by the incoming CO, releasing a CO 2 molecule upon overcoming a low activation energy ( E bar ) of 0.33 eV (TS 1 , Fig. 3), with an exothermic energy of 2.80 eV. In TS 1 , the distance between CO and O is 2.0 Å. Following the release of the generated CO 2 molecule, an O species is left on the Cr I site (step iv, Fig. 3). Consequently, the second incoming CO can also smoothly react with the protruding O atom, generating another CO 2 precursor with an exothermic energy of 2.45 eV after overcoming an even lower E bar of 0.30 eV (TS 2 , Fig. 3). Further calculations demonstrate that the desorption energy of the second CO 2 (step vi, Fig. 3) is fairly low, approximately 0.2 eV. Correspondingly, the low rate-limiting energy barrier of 0.33 eV results in a high reaction rate of about 2.86×10 6 s −1 at room-temperature (300 K), as estimated by using the Arrhenius form (R = R 0 ×exp[− E bar /(k B T)]) with a typical prefactor R 0 of 10 12 s −1 . Such a low rate-limiting E bar of 0.33 eV is significantly lower than those obtained for various other typical high-efficient noble SAC or nanocluster-based catalytic complexes, e.g., 0.79 eV for Pt 1 /FeO x 29 , 0.91 eV for Pt 1 /Fe 2 O 3 52 , 0.56 eV for Pt 1 /CeO 2 53 , 1.1 eV for Ir 1 -on-MgAl 2 O 4 54 , 0.66 eV for Pt 4 /CoNi@C 55 , and 1.71 eV for Pt-carbonyl 56 , respectively. Moreover, the calculated R ( E bar =0.33 eV) reaches 1.17×10 8 s -1 at 423 K, implying that the present 2D RM-MF Cr(h-fpyz) 2 is a promising high-performance catalyst subject to “the 150°C challenge”. As a comparison, we have also examined CO oxidation via interacting with the adsorbed O 2 on Cr III single-atom reactive site (Supplementary Fig. 5). Briefly, the high rate-limiting E bar of about 1.0 eV results in a low reaction rate of about 1.59×10 -5 s −1 at room-temperature. Specifically, compared to Cr I , reversing the LEF direction around the Cr III single-atom reactive site significantly (Fig. 2a, d) reduces the reaction rate, by approximately eleven orders of amplitude. In other words, an on-off switching for the room-temperature catalysis of SAC can be achieved by tuning the polar direction of the 2D RM-MF Cr(h-fpyz) 2. Fig. 4a presents the Bader charge analysis for the key steps in CO oxidation depicted (Fig. 3). When CO is weakly adsorbed on the vicinity of the adsorbed O 2 (step iii, Fig. 3), the O 2 -CO species acquires a charge of approximately 1.04 |e|. Specifically, the non-metal atoms in the substrate contribute about 0.81 |e|, whereas the metal Cr atoms contribute only about 0.23 |e|, indicating that the non-metal atoms dominate the charge transfer. This trend is also observed in TS 1 and all other representative steps up to TS 2 (Fig. 3), as also demonstrated in Fig. 4a and Supplementary Fig. 6a. The changes in the magnetic moment (ΔM) of the corresponding key steps. From step iii to step vi (Fig. 4b), there are substantial reductions in the local magnetic moments of both the O 2 -CO species and the Cr metal atoms. Notably, as in step iii, in almost all the other key steps, the p -block non-metal C and N atoms accommodate more MM than that of the d -block Cr reactive atom (Supplementary Fig. 6b). These findings demonstrate a delicate synergetic charge and spin accommodation mechanism occurred among the O 2 /CO molecule, d -block reactive Cr atom, and the surrounding p -block C and N atoms, occurring during both O 2 activation and CO oxidation on the multiferroic Cr(h-fpyz) 2 catalytic platform. Comparison of CO oxidation on monoferroic Cr(pyz) 2. To more clearly demonstrate the crucial role of the multiferroic orders in high-performance CO oxidation, we conducted a comparative examination of O 2 activation and CO oxidation on Cr(pyz) 2 (pyz = pyrazine). This compound was created by substituting all the F atoms in Cr(h-fpyz) 2 with H atoms (Supplementary Fig. 7a, b). Consequently, the substrate undergoes a transition from multiferroic to monoferroic, remaining only ferrimagnetic properties. Based on this, we further explored the adsorption of O 2 on the monoferroic Cr(pyz) 2 substrate (Supplementary Fig. 7c). In comparison to the adsorption on the Cr I reactive site of multiferroic Cr(h-fpyz) 2 , the optimized E ads (O 2 ) increases slightly by 0.03 eV to reach 1.13 eV. Additionally, the O-O bond length is enlarged to 1.44 Å. Similarly, CO exhibits weak adsorption on the Cr atom, characterized by an E ads (CO) of 0.38 eV, suggesting that only an E-R mechanism is viable for CO oxidation. Surprisingly, despite comparable activation of O 2 on both catalytic platforms in terms of bond length and adsorption energy, a significantly elevated rate-limiting E bar of 0.65 eV is observed for CO oxidation on the monoferroic Cr(pyz) 2 (Supplementary Fig. 8). Using the same approach, the calculated CO oxidation rate is 1.20×10 1 s -1 , which is about five orders of magnitude lower than that observed on the 2D RM-MF Cr(h-pyz) 2 at the room temperature. These findings further underscore the pivotal role of multiferroicity in enhancing the catalytic performance of the present 2D material for CO oxidation. Role of Ligand Rotation in LEF: A knob for on-off switching room-temperature catalysis . To further elucidate the observed phenomena, we conducted a comparative analysis of the local geometric structures around the Cr reactive site in multiferroic Cr(h-fpyz) 2 and monoferroic Cr(pyz) 2 , both with and without O 2 adsorption (Fig. 5). Initially, in the case of 2D RM-MF Cr(h-fpyz) 2 , prior to O 2 adsorption, each of the four h-fpyz ligands surrounding the Cr reactive site tilts approximately 37.8° away from the (100) plane (Fig. 5a) or the (010) plane (Fig. 5b). However, upon O 2 adsorption, the angles undergo symmetry-breaking evolution into two distinct classes. Specifically, the angles between the two h-fpyz rings connecting the reactive Cr atoms along [010] ([100]) direction and the (100) ((010)) plane are significantly reduced (slightly enlarged) from 37.8° to 19.3° (37.8° to 38.5°), (Fig. 5a, b). This change in orientation can be attributed in part to the electrostatic attractive interactions between the negatively charged O 2 and the nearby H cations. Meanwhile, as illustrated in the corresponding lower panels, the position of the reactive Cr atom undergoes spontaneous changes along the [001] direction relative to the pristine Cr(h-pyz) 2 substrate. Specifically, the Cr atom shifts upward, displaying significant displacements relative to the mass centers of N atom along the [010] and [100] directions (Fig. 5a, b). For instance, following O 2 adsorption (structure ii), the Cr atoms shifted modestly (considerably) upward by approximately 0.24 (0.81) Å. Similar contrasting phenomena are also observed during other critical stages of the CO oxidation process, including TS 1 , iv, TS 2 , and vi (Supplementary Fig. 9). Furthermore, qualitatively similar findings are confirmed for O 2 adsorption and CO oxidation on the monoferroic Cr(pyz) 2 . Specifically, the angles (about 47.5°) with respect to (100) ((010)) plane are slightly reduced (enlarged) to 33.6° (47.8°) (Fig. 5c-d). Meanwhile, the Cr reactive site exhibits modest (considerable) upward shifts along the [010] (0.22 Å) and [100] (0.76 Å) direction. However, quantitatively, the changes in relative angles of the organic ligands during the key steps of the CO oxidation on the multiferroic Cr(h-fpyz) 2 are more pronounced compared to those observed in the monoferroic Cr(pyz) 2 system. For instance, in the TS 1 state, the angle change reaches approximately 51.3 % (from 37.8° to 18.4°) for Cr(h-fpyz) 2 , whereas it is about 39.2 % (from 47.5° to 28.9°) for Cr(pyz) 2 . Simultaneously, the upward shift of the Cr reactive site is more significant in Cr(pyz) 2 (0.90 Å) than in Cr(h-fpyz) 2 (0.82 Å), which may correspond to the relatively higher E bar of the monoferroic Cr(pyz) 2 (0.65 eV) compared to multiferroic Cr(h-fpyz) 2 (0.33 eV). This difference is attributed to the relatively large energy cost associated with the upward shift of the Cr atom compared to the rotation of the organic ligands (Supplementary Fig. 9). The rotations of the organic ligands and the upward shift of the Cr reactive site effectively promote charge transfer from the substrate, specifically involving nearby p -block elements H and C, and d -block Cr atoms, to the O 2 molecule (Fig. 6). To investigate this phenomenon, we performed Bader charge analysis on the optimized structures of O 2 adsorption on both 2D multiferroic Cr(h-fpyz) 2 and monoferroic Cr(pyz) 2 systems, considering scenarios with and without allowing the rotations of the organic ligands and the accompanied upward shifts of the Cr atom. Specifically, when an O 2 molecule adsorbs freely on multiferroic Cr(h-fpyz) 2 , the O 2 species acquires a charge of approximately 1.02 |e|, with the underlying Cr reactive site and the nearby H atoms donating about 0.23 |e| and 0.11 |e| per H atom, respectively (Fig. 6a). However, for the case of without rotation of the organic ligands and the accompanied upward shift of the Cr atom, the charge on the adsorbed O 2 molecule decreases to about 0.70 |e|, with the reactive Cr atom and the nearby H atoms at relatively greater distances donating about 0.09 |e| and 0.08 |e| per H atom, respectively (Fig. 6b). A similar trend is also evident in the case of O 2 adsorption on the monoferroic Cr(pyz) 2 (Fig. 6c, d). Moreover, the contrasting geometric structure changes between the multiferroic Cr(h-fpyz) 2 and monoferroic Cr(pyz) 2 systems upon O 2 adsorption results in quantitively distinct charge transfers and spin accommodations between the O 2 molecule and the substrate atoms. Importantly, such disparate charge transfers upon O 2 adsorptions result in distinct LEF surrounding the O 2 species, which are destined to significantly influence the oxidation of the polar molecule CO, as confirmed in the following section. The rotations of the organic ligands and the upward shift of the Cr reactive site effectively promote charge transfer from the substrate, specifically involving nearby p -block elements H and C, and d -block Cr atoms, to the O 2 molecule (Fig. 6). To investigate this phenomenon, we performed Bader charge analysis on the optimized structures of O 2 adsorption on both 2D multiferroic Cr(h-fpyz) 2 and monoferroic Cr(pyz) 2 systems, considering scenarios with and without allowing the rotations of the organic ligands and the accompanied upward shifts of the Cr atom. Specifically, when an O 2 molecule adsorbs freely on multiferroic Cr(h-fpyz) 2 , the O 2 species acquires a charge of approximately 1.02 |e|, with the underlying Cr reactive site and the nearby H atoms donating about 0.23 |e| and 0.11 |e| per H atom, respectively (Fig. 6a). However, for the case of without rotation of the organic ligands and the accompanied upward shift of the Cr atom, the charge on the adsorbed O 2 molecule decreases to about 0.70 |e|, with the reactive Cr atom and the nearby H atoms at relatively greater distances donating about 0.09 |e| and 0.08 |e| per H atom, respectively (Fig. 6b). A similar trend is also evident in the case of O 2 adsorption on the monoferroic Cr(pyz) 2 (Fig. 6c, d). Moreover, the contrasting geometric structure changes between the multiferroic Cr(h-fpyz) 2 and monoferroic Cr(pyz) 2 systems upon O 2 adsorption results in quantitively distinct charge transfers and spin accommodations between the O 2 molecule and the substrate atoms. Importantly, such disparate charge transfers upon O 2 adsorptions result in distinct LEF surrounding the O 2 species, which are destined to significantly influence the oxidation of the polar molecule CO, as confirmed in the following section. Discussion Employing first-principles calculations based on density functional theory, we have demonstrated for the first time that the 2D multiferroic structure of Cr(h-fpyz) 2 functions effectively as a room-temperature single-atom catalyst. This is evidenced by its highly enhanced catalytic activity, highlighted by the following key findings: (i) The calculated rate-limiting energy barrier for CO oxidation on the Cr single-atom reactive site within the 2D multiferroic catalytic platform is approximately 0.33 eV, resulting in a reaction rate of 2.86×10 6 s −1 at room temperature and 1.17×10 8 s -1 at 423 K, respectively, implying that the present 2D RM-MF Cr(h-fpyz) 2 is a promising high-performance catalytic candidate subject to “the 150°C challenge” of US-DOE. This rate is five orders of magnitude higher than its monoferroic derivative, [Cr(pyz) 2 ]. Moreover, reversing the polar direction (rotating the organic ligands) of the 2D multiferroic Cr(h-fpyz) 2 structure reduces the reaction rate by eleven (eight) orders of the magnitude, enabling on-off switching of room-temperature catalysis of the 2D multiferroic system. (ii) The underlying microscopic mechanism involves the activation of spin-triplet O 2 molecule, facilitated by more flexible rotations of the organic ligand around the Cr single-atom reactive site within the multiferroic Cr(h-fpyz) 2 complex compared to its monoferroic Cr(pyz) 2 derivative. This flexibility enhances the charge transfer and spin-accommodation processes, predominantly influenced by spin-polarized p -block substrate atoms and the confined d -block Cr single-atom reactive site. (iii) Intriguingly, on the multiferroic Cr(h-fpyz) 2 , O 2 adsorption induces a significantly lower local positive electric field normal to the surface compared to the Cr(pyz) 2 , as supported by a simple point-charge model calculation. Consequently, the polar CO molecule experiences reduced repulsive electrostatic interactions and a considerably lower reaction energy barrier. Further simulations confirm that, without allowing the rotations of the organic ligands, the CO oxidation rate is dramatically reduced due to an increased rate-limiting energy barrier, by at least eight orders of magnitude. The present findings are expected to offer new insights into establishing highly efficient single-atom catalyst platforms based on 2D multiferroics for a variety of other important chemical processes where both the spin and polarity degrees of freedom play significant roles. Methods Our calculations were carried out by spin-polarized first-principles calculations based on density functional theory (DFT) 57, 58 , as implemented in the Vienna ab initio simulation package (VASP) 59, 60 , with the projector augmented wave (PAW) 61, 62 method and the revised Perdew-Burke-Ernzerhof (RPBE) 63 for the exchange-correlation functional. DFT+U method 64, 65 with U eff = 4 eV is employed to treat the localization of 3 d orbitals of Cr atoms, as suggested by previous theoretical calculations 26 . The electronic wave functions were expanded in a plane wave basis with an energy cutoff of 550 eV, and the k-space integration was performed with a 2×2×1 Monkhorst-Pack k-point mesh in the Brillouin zone for the relatively large simulation cell. A vacuum space beyond 12 Å along the c-axis is incorporated to prevent interactions between neighboring slabs. To attain the optimized structures, all the atoms were allowed to relax until all the residual force components were less than 0.02 eV/Å. The kinetic properties of CO oxidation were investigated using the climbing-image nudged elastic band (CI-NEB) method 66, 67 . Declarations Data availability The data supporting the findings of the study are included in the main text and supplementary information files. Raw data can be obtained from the corresponding author upon request. Acknowledgement F.X.Z. and P.S.W. contributed equally to this work. We thank Prof. Zhenyu Zhang for helpful discussion. This work was supported by the NSF of China (Grants No. U23A2072, 12074345, 12174349, 12204431, 12204421). The calculations were performed on the National Supercomputing Center in Zhengzhou, Henan. 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Additional Declarations There is NO Competing Interest. Supplementary Files image8.png Table of Contents Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation. SI.docx Cite Share Download PDF Status: Published Journal Publication published 12 Feb, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4937470","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":350485929,"identity":"1e655caf-e73d-46a0-899d-d78bf859c134","order_by":0,"name":"Shunfang Li","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAyklEQVRIiWNgGAWjYDAC5sMNB4CUHITHRowWtkSwFmPStIAoCEmUFvk2xsaDP/4cTp/ff8aA4UPZYQb+2Q34tRgcY2w4IMFzOLex4YwB44xzhxkk7hwgoEW+seGAgcTh3GbGHgNm3rbDDAYSCQQd1nAgweBwOhszjwHzX2K0MIAcdiDhcAIPG1ALIzFaQH452HAg3XAGD1vBwZ5z6TwSNwg6jPnwxx9/rOXl+w9vfPCjzFqOfwYhhyGDA0DMQ4L6UTAKRsEoGAW4AAC34UI8Wg8QCgAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0003-4661-6188","institution":"Zhengzhou University","correspondingAuthor":true,"prefix":"","firstName":"Shunfang","middleName":"","lastName":"Li","suffix":""},{"id":350485930,"identity":"8af6b389-d96f-4e11-81e2-a9a153b47a2d","order_by":1,"name":"Feixiang Zhang","email":"","orcid":"","institution":"Zhengzhou University","correspondingAuthor":false,"prefix":"","firstName":"Feixiang","middleName":"","lastName":"Zhang","suffix":""},{"id":350485931,"identity":"69d80ee8-b150-4df7-9015-66cc4b4aabec","order_by":2,"name":"Panshuo Wang","email":"","orcid":"","institution":"Zhengzhou University","correspondingAuthor":false,"prefix":"","firstName":"Panshuo","middleName":"","lastName":"Wang","suffix":""},{"id":350485932,"identity":"8d30e343-be3c-4269-8af5-e5403f79053f","order_by":3,"name":"Yandi Zhu","email":"","orcid":"","institution":"Zhengzhou University","correspondingAuthor":false,"prefix":"","firstName":"Yandi","middleName":"","lastName":"Zhu","suffix":""},{"id":350485933,"identity":"f9e44066-0b41-4a84-ba85-9c388a9e9a16","order_by":4,"name":"Jinlei Shi","email":"","orcid":"","institution":"Zhengzhou University","correspondingAuthor":false,"prefix":"","firstName":"Jinlei","middleName":"","lastName":"Shi","suffix":""},{"id":350485934,"identity":"7be27080-4464-4a53-9790-8a0ce49f8d62","order_by":5,"name":"Rui Pang","email":"","orcid":"","institution":"Zhengzhou University","correspondingAuthor":false,"prefix":"","firstName":"Rui","middleName":"","lastName":"Pang","suffix":""},{"id":350485935,"identity":"57b94c75-cccf-4804-abd9-a7102978a943","order_by":6,"name":"Xiaoyan Ren","email":"","orcid":"","institution":"Zhengzhou University","correspondingAuthor":false,"prefix":"","firstName":"Xiaoyan","middleName":"","lastName":"Ren","suffix":""}],"badges":[],"createdAt":"2024-08-19 09:25:52","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4937470/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4937470/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-025-56863-1","type":"published","date":"2025-02-12T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":64167146,"identity":"b978455d-2c2e-469a-83a6-11043c6480b3","added_by":"auto","created_at":"2024-09-09 09:45:55","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":319252,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGeometric and electronic structures of Cr(h-fpyz)\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e. a-c\u003c/strong\u003e Optimized geometric structure of the 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e. In (\u003cstrong\u003ea\u003c/strong\u003e), the red arrow indicates the tilted orientation of the h-fpyz ligands. Here, the center and edge Cr atoms of the primitive cell are termed Cr\u003csub\u003eI\u003c/sub\u003e and Cr\u003csub\u003eII\u003c/sub\u003e, respectively, and the rest of the Cr atoms are termed Cr\u003csub\u003eIII\u003c/sub\u003e. In (\u003cstrong\u003eb\u003c/strong\u003e), the dipoles of h-fpyz molecules are also schematically shown. \u003cstrong\u003ec\u003c/strong\u003e Side view of Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ed\u003c/strong\u003e Energy band structures and projected density of state (PDOS) of Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e. \u003cstrong\u003ee\u003c/strong\u003e Side view of the optimal structure of O\u003csub\u003e2\u003c/sub\u003e adsorption on Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/067fdb51653acd2156b43bec.png"},{"id":64168361,"identity":"0732a158-06d3-4421-a18d-268bd155e131","added_by":"auto","created_at":"2024-09-09 10:01:55","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":183067,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eLocal electric field (LEF), and the charge and magnetic moment changes upon O₂ adsorption.\u003c/strong\u003e LEF distributions along the \u003cem\u003eZ\u003c/em\u003e direction passing through the two representative types of Cr reactive atom (Cr\u003csub\u003eI \u003c/sub\u003eand\u003csub\u003e \u003c/sub\u003eCr\u003csub\u003eIII\u003c/sub\u003e) in pristine 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, the electronic charge transfer (Δρ) and magnetic moment change (ΔM) analysis on the optimized structure when an O\u003csub\u003e2 \u003c/sub\u003emolecule is adsorbed on the Cr reactive site performed by Bader analysis. The iso-surface value is 0.0198 e/Å\u003csup\u003e3\u003c/sup\u003e. (\u003cstrong\u003ea\u003c/strong\u003e)-(\u003cstrong\u003ec\u003c/strong\u003e) for the case of Cr\u003csub\u003eI\u003c/sub\u003e, and (\u003cstrong\u003ed\u003c/strong\u003e)-(\u003cstrong\u003ef\u003c/strong\u003e) for the case of Cr\u003csub\u003eIII\u003c/sub\u003e. In (\u003cstrong\u003ea\u003c/strong\u003e) and (\u003cstrong\u003ed\u003c/strong\u003e), Cr atoms are set as the position references.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/8caeaf2759c195500f07721b.png"},{"id":64167151,"identity":"7cc6e406-daeb-4327-9e12-e48770cbfcba","added_by":"auto","created_at":"2024-09-09 09:45:55","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":265814,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCatalytic pathway for CO oxidation. \u003c/strong\u003eMinimum energy pathway (MEP) for O\u003csub\u003e2\u003c/sub\u003e activation and CO oxidation via the Eley-Rideal (E-R) mechanism on Cr\u003csub\u003eI\u003c/sub\u003e reactive site in Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/a6fe7ac1158b3fba775f8c6b.png"},{"id":64167155,"identity":"1536fb27-2338-4895-bb7e-92fb427baa7a","added_by":"auto","created_at":"2024-09-09 09:45:56","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":405186,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eChanges in charge and magnetic moment during key steps of the CO oxidation.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e Charge transfer and \u003cstrong\u003eb\u003c/strong\u003e magnetic moment changes of the key steps during catalytic CO oxidation. In this context, red orange and peach represent non-metal (Non-M) and metal (M) elements respectively. And the O\u003csub\u003e2\u003c/sub\u003e-CO species is identified in sky blue.\u0026nbsp;\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/57f12f348cbec2763fb2a91a.png"},{"id":64167153,"identity":"3f7cee73-f32b-40fc-b4b1-adf8b5cc07e2","added_by":"auto","created_at":"2024-09-09 09:45:55","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":216590,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eLocal structural changes around the active sites of Cr(h-fpyz)₂ and Cr(pyz)₂. a-b \u003c/strong\u003eLocal geometric structures around the Cr reactive site of the multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e and \u003cstrong\u003ec-d\u003c/strong\u003e Monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e with (step i) and without (step ii, TS\u003csub\u003e1\u003c/sub\u003e) O\u003csub\u003e2\u003c/sub\u003e adsorption viewed from the (\u003cstrong\u003ea, c\u003c/strong\u003e) [010] and (\u003cstrong\u003eb, d\u003c/strong\u003e) [100] directions, respectively. The lower panels illustrate the displacements of the Cr atoms along the [001] direction relative to the distinct mass centers of the N atoms along the (\u003cstrong\u003ea, c\u003c/strong\u003e) [010] and (\u003cstrong\u003eb, d\u003c/strong\u003e) [100] directions, respectively.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/aaa20c521c3ddde87b6f74ad.png"},{"id":64167152,"identity":"a8ab6c88-dbd8-4425-bbde-1b2d8425ec31","added_by":"auto","created_at":"2024-09-09 09:45:55","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":211119,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eComparison of charge transfer around active sites due to ligand rotation of the two materials. \u003c/strong\u003eBader charge analysis for the cases of without and with O\u003csub\u003e2\u003c/sub\u003e adsorption on (\u003cstrong\u003ea, b\u003c/strong\u003e) Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e and (\u003cstrong\u003ec, d\u003c/strong\u003e) Cr(pyz)\u003csub\u003e2\u003c/sub\u003e systems. In (\u003cstrong\u003ea\u003c/strong\u003e) and (\u003cstrong\u003ec\u003c/strong\u003e) the structures are optimized without any constraints. In (\u003cstrong\u003eb\u003c/strong\u003e) and (\u003cstrong\u003ed\u003c/strong\u003e) the angles of the organic ligands and the positions of Cr atoms are fixed to that in the pristine Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e and Cr(pyz)\u003csub\u003e2.\u003c/sub\u003e Positive and negative values represent charge depletion and accommodation, respectively.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/1fb4db7e4aa93e70625502c0.png"},{"id":64167853,"identity":"56dc049e-bf77-48e1-8c01-c55897aa6867","added_by":"auto","created_at":"2024-09-09 09:53:55","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":331195,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEffects of ligand rotations on local electric fields and rate-limiting barriers.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e One-dimensional LEF profiles (solid lines) around the adsorbed O\u003csub\u003e2\u003c/sub\u003e along the normal directions of the substrates, as navigated by the yellow solid lines of the insets. The yellow dashed line marks the path through which the arrow runs, representing the position of the CO molecule in the transition states shown in Fig. 5a and the Supplementary Fig. 10. The dashed lines correspond to the cases of without O\u003csub\u003e2\u003c/sub\u003e adsorption, i.e., the pristine substrates. The green shaded part indicates the zone that covers the CO molecule. The insets illustrate the two-dimensional electrostatic potential contours right above the adsorbed O\u003csub\u003e2\u003c/sub\u003e and the CO-O\u003csub\u003e2\u003c/sub\u003e species of the TS state. \u003cstrong\u003eb\u003c/strong\u003e LEF obtained with the same approach as that in (\u003cstrong\u003ea\u003c/strong\u003e), nevertheless without allowing the organic ligands rotations and upward shift of the Cr atoms, as simply termed w/o R. \u003cstrong\u003ec\u003c/strong\u003e Rate-limiting activation energy barriers (\u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e) for CO oxidation with (without) allowing the organic ligands rotations and upward shift of the Cr atoms (w/ R (w/o R)). \u0026nbsp;\u003cstrong\u003ed\u003c/strong\u003e Logarithms of reaction rate of the CO oxidation on the multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e and monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e for the cases of w/R and w/o R.\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/1fe6a809f6875d1e0c9b2d89.png"},{"id":76183700,"identity":"29f72fc2-e672-4e04-81a7-e62972658361","added_by":"auto","created_at":"2025-02-13 08:08:07","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2756151,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/7759df96-4638-4cd8-b741-6433ac23d626.pdf"},{"id":64167148,"identity":"e3b79d85-24f4-424c-a008-7dff6c3ee080","added_by":"auto","created_at":"2024-09-09 09:45:55","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":66214,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTable of Contents\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eHighly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/1b4e250d7e0fabc5d22d5a9f.png"},{"id":64167855,"identity":"c3d43fbf-fb32-422a-ab80-ab3e453c10cc","added_by":"auto","created_at":"2024-09-09 09:53:55","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":6806700,"visible":true,"origin":"","legend":"","description":"","filename":"SI.docx","url":"https://assets-eu.researchsquare.com/files/rs-4937470/v1/c522906bf212b7228b717840.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation","fulltext":[{"header":"Introduction","content":"\u003cp\u003eWith the rapid advancement of modern industry and the intensifying energy crises, the development of highly efficient catalysts has become critically important for a range of complex chemical reactions. However, most catalysts encounter complex stability issues, and their practical applications are also generally constrained by the relatively high operating temperature\u003csup\u003e1, 2\u003c/sup\u003e. The U.S. Department of Energy (US-DOE) has set the goal of achieving 90% conversion of all criteria pollutants at 150\u0026deg;C－\u0026ldquo;the 150\u0026deg;C challenge\u0026rdquo;\u003csup\u003e3\u003c/sup\u003e. Nevertheless, such a temperature is still approximately 100\u0026deg;C lower than current state-of-the-art commercial automotive catalysts. In general, charge\u003csup\u003e4\u003c/sup\u003e, spin\u003csup\u003e5\u003c/sup\u003e, orbital\u003csup\u003e6\u003c/sup\u003e, and polarity\u003csup\u003e7\u003c/sup\u003e can simultaneously play significant roles in chemical processes. Correspondingly, if a catalytic platform possesses well-matched\u0026nbsp;degrees of freedom, such as spin and polarity, with those of the reactants, high-performance selective catalysis can be achieved\u003csup\u003e8-10\u003c/sup\u003e.\u0026nbsp;Recent reports have demonstrated that high spin states of the catalysts can significantly enhance various chemical processes\u003csup\u003e8-10\u003c/sup\u003e, which can be effectively explained by Wigner\u0026rsquo;s spin selection rule\u003csup\u003e9, 11-15\u003c/sup\u003e. Moreover, recent advances have confirmed that electric field\u003csup\u003e16, 17\u003c/sup\u003e and ferroelectricity can play a crucial role in enhancing the catalytic activities, such as CO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eelectrocatalytic reduction\u003csup\u003e18\u003c/sup\u003e and photocatalytic water splitting\u003csup\u003e19\u003c/sup\u003e.\u0026nbsp;This enhancement is primarily due to the significantly improved charge transfer facilitated by ferroelectric materials\u003csup\u003e20\u003c/sup\u003e. Therefore, developing highly efficient room-temperature catalysts leveraging the synergetic effects of the aforementioned degrees of freedom is both anticipated and warranted.\u003c/p\u003e\n\u003cp\u003eMultiferroics, which simultaneously encompass ferroelectric, ferromagnetic, and ferroelastic orders, have attracted significant attention from researchers due to their promising applications in various fields\u003csup\u003e21-23\u003c/sup\u003e. These applications include nonvolatile multistate data storage, magnetoelectric sensors, multifunctional and electrically controlled spin wave devices\u003csup\u003e24, 25\u003c/sup\u003e. Moreover, due to the tunable orders and the synergies of different degrees of freedom, such as charge, spin, and orbital integrated within a single phase, it is reasonable to expect that multiferroics could serve as highly efficient room-temperature catalytic candidates. Very recently, a new type of two-dimensional (2D) multiferroic material,\u0026nbsp;\u003cem\u003ei.e.\u003c/em\u003e, a 2D metal-organic framework room-temperature multiferroicity (RT-MF), specifically Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(h-fpyz = half-fluoropyrazine)\u003csup\u003e26\u003c/sup\u003e has been predicted, with stable ferroelectricitis and ferrimagnetic phase up to around 400 and 600 K, respectively. This unique 2D material can be rationally designed by introducing relatively large ferroelectricity (4.8\u0026nbsp;\u003cem\u003e\u0026mu;\u003c/em\u003eC/cm\u003csup\u003e2\u003c/sup\u003e) through fluorination\u003csup\u003e27\u003c/sup\u003e in Cr(pyz)\u003csub\u003e2\u003c/sub\u003e, while retaining the ferromagnetic coupling (3.61\u0026nbsp;\u003cem\u003e\u0026mu;\u003c/em\u003eB/Cr) between the evenly dispersed metal ions. Essentially, this 2D RT-MF structure can be understood as a derivative of the experimentally fabricated bulk metal-organic ferrimagnetic layered material\u003csup\u003e28\u003c/sup\u003e, exhibiting a high Curie critical temperature of up to 515 K and significant coercivity (7500 Oersted) at room-temperature.\u0026nbsp;Moreover, from geometric perspective, the present 2D RT-MF\u0026nbsp;Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003estructure, featuring evenly dispersed Cr species in single-atomic form stabilized by surrounding organic ligands, represents a promising candidate for high-loading single-atomic catalyst (SAC). SAC represents an\u0026nbsp;important enabling concept\u003csup\u003e29\u003c/sup\u003e and has been intensively exploited in the broad field of chemical catalysis, such as CO\u003csub\u003e2\u003c/sub\u003e reduction\u003csup\u003e30\u003c/sup\u003e, CO oxidation\u003csup\u003e31, 32\u003c/sup\u003e, O\u003csub\u003e2\u003c/sub\u003e reduction\u003csup\u003e33\u003c/sup\u003e, N\u003csub\u003e2\u003c/sub\u003e reduction\u003csup\u003e34\u003c/sup\u003e, hydrogen evolution reaction\u003csup\u003e35\u003c/sup\u003e, and oxygen evolution reaction\u003csup\u003e36\u003c/sup\u003e. Furthermore, by probing the interactions between the single-atom reactive sites and the reactants, multiple potential physical mechanisms have been established from various perspectives.\u0026nbsp;For example, insights from the aspects of geometric flexibility\u003csup\u003e37, 38\u003c/sup\u003e, charge transfer\u003csup\u003e39, 40\u003c/sup\u003e, orbital hybridizations\u003csup\u003e41, 42\u003c/sup\u003e, and spin selection\u003csup\u003e43, 44\u003c/sup\u003e have been proposed.\u0026nbsp;However, in these related investigations, the materials used as SAC platforms typically exhibit only one type of ferroic order, such as ferromagnetism\u003csup\u003e45, 46\u003c/sup\u003e, or ferroelectricity\u003csup\u003e47, 48\u003c/sup\u003e.\u0026nbsp;To date, despite extensive research on the distinctive physical properties of both 2D multiferroic materials\u003csup\u003e49-51\u003c/sup\u003e, and the catalysis of numerous SAC systems\u003csup\u003e6, 29\u003c/sup\u003e, the synergetic effect of these aspects on the room-temperature catalytic performance of 2D RT-MF SAC structures, such as\u0026nbsp;Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, remains significantly underexplored.\u003c/p\u003e\n\u003cp\u003eHere, employing state-of-the-art first-principles calculations and model analysis, taking spin-triplet O\u003csub\u003e2\u003c/sub\u003e activation and polar molecule CO oxidation as a prototypical example, we demonstrate that the present 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e can serve as a highly efficient SAC candidate operating at room-temperature. The calculated rate-limiting energy barrier is approximately 0.33 eV,\u0026nbsp;resulting in a reaction rate\u0026nbsp;of\u0026nbsp;2.86\u0026times;10\u003csup\u003e6\u003c/sup\u003e s\u003csup\u003e\u0026minus;1\u003c/sup\u003e. This rate is five orders of magnitude higher than its monoferroic derivative [Cr(pyz)\u003csub\u003e2\u003c/sub\u003e] counterpart, due to the synergetic effects of\u0026nbsp;magnetism and ferroelectricity. Specifically, the flexible rotation of the organic ligand in the multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e functions as a controllable knob, enhancing the charge transfer and spin accommodation during the activation of spin-triplet O\u003csub\u003e2\u003c/sub\u003e molecule, while simultaneously lowering the local normal positive electric field. This\u0026nbsp;synergetic mechanism results in the\u0026nbsp;polar CO molecule experiencing relatively low repulsive electrostatic interactions and a significantly reduced reaction barrier,\u0026nbsp;making the 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e a promising candidate for a room-temperature SAC system. Beyond their various applications due to the exotic physical properties, the present findings significantly broaden the potential applications of 2D multiferroics in the crucial field of chemical catalysis. Moreover, this work may direct new avenue towards developing highly efficient SAC platforms for various other important chemical processes where multiple degrees of freedom, such as spin and polarity, synergistically matter.\u003c/p\u003e"},{"header":"Results","content":"\u003cp\u003e\u003cstrong\u003eGeometric and electronic structures of the 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003cstrong\u003e\u003csub\u003e.\u0026nbsp;\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFirst, we briefly reexamined the optimized geometric structure of the 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e26\u003c/sup\u003e metal-organic framework, simulated within a unit cell comprising four Cr metal atoms and eight h-fpyz organic ligands. Here, four of the latter are connected to the central Cr atoms in a clockwise manner (Fig. 1a). Our extensive spin-polarized density-functional theory (DFT) calculations confirmed that in the 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e structure, Cr ions exhibit a preference for ferromagnetic order over antiferromagnetic order by about 0.25 eV/f.u., consistent with prior research findings\u003csup\u003e26\u003c/sup\u003e. Moreover, the calculated magnetic moment (MM) of each four-coordinated Cr ion is about 3.68 \u003cem\u003e\u0026mu;\u003c/em\u003eB, which is antiparallel to that of its four adjacent h-fpyz ligand molecules, each possessing a MM of 0.84 \u003cem\u003e\u0026mu;\u003c/em\u003eB. Thus, the ground state of 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e is ferrimagnetic, with a total MM of approximately 8.0 \u003cem\u003e\u0026mu;\u003c/em\u003eB per primitive unit cell. Furthermore, it has been identified that the 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e system exhibits an antiferroelectric (AFE) state, due to the antiparallel arrangements of the eight h-fpyz ligand molecles in the primitive cell (Fig. 1b). Fig. 1c shows the side view of Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e. The spin-polarized band structure and density of states (DOS) (Fig. 1d) demonstrate a direct energy band gap of approximately 0.55 eV, which aligns with previous DFT calculations\u003csup\u003e26\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eActivation of spin-triplet O\u003csub\u003e2\u003c/sub\u003e on 2D Cr(h-fpyz)\u003csub\u003e2.\u0026nbsp;\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSubsequently, we investigate the adsorption and activation of spin-triplet O\u003csub\u003e2\u003c/sub\u003e on 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, which is the key step for CO oxidation. It is revealed that the O\u003csub\u003e2\u003c/sub\u003e molecule preferentially adsorbs on the Cr\u003csub\u003eI\u003c/sub\u003e site, with an adsorption energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e) of 1.10 eV. This adsorption is accompanied by a significant increase in the O-O bond length from 1.24 to 1.44 \u0026Aring; (Fig. 1e). Here, we define E\u003csub\u003eads\u0026nbsp;\u003c/sub\u003e=\u0026nbsp;－\u0026nbsp;[E(O\u003csub\u003e2\u003c/sub\u003e － Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e)\u0026nbsp;－\u0026nbsp;E(O\u003csub\u003e2\u003c/sub\u003e)\u0026nbsp;－\u0026nbsp;E(Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e)]. On Cr\u003csub\u003eII\u003c/sub\u003e and Cr\u003csub\u003eIII\u003c/sub\u003e, the calculated E\u003csub\u003eads\u003c/sub\u003e are relatively low, 0.68 and 0.36 eV, respectively. These distinct adsorption behaviors at the three different sites can be attributed to the contrasting local geometric environments of the antiferroelectric state in the 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e structure. Specifically, on Cr\u003csub\u003eI\u003c/sub\u003e, Cr\u003csub\u003eII\u003c/sub\u003e, and Cr\u003csub\u003eIII\u003c/sub\u003e, the adsorbed O\u003csub\u003e2\u003c/sub\u003e is surrounded by four H atoms, two H and two F atoms, and four F atoms of the four organic ligands, respectively (Supplementary S1). In other words, the incoming O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003emolecule may experience disparate local electric field (LEF) nearby (~ 3 \u0026Aring;) above the Cr\u003csub\u003eI\u003c/sub\u003e and Cr\u003csub\u003eIII\u003c/sub\u003e atoms, as demonstrated (Figs. 2a, d). This directly influences the charge transfer, as discussed shortly, and accounts for the distinct activities of these two types of Cr single-atom reactive sites. These findings strongly indicate that the catalysis of ferroelectric materials\u003csup\u003e25-28\u0026nbsp;\u003c/sup\u003ecan be effectively modulated by the ferroelectric polarization direction down to the single-atom scale, specifically in SAC systems. Note that, here the spin-orbit coupling (SOC) effect has a negligible influence on O\u003csub\u003e2\u003c/sub\u003e adsorption and activation. Therefore, the subsequent calculations were performed without considering SOC.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eSecond, we conduct Bader charge analysis to examine the charge transfer (\u0026Delta;\u0026rho; = \u0026rho;(O\u003csub\u003e2\u003c/sub\u003e-Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e)\u0026nbsp;－\u0026nbsp;\u0026rho;(O\u003csub\u003e2\u003c/sub\u003e)\u0026nbsp;－\u0026nbsp;\u0026rho;(Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e)) between the incoming O\u003csub\u003e2\u003c/sub\u003e and the Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e catalytic substrate. Here, \u0026rho;(O\u003csub\u003e2\u003c/sub\u003e) and \u0026rho;(Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e) represent the calculated charge obtained from the isolated ground-state O\u003csub\u003e2\u003c/sub\u003e molecule and the 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e substrate, respectively. To gain a clearer understanding of the charge transfer, we conducted a Bader charge analysis on the 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e substrate (Supplementary Fig. 2). Briefly, in this pristine 2D RM-MF, both nitrogen (N) and fluorine (F) atoms accommodate charge transferred predominantly from their neighboring chromium (Cr) atoms, amounting to approximately 1.3 |e|, as well as from carbon (C) atoms. Here, C atoms can be classified into two types, which are coordinated by H and F atoms, termed C\u003csub\u003eH\u003c/sub\u003e and C\u003csub\u003eF\u003c/sub\u003e, respectively. The nearest neighboring C\u003csub\u003eH\u003c/sub\u003e and C\u003csub\u003eF\u003c/sub\u003e of Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eII\u003c/sub\u003e) donate about 0.46 (0.36) and 1.09 (0.99) |e|, respectively. Note that, when the incoming O\u003csub\u003e2\u003c/sub\u003e molecule is positioned more than 10 \u0026Aring; above the designated Cr\u003csub\u003eI\u0026nbsp;\u003c/sub\u003eactive site, as termed the initial state (IS), negligible charge transfer is observed between O\u003csub\u003e2\u003c/sub\u003e and the substrate (Supplementary Fig. 3). Upon O\u003csub\u003e2\u003c/sub\u003e adsorption on the reactive Cr\u003csub\u003eI\u0026nbsp;\u003c/sub\u003e(Cr\u003csub\u003eIII\u003c/sub\u003e) hosting site, approximately 1.02 (0.79) |e| is transferred from the substrate to O\u003csub\u003e2\u003c/sub\u003e respectively (Fig. 2b, e). Such a distinct charge transfer between Cr\u003csub\u003eI\u003c/sub\u003e and Cr\u003csub\u003eIII\u003c/sub\u003e accounts for their contrasting catalytic behaviors in CO oxidation, as discussed later. In this process, the reactive Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eIII\u003c/sub\u003e) atom, along with the remaining C, H, and F (C, N, and F) atoms donate electrons by approximately 0.23, 0.69, 0.31, and 0.06 |e| (0.21, 0.39, 0.16, and 0.08 |e|), respectively. Furthermore, Cr\u003csub\u003eII\u003c/sub\u003e and Cr\u003csub\u003eIII\u003c/sub\u003e (C\u003csub\u003eI\u003c/sub\u003e and Cr\u003csub\u003eII\u003c/sub\u003e) which positioned approximately 7.02 and 9.92 \u0026Aring; (9.92 and 7.02 \u0026Aring;) away from Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eIII\u003c/sub\u003e), respectively contribute negligible charge transfer to the adsorbed O\u003csub\u003e2\u003c/sub\u003e. It is noteworthy that, although the Cr\u003csub\u003eI\u003c/sub\u003e reactive site is directly linked by the N atom of the h-fpyz ligand, the second nearest neighboring C atoms of Cr\u003csub\u003eI\u003c/sub\u003e, in another word, the nearest neighboring C atoms of Cr\u003csub\u003eII\u003c/sub\u003e, dominate the charge transfer to the adsorbed O\u003csub\u003e2\u003c/sub\u003e (Supplementary Fig. 4). Additionally, due to the significantly lower electronegativity of H than that of F, the nearby H atoms donate significantly more charge to the adsorbed O\u003csub\u003e2\u003c/sub\u003e species than F atoms. This further rationalizes the contrasting \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e of the O\u003csub\u003e2\u003c/sub\u003e on Cr\u003csub\u003eI\u003c/sub\u003e, Cr\u003csub\u003eII\u003c/sub\u003e, and Cr\u003csub\u003eIII\u003c/sub\u003e sites.\u003c/p\u003e\n\u003cp\u003eIn contrast to charge transfer, the reactive Cr\u003csub\u003eI\u003c/sub\u003e atom, along with the substrate N, and C atoms, play a crucial synergetic role in accommodating the spin transferred from the adsorbed O\u003csub\u003e2\u003c/sub\u003e molecule. This facilitates its spin triplet-to-singlet activation of the O\u003csub\u003e2\u003c/sub\u003e molecule, which is the key step for CO oxidation. Similar to the definition of charge transfer \u0026Delta;\u0026rho;, here we define the magnetic moment transfer as \u0026Delta;M = M(O\u003csub\u003e2\u003c/sub\u003e \u0026minus; Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e) \u0026minus; M(O\u003csub\u003e2\u003c/sub\u003e) \u0026minus; M(Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e).The initial state (IS) primarily reflects the intrinsic magnetic moment of the incoming spin-triplet O\u003csub\u003e2\u003c/sub\u003e molecule and the substrate (Supplementary Fig. 3b), with negligible interactions between them. Upon O\u003csub\u003e2\u003c/sub\u003e adsorption, the total magnetic moment of the optimized O\u003csub\u003e2\u003c/sub\u003e-Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e complex remains at 8 \u003cem\u003e\u0026mu;\u003c/em\u003eB (spin quantum number\u0026nbsp;\u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e\u003csub\u003e-Cr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003e= 4). That is, the spin\u0026minus;spin coupling between the spin-triplet O\u003csub\u003e2\u003c/sub\u003e molecule (\u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e = 1) and the Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e catalyst (\u003cem\u003eS\u003c/em\u003e\u003csub\u003eCr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e = 4) follows the channel of \u0026ldquo;1 + 4 = 4\u0026rdquo;, which is a spin-allowed reaction according to Wigner\u0026rsquo;s spin selection rule\u003csup\u003e9, 11-15\u003c/sup\u003e. Such a classic rule restricts that the total spin quantum number\u0026nbsp;\u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e\u003csub\u003e-Cr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e in the spin-allowed reaction should satisfy \u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e\u003csub\u003e-Cr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e = |\u003cem\u003eS\u003c/em\u003e\u003csub\u003eCr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e \u0026minus; \u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e|, |\u003cem\u003eS\u003c/em\u003e\u003csub\u003eCr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e \u0026minus; \u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e|+1, ..., |\u003cem\u003eS\u003c/em\u003e\u003csub\u003eCr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e + \u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e|, where\u0026nbsp;\u003cem\u003eS\u003c/em\u003e\u003csub\u003eCr(h-fpyz)\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e and \u003cem\u003eS\u003c/em\u003e\u003csub\u003eO\u003c/sub\u003e\u003csub\u003e2\u003c/sub\u003e are the spin quantum numbers of the substrate Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e and an isolated ground state O\u003csub\u003e2\u003c/sub\u003e molecule, respectively.\u003c/p\u003e\n\u003cp\u003eHowever, the local spin moment of the optimized O\u003csub\u003e2\u003c/sub\u003e-Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e complex with O\u003csub\u003e2\u003c/sub\u003e adsorbed on Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eIII\u003c/sub\u003e) reactive stie changes intriguingly, as shown in Fig. 2c (f). Specifically, the magnetic moment of the adsorbed O\u003csub\u003e2\u003c/sub\u003e on Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eIII\u003c/sub\u003e) is reduced from 2.0 \u003cem\u003e\u0026mu;\u003c/em\u003eB to nearly zero, i.e., \u003cstrong\u003e-\u003c/strong\u003e0.24 (\u003cstrong\u003e-\u003c/strong\u003e0.02) \u003cem\u003e\u0026mu;\u003c/em\u003eB, indicating that the O\u003csub\u003e2\u003c/sub\u003e molecule has transitioned from a spin triplet state to singlet. Correspondingly, the magnetic moment of the Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eIII\u003c/sub\u003e) atom is reduced from 3.68 (3.69) to 3.01 (3.08) \u003cem\u003e\u0026mu;\u003c/em\u003eB, with a reduction of 0.67 (0.61) \u003cem\u003e\u0026mu;\u003c/em\u003eB. Somewhat unexpectedly, the nearby non-metal atoms, such as C and N, in the vicinity of the reactive Cr\u003csub\u003eI\u003c/sub\u003e (Cr\u003csub\u003eIII\u003c/sub\u003e) atom primarily accommodate the magnetic moments by 0.83 (0.60) \u003cem\u003e\u0026mu;\u003c/em\u003eB. However, the relatively distant transitional metal atoms, Cr\u003csub\u003eII\u003c/sub\u003e and Cr\u003csub\u003eIII\u003c/sub\u003e (Cr\u003csub\u003eI\u003c/sub\u003e and Cr\u003csub\u003eII\u003c/sub\u003e) only accommodate about 0.02(0.03) \u003cem\u003e\u0026micro;\u003c/em\u003e\u003csub\u003eB\u003c/sub\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003eupon O\u003csub\u003e2\u003c/sub\u003e adsorption and activation. These results demonstrate a significant synergetic spin communication mechanism among the O\u003csub\u003e2\u003c/sub\u003e molecules, the substrate \u003cem\u003ep\u003c/em\u003e-block C/N atoms, and the\u003cem\u003e\u0026nbsp;d\u003c/em\u003e-block Cr reactive site in activation of spin-triplet O\u003csub\u003e2\u003c/sub\u003e. Collectively, comparing the cases of O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eadsorption on Cr\u003csub\u003eI\u003c/sub\u003e and Cr\u003csub\u003eIII\u003c/sub\u003e, it is evident that the reactivity of the Cr atom increases with the synergy of charge transfer and spin communication involving the \u003cem\u003ep\u003c/em\u003e-block C/N atoms. According to Wigner\u0026rsquo;s spin selection rule, catalytic system in a low spin state (\u003cem\u003eS\u003c/em\u003e=0) typically exhibits high inertness towards spin-triplet O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e13, 14\u003c/sup\u003e. This observation convincingly demonstrates the crucial role of the magnetic order of the 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e in facilitating the activation of ground state O\u003csub\u003e2\u003c/sub\u003e molecule.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCO oxidation on 2D Cr(h-fpyz)\u003csub\u003e2.\u0026nbsp;\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNow, we continue to examine the minimum energy pathway (MEP) of CO oxidation on 2D Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e (step\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003ei,\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eFig. 3) via interacting with the adsorbed O\u003csub\u003e2\u003c/sub\u003e molecule (step\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eii,\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eFig. 3). Note that, here we have also verified the CO adsorption on the pristine Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, and the optimized \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e(CO) is merely about 0.37 eV, which is much lower than that of \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e(O\u003csub\u003e2\u003c/sub\u003e)=1.10 eV. Therefore, for the present system, CO oxidation should prefer the E-R reaction mechanism with O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003epreferentially adsorbed. It is observed that, the adsorbed O\u003csub\u003e2\u003c/sub\u003e molecule is readily attacked by the incoming CO, releasing a CO\u003csub\u003e2\u003c/sub\u003e molecule upon overcoming a low activation energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e) of 0.33 eV (TS\u003csub\u003e1\u003c/sub\u003e, Fig. 3), with an exothermic energy of 2.80 eV. In TS\u003csub\u003e1\u003c/sub\u003e, the distance between CO and O is 2.0 \u0026Aring;. Following the release of the generated CO\u003csub\u003e2\u003c/sub\u003e molecule, an O species is left on the Cr\u003csub\u003eI\u0026nbsp;\u003c/sub\u003esite (step iv, Fig. 3). Consequently, the second incoming CO can also smoothly react with the protruding O atom, generating another CO\u003csub\u003e2\u003c/sub\u003e precursor with an exothermic energy of 2.45 eV after overcoming an even lower \u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e of 0.30 eV (TS\u003csub\u003e2\u003c/sub\u003e, Fig. 3). Further calculations demonstrate that the desorption energy of the second CO\u003csub\u003e2\u003c/sub\u003e (step vi, Fig. 3) is fairly low, approximately 0.2 eV. Correspondingly, the low rate-limiting energy barrier of 0.33 eV results in a high reaction rate of about 2.86\u0026times;10\u003csup\u003e6\u0026nbsp;\u003c/sup\u003es\u003csup\u003e\u0026minus;1\u003c/sup\u003e at room-temperature (300 K), as estimated by using the Arrhenius form (R = R\u003csub\u003e0\u003c/sub\u003e\u0026times;exp[\u0026minus;\u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e/(k\u003csub\u003eB\u003c/sub\u003eT)]) with a typical prefactor R\u003csub\u003e0\u003c/sub\u003e of 10\u003csup\u003e12\u003c/sup\u003e s\u003csup\u003e\u0026minus;1\u003c/sup\u003e. Such a low rate-limiting \u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e of 0.33 eV is significantly lower than those obtained for various other typical high-efficient noble SAC or nanocluster-based catalytic complexes, e.g., 0.79 eV for Pt\u003csub\u003e1\u003c/sub\u003e/FeO\u003cem\u003e\u003csub\u003ex\u003c/sub\u003e\u003c/em\u003e\u003csup\u003e29\u003c/sup\u003e, 0.91 eV for Pt\u003csub\u003e1\u003c/sub\u003e/Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e52\u003c/sup\u003e,\u003csub\u003e\u0026nbsp;\u003c/sub\u003e0.56 eV for Pt\u003csub\u003e1\u003c/sub\u003e/CeO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e53\u003c/sup\u003e, 1.1 eV for Ir\u003csub\u003e1\u003c/sub\u003e-on-MgAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e54\u003c/sup\u003e, 0.66 eV for Pt\u003csub\u003e4\u003c/sub\u003e/CoNi@C\u003csup\u003e55\u003c/sup\u003e, and 1.71 eV for Pt-carbonyl\u003csup\u003e56\u003c/sup\u003e,\u0026nbsp;respectively. Moreover, the calculated R (\u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e=0.33 eV) reaches 1.17\u0026times;10\u003csup\u003e8\u003c/sup\u003e s\u003csup\u003e-1\u003c/sup\u003e at 423 K, implying that the present 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e is a promising high-performance catalyst subject to \u0026ldquo;the\u0026nbsp;150\u0026deg;C challenge\u0026rdquo;.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;As a comparison, we have also examined CO oxidation via interacting with the adsorbed O\u003csub\u003e2\u003c/sub\u003e on Cr\u003csub\u003eIII\u003c/sub\u003e single-atom reactive site (Supplementary Fig. 5). Briefly, the high rate-limiting \u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e of about 1.0 eV results in a low reaction rate of about 1.59\u0026times;10\u003csup\u003e-5\u0026nbsp;\u003c/sup\u003es\u003csup\u003e\u0026minus;1\u003c/sup\u003e at room-temperature. Specifically, compared to Cr\u003csub\u003eI\u003c/sub\u003e, reversing the LEF direction around the Cr\u003csub\u003eIII\u003c/sub\u003e single-atom reactive site significantly (Fig. 2a, d) reduces the reaction rate, by approximately eleven orders of amplitude. In other words, an on-off switching for the room-temperature catalysis of SAC can be achieved by tuning the polar direction of the 2D RM-MF Cr(h-fpyz)\u003csub\u003e2.\u003c/sub\u003e\u003c/p\u003e\n\u003cp\u003eFig. 4a presents the Bader charge analysis for the key steps in CO oxidation depicted (Fig. 3). When CO is weakly adsorbed on the vicinity of the adsorbed O\u003csub\u003e2\u003c/sub\u003e (step iii, Fig. 3), the O\u003csub\u003e2\u003c/sub\u003e-CO species acquires a charge of approximately 1.04 |e|. Specifically, the non-metal atoms in the substrate contribute about 0.81 |e|, whereas the metal Cr atoms contribute only about 0.23 |e|, indicating that the non-metal atoms dominate the charge transfer. This trend is also observed in TS\u003csub\u003e1\u003c/sub\u003e and all other representative steps up to TS\u003csub\u003e2\u003c/sub\u003e (Fig. 3), as also demonstrated in Fig. 4a and Supplementary Fig. 6a.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe changes in the magnetic moment (\u0026Delta;M) of the corresponding key steps. From step iii to step vi (Fig. 4b), there are substantial reductions in the local magnetic moments of both the O\u003csub\u003e2\u003c/sub\u003e-CO species and the Cr metal atoms. Notably, as in step iii, in almost all the other key steps, the \u003cem\u003ep\u003c/em\u003e-block non-metal C and N atoms accommodate more MM than that of the \u003cem\u003ed\u003c/em\u003e-block Cr reactive atom (Supplementary Fig. 6b). These findings demonstrate a delicate synergetic charge and spin accommodation mechanism occurred among the O\u003csub\u003e2\u003c/sub\u003e/CO molecule, \u003cem\u003ed\u003c/em\u003e-block reactive Cr atom, and the surrounding \u003cem\u003ep\u003c/em\u003e-block C and N atoms, occurring during both O\u003csub\u003e2\u003c/sub\u003e activation and CO oxidation on the multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003ecatalytic platform.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eComparison of CO oxidation on monoferroic Cr(pyz)\u003csub\u003e2.\u0026nbsp;\u003c/sub\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo more clearly demonstrate the crucial role of the multiferroic orders in high-performance CO oxidation, we conducted a comparative examination of O\u003csub\u003e2\u003c/sub\u003e activation and CO oxidation on Cr(pyz)\u003csub\u003e2\u003c/sub\u003e (pyz = pyrazine). This compound was created by substituting all the F atoms in Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e with H atoms (Supplementary Fig. 7a, b). Consequently, the substrate undergoes a transition from multiferroic to monoferroic, remaining only ferrimagnetic properties. Based on this, we further explored the adsorption of O\u003csub\u003e2\u003c/sub\u003e on the monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e substrate (Supplementary Fig. 7c). In comparison to the adsorption on the Cr\u003csub\u003eI\u003c/sub\u003e reactive site of multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, the optimized \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e(O\u003csub\u003e2\u003c/sub\u003e) increases slightly by 0.03 eV to reach 1.13 eV. Additionally, the O-O bond length is enlarged to 1.44 \u0026Aring;. Similarly, CO exhibits weak adsorption on the Cr atom, characterized by an \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e(CO) of 0.38 eV, suggesting that only an E-R mechanism is viable for CO oxidation.\u0026nbsp;Surprisingly, despite comparable activation of O\u003csub\u003e2\u003c/sub\u003e on both catalytic platforms in terms of bond length and adsorption energy, a significantly elevated rate-limiting \u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u003c/sub\u003e of 0.65 eV is observed for CO oxidation on the monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e (Supplementary Fig. 8). Using the same approach, the calculated CO oxidation rate is 1.20\u0026times;10\u003csup\u003e1\u003c/sup\u003e s\u003csup\u003e-1\u003c/sup\u003e, which\u0026nbsp;is about five orders of magnitude lower than that observed on the\u0026nbsp;2D RM-MF Cr(h-pyz)\u003csub\u003e2\u003c/sub\u003e at the room temperature. These findings further underscore the pivotal role of multiferroicity in enhancing the catalytic performance of the present 2D material for CO oxidation.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eRole of Ligand Rotation in LEF: A knob for on-off switching room-temperature catalysis\u003c/strong\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTo further elucidate the observed phenomena, we conducted a comparative analysis of the local geometric structures around the Cr reactive site in\u0026nbsp;multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e, both with and without O\u003csub\u003e2\u003c/sub\u003e adsorption (Fig. 5). Initially, in the case of\u0026nbsp;2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, prior to O\u003csub\u003e2\u003c/sub\u003e adsorption, each of the four h-fpyz ligands surrounding the Cr reactive site tilts approximately 37.8\u0026deg;\u0026nbsp;away from the (100) plane (Fig. 5a) or the (010) plane (Fig. 5b).\u0026nbsp;However, upon O\u003csub\u003e2\u003c/sub\u003e adsorption, the angles undergo symmetry-breaking evolution into two distinct classes. Specifically, the angles between the two h-fpyz rings connecting the reactive Cr atoms along [010] ([100]) direction and the (100) ((010)) plane are significantly reduced (slightly enlarged) from\u0026nbsp;37.8\u0026deg; to\u0026nbsp;19.3\u0026deg; (37.8\u0026deg; to\u0026nbsp;38.5\u0026deg;), (Fig. 5a, b).\u0026nbsp;This change in orientation can be attributed in part to the electrostatic attractive interactions between the negatively charged O\u003csub\u003e2\u003c/sub\u003e and the nearby H cations.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eMeanwhile, as illustrated in the corresponding lower panels, the position of the reactive Cr atom undergoes spontaneous changes along the [001] direction relative to the pristine Cr(h-pyz)\u003csub\u003e2\u003c/sub\u003e substrate. Specifically, the Cr atom shifts upward, displaying significant displacements relative to the mass centers of N atom along the [010] and [100] directions (Fig. 5a, b). For instance, following O\u003csub\u003e2\u003c/sub\u003e adsorption (structure ii), the Cr atoms shifted modestly (considerably) upward by approximately 0.24 (0.81) \u0026Aring;. Similar contrasting phenomena are also observed during other critical stages of the CO oxidation process, including TS\u003csub\u003e1\u003c/sub\u003e, iv, TS\u003csub\u003e2\u003c/sub\u003e, and vi (Supplementary Fig. 9). Furthermore, qualitatively similar findings are confirmed for O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eadsorption and CO oxidation on the\u0026nbsp;monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e.\u0026nbsp;Specifically,\u0026nbsp;the angles (about 47.5\u0026deg;)\u0026nbsp;with respect to\u0026nbsp;(100) ((010)) plane\u0026nbsp;are slightly reduced (enlarged) to 33.6\u0026deg; (47.8\u0026deg;) (Fig. 5c-d).\u0026nbsp;Meanwhile, the Cr reactive site exhibits modest (considerable) upward shifts along the [010] (0.22 \u0026Aring;) and [100] (0.76 \u0026Aring;) direction.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eHowever, quantitatively, the changes in relative angles of the organic ligands during the key steps of the CO oxidation on the\u0026nbsp;multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e are more pronounced compared to those observed in the monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e system. For instance, in the TS\u003csub\u003e1\u003c/sub\u003e state, the angle change reaches approximately 51.3 % (from 37.8\u0026deg; to 18.4\u0026deg;) for Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, whereas it is about 39.2 % (from 47.5\u0026deg; to\u0026nbsp;28.9\u0026deg;)\u0026nbsp;for Cr(pyz)\u003csub\u003e2\u003c/sub\u003e. Simultaneously, the upward shift of the Cr reactive site is more significant in Cr(pyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(0.90\u0026nbsp;\u0026Aring;) than in Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e (0.82 \u0026Aring;), which may correspond to the relatively higher \u003cem\u003eE\u003c/em\u003e\u003csub\u003ebar\u0026nbsp;\u003c/sub\u003eof the monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e (0.65 eV) compared to multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(0.33 eV). This difference is attributed to the relatively large energy cost associated with the upward shift of the Cr atom compared to the rotation of the organic ligands (Supplementary Fig. 9). \u0026nbsp;\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe rotations of the organic ligands and the upward shift of the Cr reactive site effectively promote charge transfer from the substrate, specifically involving nearby \u003cem\u003ep\u003c/em\u003e-block elements H and C, and \u003cem\u003ed\u003c/em\u003e-block Cr atoms, to the O\u003csub\u003e2\u003c/sub\u003e molecule (Fig. 6). To investigate this phenomenon, we performed Bader charge analysis on the optimized structures of O\u003csub\u003e2\u003c/sub\u003e adsorption on both 2D multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e systems, considering scenarios with and without allowing the rotations of the organic ligands and the accompanied upward shifts of the Cr atom. Specifically, when an O\u003csub\u003e2\u003c/sub\u003e molecule adsorbs freely on multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, the O\u003csub\u003e2\u003c/sub\u003e species acquires a charge of approximately 1.02 |e|, with the underlying Cr reactive site and the nearby H atoms donating about 0.23 |e| and 0.11 |e| per H atom, respectively\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e(Fig. 6a). However, for the case of without rotation of the organic ligands and the accompanied upward shift of the Cr atom, the charge on the adsorbed O\u003csub\u003e2\u003c/sub\u003e molecule decreases to about 0.70 |e|, with the reactive Cr atom and the nearby H atoms at relatively greater distances donating about 0.09 |e| and 0.08 |e| per H atom, respectively (Fig. 6b). A similar trend is also evident in the case of O\u003csub\u003e2\u003c/sub\u003e adsorption on the monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e (Fig. 6c, d). Moreover, the contrasting geometric structure changes between the multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e systems upon O\u003csub\u003e2\u003c/sub\u003e adsorption results in quantitively distinct charge transfers and spin accommodations between the O\u003csub\u003e2\u003c/sub\u003e molecule and the substrate atoms. Importantly, such disparate charge transfers upon O\u003csub\u003e2\u003c/sub\u003e adsorptions result in distinct LEF surrounding the O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003especies, which are destined to significantly influence the oxidation of the polar molecule CO, as confirmed in the following section.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe rotations of the organic ligands and the upward shift of the Cr reactive site effectively promote charge transfer from the substrate, specifically involving nearby \u003cem\u003ep\u003c/em\u003e-block elements H and C, and \u003cem\u003ed\u003c/em\u003e-block Cr atoms, to the O\u003csub\u003e2\u003c/sub\u003e molecule (Fig. 6). To investigate this phenomenon, we performed Bader charge analysis on the optimized structures of O\u003csub\u003e2\u003c/sub\u003e adsorption on both 2D\u0026nbsp;multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e systems, considering scenarios with and without allowing the rotations of the organic ligands and the accompanied upward shifts of the Cr atom. Specifically, when an O\u003csub\u003e2\u003c/sub\u003e molecule adsorbs freely on multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, the O\u003csub\u003e2\u003c/sub\u003e species acquires a charge of approximately 1.02 |e|, with the underlying Cr reactive site and the nearby H atoms donating about 0.23 |e| and 0.11 |e| per H atom, respectively\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003e(Fig. 6a). However, for the case of without rotation of the organic ligands and the accompanied upward shift of the Cr atom, the charge on the adsorbed O\u003csub\u003e2\u003c/sub\u003e molecule decreases to about 0.70 |e|, with the reactive Cr atom and the nearby H atoms at relatively greater distances donating about 0.09 |e| and 0.08 |e| per H atom, respectively (Fig. 6b). A similar trend is also evident in the case of O\u003csub\u003e2\u003c/sub\u003e adsorption on the monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e (Fig. 6c, d). Moreover,\u0026nbsp;the contrasting geometric structure changes between the\u0026nbsp;multiferroic Cr(h-fpyz)\u003csub\u003e2\u0026nbsp;\u003c/sub\u003eand monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e systems\u0026nbsp;upon O\u003csub\u003e2\u003c/sub\u003e adsorption\u0026nbsp;results in quantitively distinct charge transfers and spin accommodations between the O\u003csub\u003e2\u003c/sub\u003e molecule and the substrate atoms. Importantly, such disparate charge transfers upon O\u003csub\u003e2\u003c/sub\u003e adsorptions result in distinct LEF surrounding the O\u003csub\u003e2\u0026nbsp;\u003c/sub\u003especies, which are destined to significantly influence the oxidation of the polar molecule CO, as confirmed in the following section.\u0026nbsp;\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eEmploying first-principles calculations based on density functional theory, we have demonstrated for the first time that the 2D multiferroic structure of Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e functions effectively as a room-temperature single-atom catalyst. This is evidenced by its highly enhanced catalytic activity, highlighted by the following key findings:\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e(i)\u0026nbsp;The calculated rate-limiting energy barrier for CO oxidation on the Cr single-atom reactive site within the 2D multiferroic catalytic platform is approximately 0.33 eV,\u0026nbsp;resulting in a reaction rate\u0026nbsp;of\u0026nbsp;2.86\u0026times;10\u003csup\u003e6\u0026nbsp;\u003c/sup\u003es\u003csup\u003e\u0026minus;1\u003c/sup\u003e at room temperature and 1.17\u0026times;10\u003csup\u003e8\u003c/sup\u003e s\u003csup\u003e-1\u003c/sup\u003e at 423 K, respectively, implying that the present 2D RM-MF Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e is a promising high-performance catalytic candidate subject to \u0026ldquo;the 150\u0026deg;C challenge\u0026rdquo; of US-DOE.\u0026nbsp;\u0026nbsp;This rate is five orders of magnitude higher than its monoferroic derivative, [Cr(pyz)\u003csub\u003e2\u003c/sub\u003e]. Moreover, reversing the polar direction (rotating the organic ligands) of the\u0026nbsp;2D multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e structure reduces the reaction rate by eleven (eight) orders of the magnitude, enabling on-off switching of room-temperature catalysis of the 2D multiferroic system.\u003c/p\u003e\n\u003cp\u003e(ii) The underlying microscopic mechanism involves\u0026nbsp;the activation of spin-triplet O\u003csub\u003e2\u003c/sub\u003e molecule, facilitated by more flexible rotations of the organic ligand around the Cr single-atom reactive site within the multiferroic\u0026nbsp;Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e complex compared to its monoferroic Cr(pyz)\u003csub\u003e2\u003c/sub\u003e derivative. This flexibility enhances the charge transfer and spin-accommodation processes, predominantly influenced by spin-polarized\u003cem\u003e\u0026nbsp;p\u003c/em\u003e-block substrate atoms and the confined \u003cem\u003ed\u003c/em\u003e-block Cr single-atom reactive site.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e(iii) Intriguingly, on the multiferroic Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, O\u003csub\u003e2\u003c/sub\u003e adsorption induces a significantly lower local positive electric field normal to the surface compared to the Cr(pyz)\u003csub\u003e2\u003c/sub\u003e, as supported by a simple point-charge model calculation. Consequently, the polar CO molecule experiences reduced repulsive electrostatic interactions and a considerably lower reaction energy barrier. Further simulations confirm that, without allowing the rotations of the organic ligands, the CO oxidation rate is dramatically reduced due to an increased rate-limiting energy barrier, by at least eight orders of magnitude.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe present findings are expected to offer new insights into establishing highly efficient single-atom catalyst platforms based on 2D multiferroics for a variety of other important chemical processes where both the spin and polarity degrees of freedom play significant roles.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003eOur calculations were carried out by spin-polarized first-principles calculations based on density functional theory (DFT)\u003csup\u003e57, 58\u003c/sup\u003e, as implemented in the Vienna \u003cem\u003eab initio\u003c/em\u003e simulation package (VASP)\u003csup\u003e59, 60\u003c/sup\u003e, with the projector augmented wave (PAW)\u003csup\u003e61, 62\u003c/sup\u003e method and the revised Perdew-Burke-Ernzerhof (RPBE)\u003csup\u003e63\u003c/sup\u003e for the exchange-correlation functional. DFT+U method\u003csup\u003e64, 65\u003c/sup\u003e with U\u003csub\u003eeff\u003c/sub\u003e = 4 eV is employed to treat the localization of 3\u003cem\u003ed\u003c/em\u003e orbitals of Cr atoms, as suggested by previous theoretical calculations\u003csup\u003e26\u003c/sup\u003e. The electronic wave functions were expanded in a plane wave basis with an energy cutoff of 550 eV, and the k-space integration was performed with a 2\u0026times;2\u0026times;1 Monkhorst-Pack k-point mesh in the Brillouin zone for the relatively large simulation cell. A vacuum space beyond 12 \u0026Aring; along the c-axis is incorporated to prevent interactions between neighboring slabs. To attain the optimized structures, all the atoms were allowed to relax until all the residual force components were less than 0.02 eV/\u0026Aring;. The kinetic properties of CO oxidation were investigated using the climbing-image nudged elastic band (CI-NEB) method\u003csup\u003e66, 67\u003c/sup\u003e.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data supporting the findings of the study are included in the main text and supplementary information files. Raw data can be obtained from the corresponding author upon request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eF.X.Z. and P.S.W. contributed equally to this work. We thank Prof. Zhenyu Zhang for helpful discussion. This work was supported by the NSF of China (Grants No. U23A2072, 12074345, 12174349, 12204431, 12204421). The calculations were performed on the National Supercomputing Center in Zhengzhou, Henan.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eS.F.L. and X.Y.R. conceived the idea and designed the work; F.X.Z. performed the calculations; P.S.W. conducted the mechanism analysis and model calculations; S.F.L., X.Y.R., F.X.Z., and P.S.W. wrote the manuscript; Y.D.Z., J.L.S. and R.P. participated in the discussion. All authors contributed to the preparation of the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eJones, J., et al. 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A climbing image nudged elastic band method for finding saddle points and minimum energy paths. \u003cem\u003eJ. Chem. Phys.\u003c/em\u003e \u003cstrong\u003e113\u003c/strong\u003e, 9901-9904 (2000).\u003c/li\u003e\n\u003cli\u003eHenkelman, G.; J\u0026oacute;nsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. \u003cem\u003eJ. Chem. Phys.\u003c/em\u003e \u003cstrong\u003e113\u003c/strong\u003e, 9978-9985 (2000).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4937470/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4937470/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"In modern chemistry, the development of highly efficient room-temperature catalysts is of great significance and remains a long-standing challenge in various typical reactions. Here, we theoretically demonstrate that the two-dimensional (2D) multiferroic, Cr(half-fluoropyrazine) [Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e], is a promising single-atom catalyst (SAC) operating at room-temperature for CO oxidation. The rate-limiting barrier is merely 0.33 eV, leading to a reaction rate (i.e., 2.86×10\u003csup\u003e6\u003c/sup\u003e s\u003csup\u003e−1\u003c/sup\u003e) of five orders of magnitude higher than its monoferroic derivative [Cr(pyz)\u003csub\u003e2\u003c/sub\u003e], due to the synergetic effects of two aspects. First, the more flexible ligand rotations in Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e facilitate the activation of O\u003csub\u003e2\u003c/sub\u003e molecule, simultaneously enhancing the charge transfer and spin-accommodation process. Second, on Cr(h-fpyz)\u003csub\u003e2\u003c/sub\u003e, O\u003csub\u003e2\u003c/sub\u003e adsorption induces a distinctly lower local positive electric field, reducing the electrostatic repulsion of the polar CO molecule. These findings may also pave the way for establishing highly efficient SAC platforms based on 2D multiferroics where multidegree of freedom (e.g. spin, polarity) synergistically matter.","manuscriptTitle":"Highly enhanced room-temperature single-atom catalysis of two-dimensional organic-inorganic multiferroics Cr(half-fluoropyrazine) for CO oxidation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-09-09 09:45:51","doi":"10.21203/rs.3.rs-4937470/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"f11dbc24-c24b-496a-8072-f0759cd1d2b4","owner":[],"postedDate":"September 9th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":37215091,"name":"Physical sciences/Physics/Condensed-matter physics/Ferroelectrics and multiferroics"},{"id":37215092,"name":"Physical sciences/Chemistry/Catalysis/Catalytic mechanisms"}],"tags":[],"updatedAt":"2025-02-13T08:08:00+00:00","versionOfRecord":{"articleIdentity":"rs-4937470","link":"https://doi.org/10.1038/s41467-025-56863-1","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2025-02-12 05:00:00","publishedOnDateReadable":"February 12th, 2025"},"versionCreatedAt":"2024-09-09 09:45:51","video":"","vorDoi":"10.1038/s41467-025-56863-1","vorDoiUrl":"https://doi.org/10.1038/s41467-025-56863-1","workflowStages":[]},"version":"v1","identity":"rs-4937470","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4937470","identity":"rs-4937470","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}