Home Journals Articles Updates About
CN
image
收藏切换
Mechanistic insights into methanol steam reforming on PdCu(111) and PtCu(111) bimetallic catalysts
收藏切换
PDF
Ruiying WANG1, *, Fene GAO1, Junlan GUO1, Xi ZHANG1, Sitian LU1, Yanan LIU1, Jianfeng JIA2, *
Journal of Fuel Chemistry and Technology | 2026, 54(7) : 20260081-1389 - 20260081-1400
Less
收藏切换
Journal of Fuel Chemistry and Technology | 2026, 54(7): 20260081-1389-20260081-1400
• RESEARCH PAPER •
Mechanistic insights into methanol steam reforming on PdCu(111) and PtCu(111) bimetallic catalysts
Full
Ruiying WANG1, *, Fene GAO1, Junlan GUO1, Xi ZHANG1, Sitian LU1, Yanan LIU1, Jianfeng JIA2, *
Affiliations
  • 1School of Energy Engineering, Shanxi College of Technology, Shuozhou 036000, China
  • 2Key Laboratory of Magnetic Molecules, Magnetic Information Materials Ministry of Education, School of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China
Published: 2026-07-10 doi: 10.1016/S1872-5813(26)60752-9
Outline
收藏切换

Methanol steam reforming (MSR) stands as a pivotal process for efficient hydrogen production. In this study, density functional theory (DFT) calculations were employed to conduct a comparative analysis of the MSR reaction mechanism on PdCu(111) and PtCu(111) bimetallic surfaces. The investigation unveiled the underlying mechanism by which alloying modulates reaction pathways and overall catalytic performance. Notably, Cu sites were found to stabilize adsorption of OH and CH2O species, whereas Pd/Pt sites exhibited a preferential affinity for CO molecule. This spatial site separation facilitates progression along the formate pathway. PdCu(111) demonstrated superior overall catalytic performance compared to PtCu(111), with water dissociation identified as the rate-determining step (RDS), featuring an activation energy of only 0.74 eV. The bimetallic synergy breaks the inherent contradiction between the activity and selectivity of monometallic catalysts: Cu sites serve as a source of hydroxyl groups, while Pd/Pt sites enhance C–H bond cleavage efficiency, ultimately enabling high methanol conversion alongside low CO formation. From the perspectives of electronic structure and geometric configuration, this study establishes a theoretical framework to guide the rational design of high-performance bimetallic catalysts for MSR.

methanol steam reforming  /  PdCu(111)  /  PtCu(111)  /  reaction mechanism
王锐英, 高奋娥, 郭俊兰, 张茜, 路思甜, 刘雅楠, 贾建峰. 甲醇蒸汽重整在PdCu(111)和PtCu(111)双金属催化剂上的机理研究. 燃料化学学报（中英文）, 2026 , 54 (7) : 20260081-1389 -20260081-1400 . DOI: 10.1016/S1872-5813(26)60752-9
Ruiying WANG, Fene GAO, Junlan GUO, Xi ZHANG, Sitian LU, Yanan LIU, Jianfeng JIA. Mechanistic insights into methanol steam reforming on PdCu(111) and PtCu(111) bimetallic catalysts[J]. Journal of Fuel Chemistry and Technology, 2026 , 54 (7) : 20260081-1389 -20260081-1400 . DOI: 10.1016/S1872-5813(26)60752-9
Full Text
Less
Hydrogen is widely recognized as a quintessential clean energy carrier with potential applications across diverse fields—particularly as a fuel in fuel cells, which has garnered substantial research attention[1−4]. However, the storage and transportation of hydrogen remain formidable challenges to its widespread utilization[5−7]. Compared with other hydrocarbons, CH3OH exhibits distinct advantages as a hydrogen carrier: it has the highest hydrogen-to-carbon ratio and lacks stable carbon-carbon bonds. These structural attributes enable methanol to undergo steam reforming under relatively mild temperature conditions, thereby endowing it with significant potential for efficient hydrogen production[8−10].
Cu-based catalysts have been extensively employed in MSR reactions[11−15], and their catalytic activity and product selectivity can typically be modulated by incorporating appropriate promoters[16−19] and optimizing synthesis protocols[20−24]. Nevertheless, the inherent susceptibility of copper to sintering and deactivation at elevated reaction temperatures—stemming from its intrinsic pyrophoricity—severely constrains its long-term stability[25−26]. In contrast, Group VIII transition metal catalysts have been developed for their exceptional thermal stability. Specifically, Pd-based catalysts exhibit catalytic activity comparable to that of Cu-based systems at high temperatures[27−29] while maintaining performance stability over prolonged reaction periods. A critical limitation of such catalysts, however, is their propensity to generate CO, which can induce severe poisoning of fuel cell electrodes. Notably, Iwasa et al.[30−31] demonstrated that loading Pd onto a ZnO support enhances MSR activity and selectivity toward CO2. Experimental characterizations revealed that Pd particles alloy with Zn as temperature increases, forming a stable PdZn phase over a broad temperature range. Analogously, Pd/ZnO catalysts also exhibit low CO selectivity in MSR, a behavior attributed to the formation of PdZn alloys. Wang et al.[32] further reported that PdZn alloy formation significantly improves CO2 selectivity and overall catalytic activity, with the active phase remaining stable even at 400 °C. By contrast, catalysts that fail to form such alloy structures with ZnO (e.g., Ni, Ru, Co, Ir) typically exhibit poor methanol conversion efficiency and produce substantially higher CO concentrations, limiting their practical applicability[33].
By integrating the advantages of Cu and Pd-based catalysts, Azenha et al.[34] rationally designed and synthesized a high-performance PdCu bimetallic catalyst for low-temperature MSR. Compared with monometallic Pd catalysts, the PdCu catalyst displayed 1.5–2 times higher activity and significantly reduced CO formation. Additionally, its long-term stability was enhanced relative to monometallic Cu, with no detectable deactivation observed after 80 h of continuous operation at 240 °C. Complementarily, experimental studies by Mierczynski[35] and Zhang et al.[36] confirmed that the PdCu alloy phase markedly boosts H2 yield during MSR. This alloy adopts a stable face-centered cubic (fcc) structure, with the exposed (111) facet serving as the primary active surface. The latter report[36] further validated, via rigorous characterizations including XRD, HAADF-STEM, EDS, XAFS and XPS, that the 1∶1 stoichiometric PdCu alloy exhibits excellent catalytic activity under realistic reaction conditions. These experimental findings provide a robust structural basis for the development of our computational models.
From a theoretical perspective, comprehensive reaction mechanisms for MSR on various pure metal surfaces, including Cu(111)[37−38], Cu(110)[39], Cu(211)[38], Pd(111)[37], Pt(111)[40], Co(0001)[41] and Ni(111)[42] have been well-established, elucidating their respective reaction pathways and product selectivities. For alloy catalysts, systematic mechanistic investigations have also been reported for systems such as PdZn(111)[43], PtZn(111)[44], NiZn(111)[44] and NiCu(111)[45]. Given that Pt and Pd belong to the same group in the periodic table and share similar electronic configurations, we employed DFT calculations to systematically investigate MSR reaction pathways on PdCu(111) and PtCu(111) alloy surfaces. By probing the structure-performance relationship of these catalysts, this study advances our understanding of how alloy composition modulates catalytic behavior.
1　Computational methods and models
Less
All calculations were performed using the Vienna Ab initio Simulation Package (VASP)[46−47]. The electronic exchange-correlation interaction was described by the Perdew-Burke-Ernzerhof (PBE) functional[48] within the framework of the generalized gradient approximation (GGA) and core-valence electron interactions[49] were treated via the projector augmented wave (PAW) method. To account for van der Waals forces between adsorbates and the catalyst surface, the DFT-D3 correction was incorporated[50−51]. A plane-wave kinetic energy cutoff of 400 eV was employed, and the Brillouin zone was sampled with a 2×2×1 Monkhorst-Pack k-point mesh.
Geometric optimizations were carried out until the residual forces on all atoms converged to less than 0.02 eV/Å, with the energy difference between consecutive steps falling below 10−5 eV. For transition state (TS) searches, the force convergence criterion was relaxed to 0.05 eV/Å. To ensure reliability and accuracy, the climbing image nudged elastic band (CI-NEB) method[52−54] and dimer method[55−56] were employed in combination. TS structures were validated by the presence of exactly one imaginary vibrational frequency, whose corresponding mode strictly aligned with the bond-breaking direction involved in the reaction. Relevant energy calculations (e.g., adsorption energy (Eads), reaction energy (ΔE) and activation energy (Ea)) followed the formulations reported in our previous work[57].
Surface models of PdCu(111) and PtCu(111) were constructed using a four-layer slab with a p(4×4) surface supercell. The optimized lattice parameters for the PdCu(111) slab were a = b = 10.54 Å and c = 21.58 Å, while those for the PtCu(111) slab were a = b = 10.56 Å and c = 21.63 Å. A 15 Å vacuum layer was introduced along the z-direction to eliminate interactions between periodic images. To simulate the surface alloy structure, each slab was configured with a 1∶1 stoichiometric ratio of Pd:Cu (for PdCu(111)) and Pt∶Cu (for PtCu(111)). For free gas-phase molecule calculations, each molecule was placed in a 12 Å ×12 Å ×12 Å cubic supercell to avoid intermolecular interactions.
2　Results and discussion
Less
2.1　Stable adsorption configurations of all species on PdCu(111) and PtCu(111) surfaces
All adsorbed intermediates are categorized into four classes based on the type of atoms that directly interact with the catalyst surface: (1) O-terminated intermediates: species primarily bonded to the surface via O atom, including: H2O, CH3OH, OH, CH3O, CH2OOH, CHOOH, CH2OO, bi-CHOO and mono-CHOO; (2) C/O co-adsorbed intermediates: species adsorbed simultaneously through both C and O atoms, such as: CH2O, CHO, cis-COOH and trans-COOH; (3) C-terminated intermediates: species mainly bonded to the surface via C atom, with CO as the representative example; (4) Other species: weakly adsorbed CO2 on the surface. The adsorption sites considered primarily include top sites (Pd-top, Pt-top, Cu-top), bridge sites (Pd-Cu bridge, Pt-Cu bridge, Cu-Cu bridge), hexagonal close-packed (hcp) hollow sites (Cu-Pd-Pd, Cu-Pt-Pt, Cu-Cu-Pd, Cu-Cu-Pt) and fcc hollow sites (Cu-Pd-Pd, Cu-Pt-Pt, Cu-Cu-Pd, Cu-Cu-Pt), as illustrated in Figure 1. All adsorption structures are provided in Tables S1 and S2 of the Supporting Information, where the most stable adsorption configurations on PdCu(111) and PtCu(111) surfaces are systematically depicted in Figures 2 and 3, respectively. The corresponding adsorption energies are summarized in Table 1. Detailed descriptions of each category of species are as follows.
2.1.1　Adsorption of O-terminated intermediates
On the PdCu(111) surface, H2O preferentially adsorbs at the Cu-top site via the O atom with an adsorption energy of −0.48 eV. In this configuration, both O–H bonds lie parallel to the surface, with a bond length of 0.98 Å—slightly longer than the gas-phase value (0.97 Å), indicating partial activation of H2O. On PtCu(111), the most stable H2O adsorption occurs at the Pt-top site via the O atom, where both O–H bonds are parallel to the surface (bond length = 0.98 Å) and the adsorption energy is also −0.48 eV.
CH3OH adsorbs at the Cu-top site on both PdCu(111) and PtCu(111). The average C–H bond length is 1.10 Å for both surfaces, while the O−H bond lengths are 0.97 Å (PdCu(111)) and 0.98 Å (PtCu(111)), with corresponding adsorption energies of −0.67 and −0.69 eV, respectively.
OH preferentially adsorbs at fcc hollow sites on both surfaces. On PdCu(111), OH is stabilized at the Cu-Cu-Pd fcc site with an average O-metal distance of 2.07 Å; on PtCu(111), it adsorbs at the Cu-Cu-Pt fcc site with an O-metal distance of 2.09 Å. The O–H bond length is 0.97 Å for both surfaces, and the adsorption energies are −3.10 eV (PdCu(111)) and −2.83 eV (PtCu(111)).
CH3O shares the same preferred adsorption sites as OH: the Cu-Cu-Pd fcc site on PdCu(111) and the Cu-Cu-Pt fcc site on PtCu(111). The average O-metal distances are 2.07 Å (PdCu(111)) and 2.09 Å (PtCu(111)), while the average C−H bond length of CH3O is 1.10 Å for both surfaces. Adsorption energies are −2.54 eV (PdCu(111)) and −2.34 eV (PtCu(111)).
For CH2OOH on PdCu(111), one O atom adsorbs at the Cu-Cu-Pd fcc hollow site with an average O-metal distance of 2.13 Å; the remaining molecular moiety tilts slightly upward without direct bonding to the surface. A similar configuration is observed on PtCu(111), where one O atom occupies the Cu-Cu-Pt fcc site (O-metal distance = 2.09 Å). The adsorption energies of CH2OOH are −2.49 eV (PdCu(111)) and −2.22 eV (PtCu(111)).
CHOOH adopts a planar, top-site adsorption configuration on both surfaces, with one O atom bound to a Cu-top site. The O−Cu distances are 2.13 Å (PdCu(111)) and 2.17 Å (PtCu(111)). In the adsorbed CHOOH, the C–H bond lengths are 1.10 Å (PdCu(111)) and 1.11 Å (PtCu(111)), while both O–H bonds measure 1.03 Å. Adsorption energies are nearly identical: −0.74 eV (PdCu(111)) and −0.73 eV (PtCu(111)).
CH2OO, a competitive species to CHOOH, adsorbs via two O atoms at distinct bridge sites on both surfaces. On PdCu(111), the O atoms bind to the Cu-Cu bridge (average distance = 2.00 Å) and Pd-Pd bridge (2.17 Å), with an average C–H bond length of 1.11 Å. On PtCu(111), the O atoms occupy the Cu-Cu bridge (2.06 Å) and Pt-Pt bridge (2.16 Å), with the same average C–H bond length (1.11 Å). Adsorption energies of CH2OO are −3.96 eV (PdCu(111)) and −3.44 eV (PtCu(111)).
CHOO exhibits two adsorption modes: bidentate (bi-CHOO) and monodentate (mono-CHOO). In bi-CHOO, both O atoms coordinate with surface metal atoms; in mono-CHOO, only one O atom binds to the substrate. On PdCu(111), the most stable bi-CHOO has both O atoms bonded to Cu atoms (adsorption energy = −3.02 eV), while the most stable mono-CHOO adsorbs via one O atom at the Cu-Cu bridge (−2.49 eV). On PtCu(111), a similar trend is observed. Their adsorption energies are −2.75 eV (bi-CHOO) and −2.21 eV (mono-CHOO), respectively.
2.1.2　Adsorption of C/O co-adsorbed intermediates
On the PdCu(111) surface, the O atom of the CH2O species occupies the Cu-Cu bridge site, with an average O−Cu bond length of 2.09 Å. The CH2 moiety adsorbs at the Pd-atop site, forming a C−Pd bond of 2.10 Å, while the average C−H bond length is 1.10 Å. A similar adsorption configuration is observed on PtCu(111): the C atom binds to the Pt-top site (C-Pt distance = 2.11 Å), and the O atom bridges two Cu atoms (average O−Cu distance = 2.11 Å), with an average C–H bond length of 1.10 Å. The calculated adsorption energies are −0.84 eV (PdCu(111)) and −0.79 eV (PtCu(111)).
For CHO on PdCu(111), the O atom adsorbs at the Cu-top site (O−Cu distance = 2.11 Å), while the C atom occupies the Pd-Pd bridge site (average C−Pd bond length = 2.06 Å); the C−H bond length is 1.12 Å. A similar structure is found on PtCu(111): the O atom binds to the Cu-top site (O−Cu distance = 2.10 Å) and the C atom is located at the Pt-Pt bridge site (average C−Pt bond length = 2.09 Å), with a C−H bond length of 1.11 Å. The adsorption energies are −2.91 (PdCu(111)) and −3.05 eV (PtCu(111)).
COOH is a competitive species relative to CHOO, existing as two configurational isomers: cis-COOH and trans-COOH. In the cis isomer, the O-bound H atom and C-bound O atom lie on the same side of the molecular plane; in the trans isomer, they are on opposite sides. Calculations indicate that both cis-COOH and trans-COOH adsorb at the Pd-Pd (PdCu(111)) or Pt-Pt (PtCu(111)) bridge sites. Their adsorption energies are −2.85 (cis) and −2.84 eV (trans) on PdCu(111), and −3.09 eV for both isomers on PtCu(111).
2.1.3　Adsorption of C-terminated intermediates
On the PdCu(111) surface, CO is generated via the dehydrogenation of CHO. It adsorbs at an hcp hollow site coordinated by two Pd atoms and one Cu atom, with a C–O bond length of 1.19 Å. On the PtCu(111) surface, the C atom occupies the Pt-Pt bridge site, and the C–O bond length is also measured as 1.19 Å. The calculated adsorption energies exhibit a notable difference: −2.05 eV on PdCu(111) versus −2.20 eV for PtCu(111).
2.1.4　Adsorption of other intermediates
CO2 is generated via the dehydrogenation of either CHOO or COOH. On both PdCu(111) and PtCu(111) surfaces, the two C–O bonds of CO2 lie parallel to the surface plane. This adsorption is classified as physisorption and exhibits the lowest adsorption energy among all studied species: −0.28 eV on PdCu(111) and −0.29 eV on PtCu(111).
2.1.5　Electronic structure analysis of key intermediates
Based on the above results, regarding adsorption sites, most species (e.g., OH, CH3O, CH2O) tend to adsorb at Cu-top sites or Cu-coordinated hollow sites. This preference arises from Cu’s fully occupied 3d10 electron configuration and lower d-orbital energy, which effectively mitigates Pauli repulsion between Cu and oxygen lone pairs. In contrast, species such as CHO and CO preferentially adsorb at Pd/Pt sites (bridge or hollow sites). This selectivity stems from the higher electronegativity of Pd/Pt and their more spatially extended d-orbitals; their interaction with CO is dominated by strong π-backbonding, where metal d-electrons feed back into 2π* antibonding orbitals of CO.
In terms of adsorption energy, intermediates like OH and CH3O generally adsorb more strongly on PdCu than on PtCu surface. For instance, OH exhibits an adsorption energy of −3.10 eV on PdCu versus −2.83 eV on PtCu. This enhanced affinity aligns with the calculated d-band centers: it is located at −1.47 eV on PdCu, which is higher than that of PtCu at −1.65 eV. Conversely, intermediates such as CO and CHO bond more strongly to PtCu. Specifically, CO adsorption energies are −2.20 eV (PtCu) and −2.05 eV (PdCu), while CHO adsorption energies are −3.05 (PtCu) and −2.91 eV (PdCu). This phenomenon is attributed to Pt’s unique electronic structure: in PtCu alloys, the lower electronegativity of Cu drives electron donation to Pt and the diffuse 5d orbitals of Pt enable more effective electron feedback into the antibonding orbitals of CO and CHO. Thus, despite the overall downshift of the d-band center, the local electronic and orbital properties of Pt still stabilize these intermediates.
To further validate the origins of adsorption selectivity and π feedback, we calculated the projected density of states (PDOS) for CO adsorbed on PdCu(111) and PtCu(111), focusing on interactions between CO and directly bonded metal atoms (Figure 4). Pt’s d-band maintains a high density of states (DOS) in the −8 to −6 eV range, forming strong and effective coupling with the 3σ orbital of CO to stabilize the σ bond. In the −5 to 0 eV range, the d-band of Pt exhibits broad and dispersed DOS with substantial states near the Fermi level (0 eV), enabling effective overlap with CO’s 2π* orbital and strong π back-donation, directly enhancing the Pt–C bond. In contrast, Pd and Cu d-orbitals on PdCu show significant hybridization and overlap in the −3 to −1 eV range. Consequently, in the 2π*-dominant range (−1 to 0 eV), the effective DOS of Pd d-states is drastically reduced, limiting electrons available for π back-donation and weakening orbital overlap.
The electron density difference maps (Figure 5) visually confirm bonding strength differences between CO and the two alloy surfaces. In PtCu, a distinct electron accumulation bridge exists between Pt and CO’s C atom, indicating sufficient electron cloud overlap and strong Pt–C bonding. In PdCu, charge distribution around Pd/Cu atoms is more dispersed, with weaker electron accumulation at Pd–C/Cu–C interfaces than in PtCu. Additionally, Cu coordination induces charge delocalization and insufficient bonding electron cloud overlap, directly reflecting weakened interfacial interactions. Bader charge analysis further supports this: in PdCu, CO’s C loses 0.69 e, while two Pd atoms gain only 0.19 e, and Cu loses 0.28 e, resulting in a net system loss of 0.09 e (indicating insufficient effective bonding electrons). In PtCu, the C atom of CO loses 0.76 e and two directly bonded Pt atoms gain 0.48 e (~2.5 times the electron gain of Pd in PdCu), confirming abundant effective bonding electrons.
2.2　Elementary steps of the MSR reaction
For the MSR reaction, two primary reaction pathways are the focus of this study, as illustrated in Figure 6: the formate pathway (Pathway 1, green arrows) and the decomposition-water gas shift (WGS) pathway (Pathway 2, blue arrows). The TS geometries of reactions occurring on PdCu(111) and PtCu(111) surfaces are presented in Figures 7 and 8, respectively. The corresponding reaction energies, activation energies, and key bond lengths in the TS are summarized in Table 2.
2.2.1　Dissociation steps of initial species
R1: We first investigated the decomposition of H2O on PdCu(111). In the TS, OH remains adsorbed at a Cu-top site, while the dissociated H atom migrates to a Pd-Pd bridge site. The O–H bond length at this stage is 1.62 Å. Following complete dissociation, the H atom stabilizes at an hcp hollow site coordinated by two Pd and one Cu atom, while OH migrates to an fcc hollow site composed of one Pd and two Cu atoms. This step is exothermic with a ΔE of −0.20 eV and an Ea of 0.74 eV.
On PtCu(111), the reaction initiates with OH migrating to a Pt-Cu bridge site, while the H atom adsorbs at a Pt-top site (O–H bond length = 1.46 Å). In the product, the H atom stabilizes at a Cu-Pt-Pt fcc hollow site, and OH adsorbs at a Cu-Cu-Pt fcc hollow site. This step is slightly endothermic (ΔE = 0.09 eV), with an Ea of 0.78 eV—comparable to the energy barrier on PdCu(111).
R2: On PdCu(111), the TS of this step closely resembles the structure of the TS for the corresponding step, with the O–H bond elongated to 1.51 Å. After reaction completion, the dissociated CH3O adsorbs at a Cu-Cu-Pd fcc hollow site, and the H atom attaches to a Pd-Pd-Cu fcc hollow site. This step is exothermic (ΔE = −0.14 eV) with an Ea of 0.64 eV.
In contrast, the TS of this reaction on PtCu(111) is more similar to the product structure, with the O–H bond elongated to 2.40 Å. In the product, CH3O adsorbs at a Cu-Cu-Pt fcc hollow site, and the H atom adsorbs at a Pt-Pt-Cu hcp hollow site. This step is slightly exothermic (ΔE = −0.05 eV) but exhibits a higher Ea of 0.93 eV, making it relatively kinetically hindered.
R3: For the reaction on PdCu(111), the product CH2O adsorbs at a Cu-Cu-Pd hcp hollow site: the O atom bridges two Cu atoms, while the C atom sits atop a Pd atom. The dissociated H atom stabilizes at a Cu-Pd-Pd hcp hollow site, with a C–H distance of 2.63 Å. The TS is product-biased, with the C–H bond elongated to 1.48 Å. This step is slightly endothermic (ΔE = 0.04 eV) with an Ea of 0.66 eV.
On PtCu(111), the TS of this reaction is also product-like (C–H bond length = 1.49 Å). Notably, this step is exothermic (ΔE = −0.11 eV) with a moderate Ea of 0.54 eV.
2.2.2　Elementary steps of Pathway 1
R4: CH2O exhibits two primary evolution pathways in the reaction: (1) combination with OH (from H2O dissociation) to form CH2OOH, and (2) further dehydrogenation to CHO. Here, the former is discussed first. In the initial co-adsorption structure, both CH2O and OH adopt their most stable configurations on PdCu(111). As the reaction proceeds, the C atom of CH2O lifts away from the Pd-top site, while the O atom of OH migrates from its original fcc hollow site to a Pd site. In this TS, the C–O distance shortens to 1.98 Å, eventually forming a stable CH2OOH intermediate.
On PtCu(111), the reaction proceeds analogously. In the most stable reactant structure, the distance between CH2O and OH is 2.93 Å. Upon entering the TS, the C atom of CH2O deviates from the Pt site, indicative of nucleophilic attack by OH; the C–O distance reaches 2.37 Å at this stage. As the reaction progresses, a C–O bond forms with a final length of 1.40 Å. Energetically, this step is kinetically facile on both surfaces: PdCu(111) and PtCu(111) exhibit ΔE of −0.24 and −0.38 eV, and Ea of 0.49 and 0.23 eV, respectively.
R5: Cleavage of the C–H bond in CH2OOH generates CHOOH, typically a planar molecule. On PdCu(111), CHOOH binds to the surface via one O atom coordinated to a Cu atom, while the dissociated H atom stabilizes at a Pd-Pd-Cu fcc hollow site. The C–H bond length of the TS is 1.50 Å. This step is exothermic (ΔE = −0.83 eV) with an Ea of 0.63 eV. Similarly, CHOOH on PtCu(111) adopts a planar structure, with a C−H bond length of 1.13 Å in the TS; it is highly exothermic (ΔE = −1.13 eV) with an Ea of 0.56 eV.
R6: On PdCu(111), dissociation of the H atom from the hydroxyl O of CH2OOH yields CH2OO, which stabilizes in its most favorable configuration: two O atoms occupy Pd-Pd and Cu-Cu bridge sites, respectively. The TS O–H bond length is 1.75 Å. On PtCu(111), CH2OO adopts an analogous structure, with a TS O–H bond length of 1.68 Å. This step is endothermic (ΔE values of 0.38 eV (PdCu) and 0.47 eV (PtCu)) with comparable Ea values (0.85 and 0.84 eV, respectively). Collectively, thermodynamic and kinetic data indicate that the CH2OO formation pathway is less favorable than CHOOH formation on both surfaces.
R7: Like CH2OOH, CHOOH undergoes dehydrogenation via two competing pathways: C–H or O–H bond cleavage. We first discuss the pathway corresponding to CHOOH→bi-CHOO + H. On PdCu(111), one H atom detaches from the hydroxyl O of CHOOH and migrates to a Cu-Cu-Pd fcc hollow site; the remaining bi-CHOO binds bidentately to one Pd and one Cu atom. The TS O–H bond length is 1.70 Å.
On PtCu(111), the TS O–H bond length is 2.12 Å (more elongated than on PdCu(111)). This step is exothermic on both surfaces (ΔE values of −0.25 (PdCu) and −0.31 eV (PtCu)) with low Ea values (0.24 and 0.30 eV, respectively).
R8: This step competes with R7. On PdCu(111), the cis-COOH product features one O atom at a Cu-top site, the C atom at a Pd-Pd bridge site, and OH pointing upward; the dissociated H atom stabilizes at a Pd-Pd-Cu fcc hollow site. In the TS, the departing H atom and C atom are co-coordinated to the same Pd atom, with an H–C distance of 1.47 Å.
On PtCu(111), cis-COOH has one O atom at a Cu-top site, the C atom above a Pt-top site, and the dissociated H atom at a Pt-Pt bridge site; the TS C–H bond length is 1.55 Å. This step is kinetically more hindered than bi-CHOO formation, with significantly higher Ea values (0.69 eV for PdCu and 0.72 eV for PtCu) and ΔE values of −0.25 and −0.46 eV, respectively.
R9: In bi-CHOO, the H atom is farthest from the surface. Thus, conformational rearrangement of CHOOH is required before further conversion to CO2. On PdCu(111), bi-CHOO first migrates to a Cu-Cu bridge site (Ea = 0.10 eV, negligible). It then undergoes a bidentate-to-monodentate coordination transformation, with Ea (0.54 eV) nearly equal to ΔE (0.50 eV). On PtCu(111), this rotational conformation change occurs in a single step, with ΔE = 0.51 eV and Ea = 0.63 eV.
R10: This step is kinetically facile and highly exothermic on both surfaces: ΔE = −0.77 (PdCu) and −1.10 eV (PtCu), with Ea values of 0.13 and 0.28 eV, respectively. The TS C–H bond lengths are 1.38 (PdCu) and 1.15 Å (PtCu). In the product, the detached H atom stabilizes at a Pd-Pd-Cu or Pt-Pt-Cu fcc hollow site, while CO2 desorbs to a physisorbed state (floating on the surface). The final C–H bond distances reach 3.49 (PdCu) and 3.92 Å (PtCu).
2.2.3　Elementary steps of Pathway 2
R11: This step competes with R4. On PdCu(111), the CHO product adopts its thermodynamically most stable adsorption configuration, while the dissociated H atom stabilizes at a Cu-Pd-Pd fcc hollow site (C–H distance = 2.93 Å). The TS features a C–H bond length of 1.40 Å. This step is exothermic (ΔE = −0.64 eV) with an Ea of 0.25 eV. On PtCu(111), the TS is characterized by co-coordination of the dissociated H and C atoms to the same Pt atom (C–H bond length = 1.31 Å) with an Ea of 0.17 and ΔE of −0.67 eV.
R12: CO formation on PdCu(111) is highly exothermic (ΔE =−1.32 eV). The TS closely resembles the reactant structure, with the key difference being a modified bond angle and a C–H bond length of 1.15 Å. The Ea of 0.09 eV is the lowest among all considered steps. Similarly, on PtCu(111), the TS’s C–H bond length is 1.17 Å, with ΔE = −1.27 eV and a low Ea of 0.14 eV.
R13: While CO formation is kinetically facile, its desorption energies on PdCu(111) and PtCu(111) are as high as 2.05 and 2.20 eV, respectively. Thus, we propose that adsorbed CO participates in the WGS reaction. On PdCu(111), this step is kinetically demanding (Ea = 1.12 eV, the highest in the reaction network), likely due to the strong co-adsorption of reactants: CO occupies a Pd-Pd-Cu site, and OH binds to a Cu-Cu-Pd site, with both species coordinated to three surface metal atoms. Breaking this stable co-adsorption structure requires overcoming a substantial barrier. In the TS, CO and OH migrate to Pd-top and Cu-top sites, respectively (C–O distance = 1.98 Å), forming cis-COOH (ΔE = 0.70 eV, endothermic). On PtCu(111), the step is also endothermic (ΔE = 0.59 eV). In the initial state, OH anchors at a Pt-Cu-Cu fcc hollow site, and CO resides at a Pt-Pt bridge site. In the TS, OH migrates to a Cu-top site (C–O distance = 1.83 Å) with an Ea of 1.02 eV—the highest barrier for PtCu(111)).
R14: The cis-COOH formed by direct CO-OH coupling (H atom pointing away from the surface) is not thermodynamically stable. Thus, cis-to-trans isomerization is required before CO2 formation. This step involves only O–H bond rotation (no bond cleavage) and is kinetically facile on both surfaces: Ea = 0.38 (PdCu) and 0.36 eV (PtCu), with weak exothermicity (ΔE = −0.10 and −0.12 eV, respectively).
R15: In addition to the R10 pathway, CO2 can form via dehydrogenation of trans-COOH. On PdCu(111), this step proceeds with moderate difficulty (Ea = 0.50 eV): linear CO2 desorbs completely, and the dissociated H atom stabilizes at a Cu-Pd-Pd hcp hollow site. The TS features an H atom at a Pd-top site (O–H bond length = 1.46 Å), with ΔE = −0.44 eV. On PtCu(111), the H atom dissociates from O and migrates to a Pt-top site (O–H distance = 1.50 Å), with ΔE = −0.27 eV and Ea = 0.47 eV (comparable to that of PdCu(111)).
2.3　Discussion
2.3.1　Bonding analysis of CO and effect on the MSR reaction
To further quantitatively assess the orbital hybridization and bonding strength between metal d-orbitals and adsorbed CO molecular orbitals, we performed crystal orbital Hamiltonian population (COHP) analysis, with results presented in Figure 9. A positive value of -COHP indicates bonding interactions, while a negative value denotes antibonding interactions. The Integrated COHP (ICOHP) serves as a quantitative descriptor for bond strength[58−59]: a larger absolute value corresponds to a stronger bond. Calculations show that the absolute ICOHP value for the PtCu system (−1.65 eV) is far greater than that for the PdCu system (−0.07 eV). Thus, the orbital hybridization and bonding interactions between Pt d-orbitals and CO molecular orbitals in the PtCu system are significantly stronger than those between Pd d-orbitals and CO molecular orbitals in the PdCu system.
Notably, despite the stronger CO adsorption on PtCu, this does not impede its subsequent conversion. The ΔE of the key elementary reaction CO + OH→COOH is slightly lower on PtCu than that on PdCu. This phenomenon can be rationalized by the reaction thermodynamics and TS stabilization principles: the reaction on PtCu exhibits less endothermicity, and the strong metal-adsorbate interaction effectively stabilizes the CO–OH TS, thereby lowering the ΔE barrier to a certain extent.
2.3.2　Optimal MSR reaction pathways on PdCu(111) and PtCu(111) surfaces
As illustrated in Figures 10 and 11, we systematically compared the energy profiles of competing pathways to further elucidate the reaction pathway selectivity of bimetallic surfaces. While the CHO pathway is kinetically favorable in the early reaction stage, the subsequent CO oxidation step presents the highest Ea barrier across the entire reaction network (typically>1.00 eV). In contrast, the formate pathway initiated by the coupling of CH2O and OH—displays a more balanced distribution of activation energies across elementary steps. For instance, the sequential conversion of CH2OOH to CO2 on PdCu(111) features energy barriers mostly within the range of 0.13–0.63 eV, with no prominent high-energy bottlenecks, rendering the formate pathway kinetically dominant.
Accordingly, the optimal MSR reaction pathway on both PdCu(111) and PtCu(111) is: CH3OH→CH3O→CH2O→CH2OOH→CHOOH→CHOO→CO2. Notably, PdCu(111) outperforms PtCu(111): the RDS on PdCu(111) is water dissociation (Ea = 0.74 eV), whereas that on PtCu(111) is limited by the initial O–H bond cleavage of methanol (Ea = 0.93 eV, a significantly higher barrier).
2.3.3　Performance comparison with pure Cu, Pd and Pt catalysts
In the MSR reaction, monometallic catalysts generally face inherent challenges. As shown in Table 3, while pure Cu(111) exhibits excellent CO2 selectivity, its intrinsic catalytic activity is extremely low. Its RDS is the methoxy dehydrogenation step, with an Ea as high as 1.27 eV[37]. This high energy barrier severely limits the reaction rate, making it difficult to meet the requirements for large-scale hydrogen production. Pure Pd(111) and Pt(111) have relatively high reaction activity, with RDS activation energies of 1.07 and 0.83 eV, respectively; however, both surfaces tend to directly decompose intermediates into CO instead of CO2[37,40].
However, the PdCu(111) and PtCu(111) bimetallic alloys designed in our study successfully overcome this activity-selectivity trade-off through synergistic optimization. Notably, for PdCu(111), the RDS shifts to water dissociation, with the Ea significantly reduced to only 0.74 eV, far lower than those of pure Cu and pure Pd. Meanwhile, the ΔE of this step is −0.20 eV, indicating a thermodynamically spontaneous process. This step can rapidly supply sufficient surface OH species for the reaction, which serves as a critical prerequisite for the subsequent oxidation of species such as CH2O and CO to CO2.
Additionally, a clear site-specific division of labor exists in the system: Cu sites exhibit stronger adsorption capacity for intermediates like OH and CH2O, while Pd and Pt sites are more favorable for the adsorption and activation of CO molecules. This spatial separation of active sites allows formate formation to occur in the Cu region without being hindered by the presence of CO on Pd/Pt sites.
3　Conclusion
Less
Herein, we systematically investigated the catalytic mechanism of the MSR reaction on PdCu(111) and PtCu(111) bimetallic surfaces via DFT calculations, with a focus on analyzing the adsorption configurations, reaction pathways, and energy evolution profiles of all intermediates. The results indicate that Cu sites exhibit strong adsorption affinity for key species such as OH, CH3O and CH2O, whereas Pd and Pt sites preferentially bind CO and CHO. Electronic structure analyses including PDOS, charge density difference, and COHP confirm that the 5d orbitals of Pt show stronger orbital overlap and π feedback with the 2π* orbital of CO, rendering this intermediate more stably adsorbed on PtCu(111). In contrast, the higher d-band center of PdCu(111) enhances its surface ability to adsorb and activate most intermediates.
Mechanistic studies reveal that the MSR reaction proceeds via an efficient formate pathway on both bimetallic catalysts, with PdCu(111) outperforming PtCu(111) in overall catalytic performance. The RDS on PdCu(111) is water dissociation (Ea = 0.74 eV), whereas the RDS on PtCu(111) is limited by the initial O–H bond cleavage of methanol (Ea = 0.93 eV, a relatively higher barrier). Both alloy catalysts overcome the inherent limitations of traditional monometallic catalysts, namely the inability to balance activity and selectivity. By integrating excellent surface water activation and adsorption properties of Cu with the superior C–H bond cleavage abilities of Pd and Pt, high methanol conversion is achieved while maintaining high CO2 selectivity. These findings uncover the bimetallic catalytic mechanism at the atomic level, providing a reliable basis for the rational design of high-performance reforming catalysts.
References
Less
1
DAWOOD F, ANDA M, SHAFIULLAH G M, et al. Hydrogen production for energy: An overview[J]. Int J Hydrogen Energy, 2020, 45(7): 3847−3869.
2
LEBROUHI B E, DJOUPO J J, LAMRANI B, et al. Global hydrogen development-A technological and geopolitical overview[J]. Int J Hydrogen Energy, 2022, 47(11): 7016−7048.
3
ATAK N N, DOGAN B, YESILYURT M K. Investigation of the performance parameters for a PEMFC by thermodynamic analyses: Effects of operating temperature and pressure[J]. Energy, 2023, 282: 128907.
4
TU J, ZHOU P, CHEN S, et al. Solid-state hydrogen storage alloys for production-storage and transportation-application coupling at ambient temperature: A review[J]. Mater Sci Eng R Rep, 2026, 167: 101089.
5
CAI F, LU P, IBRAHIM J J, et al. Investigation of the role of Nb on Pd-Zr-Zn catalyst in methanol steam reforming for hydrogen production[J]. Int J Hydrogen Energy, 2019, 44(23): 11717−11733.
6
MIDILLI A, KUCUK H, TOPAL M E, et al. A comprehensive review on hydrogen production from coal gasification: Challenges and Opportunities[J]. Int J Hydrogen Energy, 2021, 46(50): 25385−25412.
7
HABIBI M, HOSSEINI M G, WANG K. Toward sustainable energy: A comprehensive review of hydrogen production, storage, and utilization[J]. Renewable Sustainable Energy Rev, 2026, 226: 116193.
8
JIANG W, MA X, ZHANG D, et al. Highly efficient catalysts for hydrogen generation through methanol steam reforming: A critical analysis of modification strategies, deactivation, mechanisms and kinetics[J]. J Ind Eng Chem, 2024, 130: 54−72.
9
ABBAS A H M, CHERALATHAN K K, PORPATHAM E, et al. Hydrogen generation using methanol steam reforming-catalysts, reactors, and thermo-chemical recuperation[J]. Renewable Sustainable Energy Rev, 2024, 191: 114147.
10
ZHANG M, LIU D, WANG Y, et al. Recent advances in methanol steam reforming catalysts for hydrogen production[J]. Catalysts, 2025, 15(1): 36.
11
CHIH Y K, KUO S R, WANG J J, et al. Statistical and mechanistic analysis of synergetic methanol steam reforming over Ti-based add./Cu-Zn catalysts[J]. Fuel, 2026, 416: 138597.
12
JIAO C Y, WU Q R, DU Z Y, et al. Cu0.1In0.01/S-1 catalysts with high efficiency towards methanol steam reforming[J]. Int J Hydrogen Energy, 2024, 85: 804−817.
13
TANG X, WU Y, FANG Z, et al. Syntheses, catalytic performances and DFT investigations: A recent review of copper-based catalysts of methanol steam reforming for hydrogen production[J]. Energy, 2024, 295(8): 131091.
14
LIU X, WANG K, RAN Q, et al. Synergetic Cu0 and Cu+ on the surface of Al2O3 support enhancing methanol steam reforming reaction[J]. Surf Interfaces, 2024, 51(9): 104633.
15
LU M, ZHENG Z, LU W, et al. Stable Cu/Cu2O/CuN3@NC catalysts for aqueous phase reforming of methanol[J]. ACS Nano, 2024, 18(37): 25636−25646.
16
CLANCY P, BREEN J P, ROSS J R H. The preparation and properties of coprecipitated Cu-Zr-Y and Cu-Zr-La catalysts used for the steam reforming of methanol[J]. Catal Today, 2007, 127(1): 291−294.
17
WU G S, MAO D S, LU G Z, et al. The Role of the promoters in Cu based catalysts for methanol steam reforming[J]. Catal Lett, 2009, 130(1): 177−184.
18
FENG J, ZHANG T, ZHAO G, et al. Mechanism of methanol steam reforming with inverse ZrO2/Cu catalyst[J]. RSC Adv, 2025, 15(57): 49301−49306.
19
ZHU M, LI D, JIANG Z, et al. Rational design of Cu-based catalysts for methanol steam reforming: Importance of understanding low-performance catalysts[J]. Chem Eng Sci, 2026, 324: 123360.
20
AGUILA G, JIMENEZ J, GUERRERO S, et al. A novel method for preparing high surface area copper zirconia catalysts: Influence of the preparation variables[J]. Appl Catal A: Gen, 2009, 360(1): 98−105.
21
JAKDETCHAI O, TAKAYAMA N, NAKAJIMA T. Activity enhancement of CuZn-impregnated FSM-16 by modification with 1, 3-butanediol for steam reforming of methanol[J]. Kinet Catal, 2005, 46(1): 56−64.
22
SHEN J P, SONG C. Influence of preparation method on performance of Cu/Zn-based catalysts for low-temperature steam reforming and oxidative steam reforming of methanol for H2 production for fuel cells[J]. Catal Today, 2002, 77(1): 89−98.
23
SHISHIDO T, YAMAMOTO Y, MORIOKA H, et al. Active Cu/ZnO and Cu/ZnO/Al2O3 catalysts prepared by homogeneous precipitation method in steam reforming of methanol[J]. Appl Catal A: Gen, 2004, 263(2): 249−253.
24
YAO C Z, WANG L C, LIU Y M, et al. Effect of preparation method on the hydrogen production from methanol steam reforming over binary Cu/ZrO2 catalysts[J]. Appl Catal A: Gen, 2006, 297(2): 151−158.
25
EBLAGON K M, CONCEPCION P H, SILVA H, et al. Ultraselective low temperature steam reforming of methanol over PdZn/ZnO catalysts-Influence of induced support defects on catalytic performance[J]. Appl Catal B: Environ, 2014, 154−155: 316−328.
26
LI D, XU F, TANG X, et al. Induced activation of the commercial Cu/ZnO/Al2O3 catalyst for the steam reforming of methanol[J]. Nat Catal, 2022, 5(2): 99−108.
27
XU X, SHUAI K, XU B. Review on copper and palladium based catalysts for methanol steam reforming to produce hydrogen[J]. Catalysts, 2017, 7(6): 183.
28
YAO X, YUAN S, LI C, et al. ZnO-supported palladium catalysts via ball milling as an effective heterogeneous catalyst for methanol steam reforming[J]. Fuel, 2024, 358: 130133.
29
SHEN X, LONG Q, YANG W, et al. PdZnβ catalyst with a low Pd loading on a ZnTiO3 perovskite for high-temperature methanol steam reforming[J]. Catal Sci Technol, 2026, 16(2): 579−590.
30
IWASA N, KUDO S, TAKAHASHI H, et al. Highly selective supported Pd catalysts for steam reforming of methanol[J]. Catal Lett, 1993, 19(2): 211−216.
31
IWASA N, MASUDA S, OGAWA N, et al. Steam reforming of methanol over Pd/ZnO: Effect of the formation of PdZn alloys upon the reaction[J]. Appl Catal A: Gen, 1995, 125(1): 145−157.
32
WANG H, FANG Z, WANG Y, et al. The study of strong metal-support interaction enhanced PdZn alloy nanocatalysts for methanol steam reforming[J]. J Alloys Compd, 2024, 986: 174006.
33
IWASA N, MASUDA S, TAKEZAWA N. Steam reforming of methanol over Ni, Co, Pd and Pt supported on ZnO[J]. React Kinet Catal Lett, 1995, 55(2): 349−353.
34
AZENHA C, LAGARTEIRA T, MATEOS-PEDRERO C, et al. Production of hydrogen from methanol steam reforming using CuPd/ZrO2 catalysts-Influence of the catalytic surface on methanol conversion and CO selectivity[J]. Int J Hydrogen Energy, 2021, 46(33): 17490−17499.
35
MIERCZYNSKI P, VASILEV K, MIERCZYNSKA A, et al. Highly selective Pd-Cu/ZnAl2O4 catalyst for hydrogen production[J]. Appl Catal A: Gen, 2014, 479: 26−34.
36
ZHANG M, LIU Z, YAN Y, et al. Optimizing selectivity via steering dominant reaction mechanisms in steam reforming of methanol for hydrogen production[J]. Nat Commun, 2025, 16(1): 1943.
37
GU X K, LI W X. First-principles study on the origin of the different selectivities for methanol steam reforming on Cu(111) and Pd(111)[J]. J Phys Chem C, 2010, 114(49): 21539−21547.
38
ZHANG X, YANG B. First-principles-based microkinetic modeling of methanol steam reforming over Cu(111) and Cu(211): structure sensitive activity and selectivity[J]. Dalton Trans, 2024, 53(42): 17190−17199.
39
WANG Y X, ZHANG H L, AN P, et al. Effect of potassium on methanol steam reforming on the Cu(111) and Cu(110) surfaces: A DFT study[J]. J Phys Chem C, 2021, 125(38): 20905−20918.
40
JIN Y X, WANG Y F, ZHANG R X, et al. Theoretical insight into hydrogen production from methanol steam reforming on Pt(111)[J]. Mol Catal, 2022, 532: 112745.
41
LUO W, ASTHAGIRI A. Density functional theory study of methanol steam reforming on Co(0001) and Co(111) surfaces[J]. J Phys Chem C, 2014, 118(28): 15274−15285.
42
KE C, LIN Z. Density functional theory based micro- and macro-kinetic studies of Ni-catalyzed methanol steam reforming[J]. Catalysts, 2020, 10(3): 349.
43
LIN S, XIE D, GUO H. Pathways of methanol steam reforming on PdZn and comparison with Cu[J]. J Phys Chem C, 2011, 115(42): 20583−20589.
44
KRAJCI M, TSAI A P, HAFNER J. Understanding the selectivity of methanol steam reforming on the (111) surfaces of NiZn, PdZn and PtZn: Insights from DFT[J]. J Catal, 2015, 330: 6−18.
45
FAJIN J L C, CORDEIRO M N D S. Insights into the mechanism of methanol steam reforming for hydrogen production over Ni-Cu-based catalysts[J]. ACS Catal, 2022, 12(1): 512−526.
46
KRESSE G, FURTHMULLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[J]. Comput Mater Sci, 1996, 6(1): 15−50.
47
KRESSE G, FURTHMULLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Phys Rev B, 1996, 54(16): 11169−11186.
48
PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Phys Rev Lett, 1996, 77(18): 3865−3868.
49
KRESSE G, JOUBERT D. From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Phys Rev B, 1999, 59(3): 1758−1775.
50
GRIMME S, ANTONY J, EHRLICH S, et al. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu[J]. J Chem Phys, 2010, 132(15): 154104.
51
GRIMME S, EHRLICH S, GOERIGK L. Effect of the damping function in dispersion corrected density functional theory[J]. J Comput Chem, 2011, 32(7): 1456−1465.
52
HENKELMAN G, UBERUAGA B P, JONSSON H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths[J]. J Chem Phys, 2000, 113(22): 9901−9904.
53
HENKELMAN G, JONSSON H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points[J]. J Chem Phys, 2000, 113(22): 9978−9985.
54
SHEPPARD D, TERRELL R, HENKELMAN G. Optimization methods for finding minimum energy paths[J]. J Chem Phys, 2008, 128(13): 134106.
55
HENKELMAN G, JONSSON H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives[J]. J Chem Phys, 1999, 111(15): 7010−7022.
56
HEYDEN A, BELL A T, KEIL F J. Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method[J]. J Chem Phys, 2005, 123(22): 224101.
57
WANG R, YANG X, WANG Y, et al. Mechanism of methanol steam reforming on dual-atom catalysts of PtZn/TiO2 and PdZn/TiO2: Density functional theory studies[J]. Mater Today Commun, 2023, 35: 106125.
58
DRONSKOWSKI R, BLOECHL P E. Crystal orbital Hamilton populations (COHP): Energy-resolved visualization of chemical bonding in solids based on density-functional calculations[J]. J Phys Chem, 1993, 97: 8617−8624.
59
DERINGER V L, TCHOUGRÉEFF A L, DRONSKOWSKI R. Crystal Orbital Hamilton Population (COHP) analysis as projected from plane-wave basis sets[J]. J Phys Chem A, 2011, 115(21): 5461−5466.
Appendix
Less
Year 2026 volume 54 Issue 7
PDF
149
63
Cite this Article
BibTeX
Article Info
doi: 10.1016/S1872-5813(26)60752-9
  • Receive Date：2026-03-06
  • Online Date：2026-09-23
  • Published：2026-07-10
Article Data
Affiliations
History
  • Received：2026-03-06
  • Revised：2026-04-17
  • Accepted：2026-05-15
Affiliations
    1School of Energy Engineering, Shanxi College of Technology, Shuozhou 036000, China
    2Key Laboratory of Magnetic Molecules, Magnetic Information Materials Ministry of Education, School of Chemistry and Chemical Engineering, Shanxi Normal University, Taiyuan 030031, China

Corresponding:

Tel: 18335761230, 18636788078, E-mail:
References
Share
https://castjournals.cast.org.cn/joweb/rlhxxb/EN/10.1016/S1872-5813(26)60752-9
Share to
QR

Scan QR to access full text

Cite this article
BibTeX
Citations
表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
关闭全屏
  • BibTeX
  • EndNote
  • RefWorks
  • TxT
Links
Articles
Latest Articles
Most Read
Collections
Updates
Events
News
Multimedia
About
About Us
Contact
No. 86 Xueyuan South Road, Haidian District, Beijing
100081
010-62662699(Operation and Technical Support)
qkjq@cast.org.cn

Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House