Deciphering orbital hybridization in heterogeneous catalysis

Abstract

The catalytic coordinate is essentially the evolving frontier orbital interaction while feeding with catalytic materials and adsorbates under proper reaction conditions. The heterogeneous catalytic reaction mechanism involves the initial adsorption and activation of reactants, subsequent intermediate transformation, final target product desorption, and regeneration of catalytic materials. In these catalytic processes, interaction modulations in terms of orbital hybridization/coupling allow an intrinsic control on both thermodynamics and kinetics. Concerned charge transfer and redistribution, orbital splitting and rearrangement with specific orientation, and spin change and crossover pose a formidable challenge on mechanism elucidation; it is hard to precisely correlate the apparent activity and selectivity, let alone rational modulations on it. Therefore, deciphering the orbital couplings inside a catalytic round is highly desirable and the dependent descriptor further provides in‐depth insights into catalyst design at the molecule orbital level. This review hopes to provide a comprehensive understanding on orbital hybridizations, modulations, and correlated descriptors in heterogeneous catalysis.

Keywords

catalysis / catalyst design and prediction / descriptors / interactions / orbital hybridization

References

[1] InoueT, Fujishima A, KonishiS, HondaK. Photoelectrocatalytic reduction of carbon dioxide in aqueous suspensions of semiconductor powders. Nature. 1979;277:637.

[2] ZhongW, XuJ, ZhangX, Zhang J, WangX, YuH. Charging dorbital electron of ReS_2+x cocatalyst enables splendid alkaline photocatalytic H₂ evolution. Adv Funct Mater. 2023;33(36):2302325.

[3] ChenK, XiaoJ, VequizoJJM, et al. Overall water splitting by a SrTaO₂N-based photocatalyst decorated with an Ir-promoted Ru-based cocatalyst. J Am Chem Soc. 2023;145(7):3839-3843.

[4] ZhaoY, HuangL, ZhaoD, Yang Lee J. Fast polysulfide conversion catalysis and reversible anode operation by a single cathode modifier in Li-metal anode-free lithium-sulfur batteries. Angew Chem Int Ed. 2023;62(36):e202308976.

[5] CuiX, LiW, RyabchukP, Junge K, BellerM. Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts. Nat Catal. 2018;1(6):385-397.

[6] ChenX, ChenJ, ChenH, et al. Promoting water dissociation for efficient solar driven CO₂ electroreduction via improving hydroxyl adsorption. Nat Commun. 2023;14(1):751.

[7] YuanM, ZhangH, XuY, et al. Artificial frustrated Lewis pairs facilitating the electrochemical N₂ and CO₂ conversion to urea. Chem Catal. 2022;2:309-320.

[8] HisatomiT, DomenK. Reaction systems for solar hydrogen production via water splitting with particulate semiconductor photocatalysts. Nat Catal. 2019;2(5):387-399.

[9] ZhuY, WangJ, ChuH, ChuY-C, ChenHM. In situ/operando studies for designing next-generation electrocatalysts. ACS Energy Lett. 2020;5(4):1281-1291.

[10] LiY, YuZG, WangL, et al. Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs. Nat Commun. 2019;10(1):3149.

[11] DuX, HuangJ, ZhangJ, et al. Modulating electronic structures of inorganic nanomaterials for efficient electrocatalytic water splitting. Angew Chem Int Ed. 2019;58(14):4484-4502.

[12] DyllaMT, KangSD, SnyderGJ. Effect of two-dimensional crystal orbitals on Fermi surfaces and electron transport in three-dimensional perovskite oxides. Angew Chem Int Ed. 2019;58(17):5503-5512.

[13] GiulimondiV, Mitchell S, Perez-RamirezJ. Challenges and opportunities in engineering the electronic structure of single-atom catalysts. ACS Catal. 2023;13(5):2981-2997.

[14] WangY, LiangY, BoT, MengS, LiuM. Orbital dependence in single-atom electrocatalytic reactions. J Phys Chem Lett. 2022;13(25):5969-5976.

[15] ZuoJM, KimM, O’KeeffeM, SpenceJCH. Direct observation of d-orbital holes and Cu-Cu bonding in Cu₂O. Nature. 1999;401(6748):49-52.

[16] ScerriER. Have orbitals really been observed? J Chem Educ. 2000;77(11):1492.

[17] LiX, YuJ, JaroniecM, Chen X. Cocatalysts for selective photoreduction of CO₂ into solar fuels. Chem Rev. 2019;119(6):3962-4179.

[18] WangX, ZhuY, LiH, LeeJM, TangY, Fu G. Rare-earth singleatom catalysts: a new frontier in photo/electrocatalysis. Small Methods. 2022;6(8):e2200413.

[19] NilssonA, Pettersson LGM, HammerB, BligaardT, Christensen CH, NøskovJK. The electronic structure effect in heterogeneous catalysis. Catal Lett. 2005;100(3/4):111-114.

[20] XuZF, XuK, FengHF, Du Y, HaoWC. s-p orbital hybridization: a strategy for developing efficient photocatalysts with high carrier mobility. Sci Bull. 2018;63(8):465-468.

[21] WuY, CaiJ, XieY, et al. Regulating the interfacial electronic coupling of Fe₂N via orbital steering for hydrogen evolution catalysis. Adv Mater. 2020;32(26):e1904346.

[22] ChenZ, SongY, CaiJ, et al. Tailoring the d-band centers enables Co₄N nanosheets to be highly active for hydrogen evolution catalysis. Angew Chem Int Ed. 2018;57(18): 5076-5080.

[23] FangY, WeiC, NiuS, et al. Strong Cr–O hybridization prevents active Cu(II) from cathodic reconstruction for alkaline hydrogen evolution catalysis. Small Struct. 2022;3(12):2200133.

[24] ChangX, WangT, GongJ. CO₂ photo-reduction: insights into CO₂ activation and reaction on surfaces of photocatalysts. Energy Environ Sci. 2016;9(7):2177-2196.

[25] WangL, HuaW, WanX, et al. Design rules of a sulfur redox electrocatalyst for lithium–sulfur batteries. Adv Mater. 2022;34(14):e2110279.

[26] RothenbergG. Catalysis: Concepts and Green Applications. Wiley-VCH;2008:65.

[27] WangJM, ZhuQY, LeeJH, et al. Asymmetric gradient orbital interaction of hetero-diatomic active sites for promoting C–C coupling. Nat Commun. 2023;14(1):3808.

[28] LiH, ShiP, WangL, et al. Cooperative catalysis of polysulfides in lithium-sulfur batteries through adsorption competition by tuning cationic geometric configuration of dual-active sites in spinel oxides. Angew Chem Int Ed. 2023;62(8):e202216286.

[29] MoltvedKA, KeppKP. The chemical bond between transition metals and oxygen: electronegativity, d-orbital effects, and oxophilicity as descriptors of metal-oxygen interactions. J Phys Chem C. 2019;123(30):18432-18444.

[30] WangC, WangX, ZhangT, Qian P, LookmanT, SuY. A descriptor for the design of 2D MXene hydrogen evolution reaction electrocatalysts. J Mater Chem A. 2022;10(35): 18195-18205.

[31] HuC, WangX, YaoT, et al. Enhanced electrocatalytic oxygen evolution activity by tuning both the oxygen vacancy and orbital occupancy of B-site metal cation in NdNiO₃. Adv Funct Mater. 2019;29(30):1902449.

[32] ZhaoZ-J, LiuS, ZhaS, et al. Theory-guided design of catalytic materials using scaling relationships and reactivity descriptors. Nat Rev Mater. 2019;4(12):792-804.

[33] WangJ, HuangY-C, WangY, et al. Atomically dispersed metal-nitrogen-carbon catalysts with d-orbital electronic configuration-dependent selectivity for electrochemical CO₂-to-CO reduction. ACS Catal. 2023;13(4):2374-2385.

[34] LiG, Stenlid JH, AhlquistMSG, BrinckT. Utilizing the surface electrostatic potential to predict the interactions of Pt and Ni nanoparticles with Lewis acids and bases—σ-lumps and σ-holes govern the catalytic activities. J Phys Chem C. 2020;124(27):14696-14705.

[35] ZhuC, ZhangZ, ZhongL, et al. Product-specific active site motifs of Cu for electrochemical CO₂ reduction. Chem. 2021;7(2):406-420.

[36] HuQ, GaoK, WangX, et al. Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction. Nat Commun. 2022;13(1):3958.

[37] LiL, YuanK, ChenY. Breaking the scaling relationship limit: from single-atom to dual-atom catalysts. Acc Mater Res. 2022;3(6):584-596.

[38] LiA, BrodMK, WangY, et al. Opening the bandgap of metallic Half-Heuslers via the introduction of d–d orbital interactions. Adv Sci. 2023:e2302086.

[39] CaoY, WangD, LinY, et al. Single Pt atom with highly vacant d-orbital for accelerating photocatalytic H₂ evolution. ACS Appl Energy Mater. 2018;1(11):6082-6088.

[40] LiF, HanGF, NohHJ, et al. Balancing hydrogen adsorption/ desorption by orbital modulation for efficient hydrogen evolution catalysis. Nat Commun. 2019;10(1):4060.

[41] WangG, JiangX-L, JiangY-F, Wang Y-G, LiJ. Screened Fe₃ and Ru₃ single-cluster catalysts anchored on MoS₂ supports for selective hydrogenation of CO₂. ACS Catal. 2023;13: 8413-8422.

[42] DongY, GhumanKK, PopescuR, et al. Solar fuels: tailoring surface frustrated Lewis pairs of In₂O_3–x(OH)_y for gas-phase heterogeneous photocatalytic reduction of CO₂ by isomorphous substitution of In³⁺ with Bi³⁺. Adv Sci. 2018;5(6):1700732.

[43] ZhouQ, LiaoL, BianQ, et al. Engineering in-plane nickel phosphide heterointerfaces with interfacial sp H–P hybridization for highly efficient and durable hydrogen evolution at 2 A cm⁻². Small. 2022;18(4):2105642.

[44] HaoY, WangY-T, XuL-C, Yang Z, LiuR-p, LiX-y. 1T-MoS₂ monolayer doped with isolated Ni atoms as highly active hydrogen evolution catalysts: a density functional study. Appl Surf Sci. 2019;469:292-297.

[45] BiswasR, Dastider SG, AhmedI, BaruaS, MondalK, HaldarKK. Unraveling the role of orbital interaction in the electrochemical HER of the trimetallic AgAuCu nanobowl catalyst. J Phys Chem Lett. 2023;14(13):3146-3151.

[46] ZhangF, YiD, WangX, Li S. Orbital orientation-based theoretical design of single-atom catalysts for the hydrogen evolution reaction. J Phys Chem C. 2022;126(39):16656-16662.

[47] TianD, SongX, QiuY, et al. Basal-plane-activated molybdenum sulfide nanosheets with suitable orbital orientation as efficient electrocatalysts for lithium–sulfur batteries. ACS Nano. 2021;15(10):16515-16524.

[48] YangC, ZhuY, LiuJ, et al. Defect engineering for electrochemical nitrogen reduction reaction to ammonia. Nano Energy. 2020;77:105126.

[49] FengJ, WuL, LiuS, et al. Improving CO₂-to-C₂₊ product electroreduction efficiency via atomic lanthanide dopantinduced tensile-strained CuO_x catalysts. J Am Chem Soc. 2023;145(17):9857-9866.

[50] WangX, TongY, FengW, et al. Embedding oxophilic rareearth single atom in platinum nanoclusters for efficient hydrogen electro-oxidation. Nat Commun. 2023;14(1):3767.

[51] NaghaviSS, EmeryAA, HansenHA, Zhou F, OzolinsV, WolvertonC. Giant onsite electronic entropy enhances the performance of ceria for water splitting. Nat Commun. 2017;8(1):285.

[52] ChuehWC, FalterC, AbbottM, et al. High-flux solar-driven thermochemical dissociation of CO₂ and H₂O using non-stoichiometric ceria. Science. 2010;330(6012):1797-1801.

[53] ZhangL, LiuC, WangL, Liu C, WangK, ZouB. Pressureinduced emission enhancement, band-gap narrowing, and metallization of halide perovskite Cs₃Bi₂I₉. Angew Chem Int Ed. 2018;57(35):11213-11217.

[54] LiuS, LiZ, WangC, et al. Turning main-group element magnesium into a highly active electrocatalyst for oxygen reduction reaction. Nat Commun. 2020;11(1):938.

[55] WangH, ZhaoY, LiJ, et al. Boosting the acidic oxygen reduction activity of p-block single-atomic catalyst via p–p orbital coupling and pore engineering. Small Struct. 2023;4(9):2300007.

[56] WangT, CaoX, QinH, et al. P-block atomically dispersed antimony catalyst for highly efficient oxygen reduction reaction. Angew Chem Int Ed. 2021;60(39):21237-21241.

[57] DuanJ, LiuT, ZhaoY, et al. Active and conductive layer stacked superlattices for highly selective CO₂ electroreduction. Nat Commun. 2022;13(1):2039.

[58] YueX, ChengL, LiF, FanJ, XiangQ. Highly strained Bi-MOF on bismuth oxyhalide support with tailored intermediate adsorption/desorption capability for robust CO₂ photore-duction. Angew Chem Int Ed. 2022;61(40):e202208414.

[59] HaoY-C, GuoY, ChenL-W, et al. Promoting nitrogen electroreduction to ammonia with bismuth nanocrystals and potassium cations in water. Nat Catal. 2019;2(5):448-456.

[60] WangK, HuangB, LinF, et al. Wrinkled Rh₂P nanosheets as superior pH-universal electrocatalysts for hydrogen evolution catalysis. Adv Energy Mater. 2018;8(27):1801891.

[61] ZhangY, KangC, ZhaoW, et al. d-p hybridization-induced “trapping-coupling-conversion” enables high-efficiency Nb single-atom catalysis for Li–S batteries. J Am Chem Soc. 2023;145(3):1728-1739.

[62] HungSF, ChanYT, ChangCC, et al. Identification of stabilizing high-valent active sites by operando high-energy resolution fluorescence-detected x-ray absorption spectroscopy for high-efficiency water oxidation. J Am Chem Soc. 2018;140:17263.

[63] BhagatBR, Dashora A. Understanding the synergistic effect of co-loading and B-doping in g-C₃N₄ for enhanced photocatalytic activity for overall solar water splitting. Carbon. 2021;178:666.

[64] SunM, Dougherty AW, HuangB, LiY, YanCH. Accelerating atomic catalyst discovery by theoretical calculationsmachine learning strategy. Adv Energy Mater. 2020;10(12):1903949.

[65] LvZ, LiZ, LiuH, et al. Simultaneously enhancing adsorbed hydrogen and dinitrogen to enable efficient electrochemical NH₃ synthesis on Sm(OH)₃. Small Struct. 2023;4(11):2300158.

[66] LiuX, MiJ, ShiL, et al. In situ modulation of A-site vacancies in LaMnO_3.15 perovskite for surface lattice oxygen activation and boosted redox reactions. Angew Chem Int Ed. 2021;60(51):26747-26754.

[67] TongW, HuangB, WangP, Li L, ShaoQ, HuangX. Crystalphase-engineered PdCu electrocatalyst for enhanced ammonia synthesis. Angew Chem Int Ed. 2020;59(7): 2649-2653.

[68] WangY, ParkBJ, PaidiVK, et al. Precisely constructing orbital coupling-modulated dual-atom Fe pair sites for synergistic CO₂ electroreduction. ACS Energy Lett. 2022;7(2):640-649.

[69] ZengL, ChenY, SunM, et al. Cooperative Rh-O₅/Ni(Fe) site for efficient biomass upgrading coupled with H₂ production. J Am Chem Soc. 2023;145(32):17577-17587.

[70] SunM, WuT, DoughertyAW, et al. Self-validated machine learning study of graphdiyne-based dual atomic catalyst. Adv Energy Mater. 2021;11:2003796.

[71] ChengL, YueX, WangL, et al. Dual-single-atom tailoring with bifunctional integration for high-performance CO₂ photoreduction. Adv Mater. 2021;33:2105135.

[72] ZhangS, WuJ, ZhengM, et al. Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia. Nat Commun. 2023;14:3634.

[73] LiuJ, TangC, KeZ, et al. Optimizing hydrogen adsorption by d-d orbital modulation for efficient hydrogen evolution catalysis. Adv Energy Mater. 2022;12:2103301.

[74] ChengL, YueX, FanJ, XiangQ. Site-specific electron-driving observations of CO₂-to-CH₄ photoreduction on co-doped CeO₂/crystalline carbon nitride S-scheme heterojunctions. Adv Mater. 2022;34:2200929.

[75] HaoY, WangL, HuangLF. Lanthanide-doped MoS₂ with enhanced oxygen reduction activity and biperiodic chemical trends. Nat Commun. 2023;14:3256.

[76] WangY, ChenJ, ChenL, Li Y. Breaking the linear scaling relationship of the reverse water–gas–shift reaction via construction of dual-atom Pt–Ni pairs. ACS Catal. 2023;13:3735.

[77] WangX, WangJ, WangP, et al. Engineering 3d–2p–4f gradient orbital coupling to enhance electrocatalytic oxygen reduction. Adv Mater. 2022;34(42):2206540.

[78] ShanY, GaoQ, ZhuY, WangY, WuS, LiT. Indirect orbital hybridization induced by nonbonding interaction at Liintercalated IrO₂ monolayers for oxygen evolution reaction. Phys Status Solidi Rapid Res Lett. 2023;17(10):2300093.

[79] LaiJ, HuangB, ChaoY, Chen X, GuoS. Strongly coupled nickel–cobalt nitrides/carbon hybrid nanocages with Pt-like activity for hydrogen evolution catalysis. Adv Mater. 2019;31(2):1805541.

[80] QiaoW, XuW, XuX, WuL, YanS, WangD. Construction of active orbital via single-atom cobalt anchoring on the surface of 1T-MoS₂ basal plane toward efficient hydrogen evolution. ACS Appl Energy Mater. 2020;3:2315-2322.

[81] HuB, WangB, BaiZ, et al. Regulating MoS₂ edge site for photocatalytic nitrogen fixation: a theoretical and experimental study. Chem Eng J. 2022;442:136211.

[82] SunZ, LinL, HeJ, et al. Regulating the spin state of Fe^III enhances the magnetic effect of the molecular catalysis mechanism. J Am Chem Soc. 2022;144(18):8204-8213.

[83] TianB, ShinH, LiuS, et al. Double-exchange-induced in situ conductivity in nickel-based oxyhydroxides: an effective descriptor for electrocatalytic oxygen evolution. Angew Chem Int Ed. 2021;60(30):16448-16456.

[84] LiZ, MaR, JuQ, et al. Spin engineering of single-site metal catalysts. Innovation. 2022;3(4):100268.

[85] SunY, SunS, YangH, Xi S, GraciaJ, XuZJ. Spin-related electron transfer and orbital interactions in oxygen electrocatalysis. Adv Mater. 2020;32(39):2003297.

[86] LiX, CaoC-S, HungS-F, et al. Identification of the electronic and structural dynamics of catalytic centers in single-Featom material. Chem. 2020;6(12):3440-3454.

[87] LiR, GuoW. Screening of transition metal single-atom catalysts supported by a WS₂ monolayer for electrocatalytic nitrogen reduction reaction: insights from activity trend and descriptor. Phys Chem Chem Phys. 2022;24(21):13384-13398.

[88] ZhangE, WangT, YuK, et al. Bismuth single atoms resulting from transformation of metal–organic frameworks and their use as electrocatalysts for CO₂ reduction. J Am Chem Soc. 2019;141(42):16569-16573.

[89] CaoS, WeiS, WeiX, et al. Can N, S cocoordination promote single atom catalyst performance in CO₂ RR? Fe-N₂S₂ porphyrin versus Fe-N₄ porphyrin. Small. 2021;17(29):2100949.

[90] GuoX, GuJ, LinS, ZhangS, ChenZ, Huang S. Tackling the activity and selectivity challenges of electrocatalysts toward the nitrogen reduction reaction via atomically dispersed biatom catalysts. J Am Chem Soc. 2020;142(12):5709-5721.

[91] WangZ, WangW, WangJ, et al. Single-atom catalysts with ultrahigh catalase-like activity through electron filling and orbital energy regulation. Adv Funct Mater. 2022;33:2209560.

[92] ComerBM, LiJ, Abild-PedersenF, BajdichM, Winther KT. Unraveling electronic trends in O* and OH* surface adsorption in the MO₂ transition-metal oxide series. J Phys Chem C. 2022;126:7903.

[93] SanadMF, Puente Santiago AR, TolbaSA, et al. Co–Cu bimetallic metal organic framework catalyst outperforms the Pt/C benchmark for oxygen reduction. J Am Chem Soc. 2021;143:4064.

[94] GuY, XiBJ, ZhangH, Ma YC, XiongSL. Activation of main-group antimony atomic sites for oxygen reduction catalysis. Angew Chem Int Ed. 2022;61:202202200.

[95] YuJ, YongX, LuS. p-d orbital hybridization engineered single-atom catalyst for electrocatalytic ammonia synthesis. Energy Environ Mater. 2023;0:e12587.

[96] ZhaoKM, LiuS, LiYY, et al. Insight into the mechanism of axial ligands regulating the catalytic activity of Fe–N₄ sites for oxygen reduction reaction. Adv Energy Mater. 2022;12(11):2103588.

[97] XieY, CaiJ, WuY, et al. Water splitting: boosting water dissociation kinetics on Pt–Ni nanowires by N-induced orbital tuning. Adv Mater. 2019;31(16):1807780.

[98] HanJ, AnP, LiuS, et al. Reordering d orbital energies of single-site catalysts for CO₂ electroreduction. Angew Chem Int Ed. 2019;58(36):12711-12716.

[99] Calle-VallejoF, InogluNG, SuH-Y, et al. Number of outer electrons as descriptor for adsorption processes on transition metals and their oxides. Chem Sci. 2013;4(3):1245.

[100] ZhouG, WangP, HuB, et al. Spin-related symmetry breaking induced by half-disordered hybridization in Bi_xEr_2-xRu₂O₇ pyrochlores for acidic oxygen evolution. Nat Commun. 2022;13(1):4106.

[101] ZangY, NiuS, WuY, et al. Tuning orbital orientation endows molybdenum disulfide with exceptional alkaline hydrogen evolution capability. Nat Commun. 2019;10(1):1217.

[102] SuntivichJ, MayKJ, GasteigerHA, Goodenough JB, Shao-HornY. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science. 2011;334(6061):1383-1385.

[103] SuntivichJ, Gasteiger HA, YabuuchiN, NakanishiH, Goodenough JB, Shao-HornY. Design principles for oxygenreduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries. Nat Chem. 2011;3(7):546-550.

[104] XiaD, YangX, XieL, et al. Direct growth of carbon nanotubes doped with single atomic Fe–N₄ active sites and neighboring graphitic nitrogen for efficient and stable oxygen reduction electrocatalysis. Adv Funct Mater. 2019;29:1906174.

[105] ZhangL, RenX, ZhaoX, et al. Synergetic charge transfer and spin selection in CO oxidation at neighboring magnetic single-atom catalyst sites. Nano Lett. 2022;22:3744.

[106] HammerB, Norskov JK. Why gold is the noblest of all the metals. Nature. 1995;376(6537):238-240.

[107] NorskovJK, Abild-Pedersen F, StudtF, BligaardT. Density functional theory in surface chemistry and catalysis. Proc Natl Acad Sci USA. 2011;108(3):937-943.

[108] WeiC, SunY, SchererGG, et al. Surface composition dependent ligand effect in tuning the activity of nickel–copper bimetallic electrocatalysts toward hydrogen evolution in alkaline. J Am Chem Soc. 2020;142(17):7765-7775.

[109] DaiL, YaoF, YuL, et al. Boosting alkaline hydrogen evolution on stoichiometric molybdenum carbonitride via an interstitial vacancy-elimination strategy. Adv Energy Mater. 2022;12(25):2200974.

[110] HeS, NiF, JiY, et al. The p-orbital delocalization of maingroup metals to boost CO₂ electroreduction. Angew Chem Int Ed. 2018;57(49):16114-16119.

[111] WangJ, ZhangZ, SongH, et al. Water dissociation kineticoriented design of nickel sulfides via tailored dual sites for efficient alkaline hydrogen evolution. Adv Funct Mater. 2021;31(9):2008578.

[112] WangX, LuL, WangB, et al. Frustrated Lewis pairs accelerating CO₂ reduction on oxyhydroxide photocatalysts with surface lattice hydroxyls as a solid-state proton donor. Adv Funct Mater. 2018;28(43):1804191.

[113] BhattacharjeeS, Waghmare UV, LeeSC. An improved d-band model of the catalytic activity of magnetic transition metal surfaces. Sci Rep. 2016;6(1):35916.

[114] XinH, Vojvodic A, VossJ, NøskovJK, Abild-Pedersen F. Effects of d-band shape on the surface reactivity of transitionmetal alloys. Phys Rev B. 2014;89(11):115114.

[115] BuL, ShaoQ, PiY, et al. Coupled s-p-d exchange in facetcontrolled Pd3Pb tripods enhances oxygen reduction catalysis. Chem. 2018;4(2):359-371.

[116] ZhouY, SunS, SongJ, et al. Enlarged Co–O covalency in octahedral sites leading to highly efficient spinel oxides for oxygen evolution reaction. Adv Mater. 2018;30(32):1802912.

[117] GreeleyJ, Stephens IE, BondarenkoAS, et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat Chem. 2009;1(7):552-556.

[118] YangH, KoY, LeeW, Züttel A, KimW. Nitrogen-doped carbon black supported Pt–M (M = Pd, Fe, Ni) alloy catalysts for oxygen reduction reaction in proton exchange membrane fuel cell. Mater Today Energy. 2019;13:374-381.

[119] LuY, JiangY, GaoX, WangX, ChenW. Strongly coupled Pd nanotetrahedron/tungsten oxide nanosheet hybrids with enhanced catalytic activity and stability as oxygen reduction electrocatalysts. J Am Chem Soc. 2014;136(33):11687-11697.

[120] DongY, CaiD, LiT, et al. Sulfur reduction catalyst design inspired by elemental periodic expansion concept for lithium-sulfur batteries. ACS Nano. 2022;16(4):6414-6425.

[121] AlkhalifahMA, Howchen B, StaddonJ, CelorrioV, TiwariD, FerminDJ. Correlating orbital composition and activity of LaMn_xNi_1-xO₃ nanostructures toward oxygen electrocatalysis. J Am Chem Soc. 2022;144(10):4439-4447.

[122] GeX, CaoY, YanK, et al. Increasing the distance of adjacent palladium atoms for configuration matching in selective hydrogenation. Angew Chem Int Ed. 2022;61(51):e202215225.

[123] ZhangD, Prezhdo OV, XuL. Design of a four-atom cluster embedded in carbon nitride for electrocatalytic generation of multi-carbon products. J Am Chem Soc. 2023;145(12): 7030-7039.

[124] ChattotR, Le Bacq O, BeermannV, et al. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Nat Mater. 2018;17(9):827-833.

RIGHTS & PERMISSIONS

2024 2024 The Authors. Electron published by Harbin Institute of Technology and John Wiley & Sons Australia, Ltd.