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Kaidi Zhang, Yun Yu, Stephen Carr, Mohammad Babar, Ziyan Zhu, Bryan Junsuh Kim, Catherine Groschner, Nikta Khaloo, [Takashi Taniguchi](https://orcid.org/0000-0002-1467-3105), [Kenji Watanabe](https://orcid.org/0000-0003-3701-8119), Venkatasubramanian Viswanathan, D. Kwabena Bediako

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[Anomalous Interfacial Electron-Transfer Kinetics in Twisted Trilayer Graphene Caused by Layer-Specific Localization](https://mdr.nims.go.jp/datasets/49e0d9ed-99d9-4fd1-a95b-94cd0e70f97e)

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Anomalous Interfacial Electron-Transfer Kinetics in Twisted Trilayer Graphene Caused by Layer-Specific LocalizationAnomalous Interfacial Electron-Transfer Kinetics in Twisted TrilayerGraphene Caused by Layer-Specific LocalizationKaidi Zhang, Yun Yu, Stephen Carr, Mohammad Babar, Ziyan Zhu, Bryan Junsuh Kim,Catherine Groschner, Nikta Khaloo, Takashi Taniguchi, Kenji Watanabe,Venkatasubramanian Viswanathan, and D. Kwabena Bediako*Cite This: ACS Cent. Sci. 2023, 9, 1119−1128 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Interfacial electron-transfer (ET) reactions under-pin the interconversion of electrical and chemical energy. It isknown that the electronic state of electrodes strongly influencesET rates because of differences in the electronic density of states(DOS) across metals, semimetals, and semiconductors. Here, bycontrolling interlayer twists in well-defined trilayer graphenemoireś, we show that ET rates are strikingly dependent onelectronic localization in each atomic layer and not the overallDOS. The large degree of tunability inherent to moire ́ electrodesleads to local ET kinetics that range over 3 orders of magnitudeacross different constructions of only three atomic layers, evenexceeding rates at bulk metals. Our results demonstrate thatbeyond the ensemble DOS, electronic localization is critical infacilitating interfacial ET, with implications for understanding the origin of high interfacial reactivity typically exhibited by defects atelectrode−electrolyte interfaces.■ INTRODUCTIONElectron-transfer (ET) reactions at electrode−electrolyteinterfaces are fundamental to electrochemical energy con-version.1−3 The collective of microscopic theories and modelsfor interfacial ET, inclucing the Marcus−Gerischer formal-ism,4−9 the so-called Marcus−Hush−Chidsey (MHC)model,10,11 and the density of states (DOS)−incorporatedMHC (MHC−DOS) model,12 highlight the importance of theelectronic structure of an electrode on heterogeneous electro-chemical rates. These frameworks motivate the discovery ofnew approaches to manipulate the band structure of electrodesas a means of controlling the performance limits of energyconversion and storage devices. Even though the electrodeDOS was originally treated as invariant with energy/over-potential and delocalized, recent work has shown that theenergy-dependence of the DOS can be an important factor inelectrochemical reactions.12 Furthermore, the effect of localDOS beyond the global electrode DOS has been identified ascritical in understanding interfacial ET kinetics. On semi-conductor or semimetallic electrodes, local electronic structuredifferences have been shown to affect ET kinetics,13 andatomic defects at electrode surfaces provide a striking, albeitchallenging to control, example of the pronounced effect oflocal structural/electronic modifications on interfacial reac-tivity. Atomic vacancies,14 kinks, and step edges15−17 aretypically associated with massively enhanced interfacialreactivity compared to atomically pristine surfaces. The effectof these defects is typically explained in the context ofproviding increased DOS at energies that are desirable forcharge transfer or the formation of a surface-bound catalyticintermediate (such as midgap states in a semiconductingmaterial.14,15) However, the dangling bonds at such sites wouldinvariably introduce a strong spatial localization of these largeelectronic DOS. For this reason, beyond the augmented DOSmagnitude, we might consider that localization may play a keyrole in facilitating interfacial ET to the necessarily localizedelectronic states on the solution-phase molecule/complex/ion.However, a systematic experimental examination of the effectsof electronic localization on heterogeneous interfacial chargetransfer has been intractable owing to the considerablesynthetic challenge of constructing pristine electrode materialsthat would allow a deterministic modulation of this propertyseparate from the overall DOS.Azimuthal misalignment of atomically thin layers producesmoire ́ superlattices and alters the electronic band structure, inReceived: March 17, 2023Published: May 15, 2023Research Articlehttp://pubs.acs.org/journal/acscii© 2023 The Authors. Published byAmerican Chemical Society1119https://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−1128Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on July 1, 2023 at 01:11:29 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kaidi+Zhang"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yun+Yu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Stephen+Carr"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mohammad+Babar"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Ziyan+Zhu"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Bryan+Junsuh+Kim"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Catherine+Groschner"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Catherine+Groschner"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Nikta+Khaloo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Takashi+Taniguchi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Kenji+Watanabe"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Venkatasubramanian+Viswanathan"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Venkatasubramanian+Viswanathan"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="D.+Kwabena+Bediako"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acscentsci.3c00326&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/acscii/9/6?ref=pdfhttps://pubs.acs.org/toc/acscii/9/6?ref=pdfhttps://pubs.acs.org/toc/acscii/9/6?ref=pdfhttps://pubs.acs.org/toc/acscii/9/6?ref=pdfhttp://pubs.acs.org/journal/acscii?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://http://pubs.acs.org/journal/acscii?ref=pdfhttps://http://pubs.acs.org/journal/acscii?ref=pdfhttps://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/https://acsopenscience.org/open-access/licensing-options/a manner that is systematically dependent on the interlayertwist angle.18,19 The formation of flat electronic bands,particularly at a series of “magic” moire ́ angles, leads to adiversity of correlated electron physics.20−23 Notably, these flatbands imply a large DOS that is highly localized in real space.24Small-angle twisted bilayer graphene (TBG) exhibits recentlydiscovered angle-dependent electrochemical behavior,25 whereouter-sphere ET kinetics can be tuned nearly 10-fold simply byvarying the moire ́ twist angle, θm, between 0 and 2°.The stacking order of graphene in multilayers strongly altersthe resulting electronic properties of the system.21,26−34 Asshown in SI Figure 1, whereas Bernal (ABA-stacked) trilayergraphene displays dispersive bands, rhombohedral (ABC)graphene possesses a nondispersive, or “flat”, electronic bandclose to the Fermi level, which is responsible for the emergenceof correlated electron phenomena at low temperatures.35,36More pronounced flat bands are produced in twisted trilayergraphene (TTG) structures. A rotationally misaligned (by amoire ́ “twist” angle θm) monolayer and a Bernal stacked bilayerform a “monolayer-twist-bilayer” (M-t-B) heterostructure(Figure 1A).37,38 Systematically alternating the angle betweenadjacent graphene layers such that the top layer is perfectlyaligned with the bottom layer results in an “A-t-A”heterostructure (Figure 1B)21,27,34 that possesses extremelyflat bands at a magic angle of around 1.5° (SI Figure 1). Theseflattened electronic bands, which manifest as a large DOS thatis localized on AAB and AAA sites in M-t-B and A-t-A TTG,respectively (Figure 1C,D), now introduce distinctivepossibilities for systematically probing the dependence ofinterfacial ET on electronic structure generally and, inparticular, the effects of electronic localization. For example,even within the TTG family, larger DOSs are found in A-t-A ascompared to M-t-B near their respective magic angles (Figure1C,D), properties that naively might be expected to correlatewith interfacial ET rates, based on the MHC model.■ RESULTS AND DISCUSSIONScanning electrochemical cell microscopy (SECCM)17 meas-urements were carried out on nontwisted (ABA, ABC) andtwisted trilayer graphene samples that were fabricated intodevices (see Materials and Methods).25 As shown in Figure 2A,naturally occurring ABA and ABC trilayers were mechanicallyexfoliated from bulk graphite and identified using opticalmicroscopy together with confocal Raman spectroscopy (seeMaterials and Methods and Supporting Information).39,40 M-t-B and A-t-A TTG samples were prepared by the “cut-and-stack” approach (see Materials and Methods), resulting insamples possessing uniform θm around the magic angles ofabout 1.34° for an M-t-B device and 1.53° for an A-t-A device.Piezoelectric force microscopy (PFM) and scanning tunnelingmicroscopy (STM) were used to evaluate the twist angledistribution and uniformity across the moire ́ samples (Figure2B).41 Using SECCM, cyclic voltammograms (CVs) weremeasured with 2.0 mM Ru(NH3)63+−an ideal and well-established redox couple for interrogating outer-sphere ETkinetics16,25−and 0.10 M KCl as the supporting electrolyte. InFigure 2C, a representative set of CVs collected from thesedifferent trilayer samples is shown. We find that the ABAdomain of the flake shown in Figure 2A exhibited the mostsluggish rates of Ru(NH3)63+ electro-reduction, as evinced by ahalf-wave potential (E1/2) of −0.32 V, which is cathodicallyshifted substantially from the equilibrium potential, E0, of−0.25 V for Ru(NH3)63+/2+ (all potentials are reported relativeto the Ag/AgCl quasi-counter/reference electrode). However,the E1/2 measured from the CV acquired in region II (ABCdomain) of the same flake was −0.27 V, pointing toconsiderably more facile electroreduction kinetics on therhombohedral trilayer as compared to the Bernal trilayer. Forboth TTG samples, reversible CVs with E1/2 ≈ −0.25 V wereobtained, indicative of highly facile electrokinetics andheterogeneous electrochemical rate constants that exceedthose of both ABA and ABC graphene considerably. Theseobservations motivated the measurement of the variation ofinterfacial ET rates with θm.To quantitatively assess differences in interfacial kineticsassociated with disparate electronic structures, we comparedexperimental CVs to those simulated with different standardrate constants, k0, calculated with the Butler−Volmer model(see Materials and Methods and the Supporting Information).Here, it is critical to account for the relatively small andpotential-dependent quantum capacitance, Cq (see Materialsand Methods and Supporting Information)16,25 in these low-dimensional electrodes, which for a given applied potential,Vapp, produces a dynamic electron or hole doping of the few-layer graphene by an energy of eVq (where e is the elementarycharge and Vq is the chemical potential relative to the chargeneutrality potential). The remainder, Vdl, persists as a dropacross the electric double layer (so that Vapp = Vq + Vdl).Cq(Vq) was calculated for all trilayer systems (ABA and ABC aswell as M-t-B and A-t-A at various θm values) (Figure 3A)using the respective computed band structures and DOSprofiles (see Materials and Methods). The corresponding plotsof Vdl/Vapp as a function of Vapp are shown in Figure 3B. TakenFigure 1. Polytypes of twisted trilayer graphene. (A, B) Illustrations oftwo twisted trilayer graphene polytypes, with moire ́ wavelength λ. Theblack parallelogram outlines the moire ́ unit cell in each case. (C, D)Computed local DOS (see Materials and Methods) for 1.2° M-t-B(C) and 1.5° A-t-A (D).ACS Central Science http://pubs.acs.org/journal/acscii Research Articlehttps://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−11281120https://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig1&ref=pdfhttp://pubs.acs.org/journal/acscii?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-astogether, these data reveal that flat electronic bands result in amore significant fraction of Vapp partitioning into Vdl near thecharge neutrality potential. Notably, as shown in Figure 3A,changes in θm tune Cq(Vq) and magic-angle (∼1.5°) A-t-Adisplays a higher Cq than magic-angle (1.2−1.3°) M-t-B,consistent with its overall greater DOS (Figure 1D).After determining Vdl in this manner, we extracted k0 valuesby identifying the simulated CV that was in closest agreementwith the experiment25 (see Materials and Methods andSupporting Information). The θm dependence of k0 wasmeasured by preparing M-t-B TTG devices with varying θmbetween 0.08 and 8.0° (see Materials and Methods) andacquiring CVs of Ru(NH3)63+ electroreduction by SECCM foreach sample. Figure 3C shows the strong, nonmonotonicvariation in k0 over 2 orders of magnitude from ABA and ABCgraphene to θm = 8° M-t-B. For samples with 1° ≤ θm ≤ 2°, ETappears to be reversible within our accessible scan rates, so wecannot extract any kinetic information beyond noting thatwithin this range of θm, k0 ≥ 0.35 cm/s. The quencheddependence of θm on k0 (blue markers in Figure 3C) inanalogous electrochemical measurements of the trisphenan-throline cobalt(III/II) redox couple, Co(phen)33+/2+ (seeFigure 2. Fabrication and electrochemistry of twisted trilayer graphene. (A) Left: Optical micrograph of a device fabricated from an exfoliatedtrilayer graphene flake on hBN. Right: Confocal Raman spectra acquired in the sites in A marked with red (ABC domain) and blue (ABA domain)dots, along with the Raman map of the region indicated with a yellow box in A. Scale bars: 10 μm. (B) Left: Optical micrograph of an M-t-B deviceon hBN (Scale bar: 10 μm). Right: A lateral PFM phase image over the yellow boxed region in B reveals the moire ́ superlattice pattern. Scale bar:50 nm. (C) Representative steady-state voltammograms of 2 mM Ru(NH3)63+ in 0.1 M KCl solution obtained at ABA and ABC trilayer graphene,along with 1.3° M-t-B and 1.5° A-t-A, compared to that obtained at an ∼40-nm-thick platinum film. Scan rate, 100 mV s−1. The inset illustrates theSECCM technique.Figure 3. Angle-dependent quantum capacitance and interfacial ET. (A) Calculated Cq as a function of the chemical potential (Vq) for ABA, ABC,and TTG using the respective computed band structures and DOS profiles (see Materials and Methods). (B) Calculated fraction of appliedpotential on the double layer (Vdl/Vapp) as a function of the applied potential (Vapp) for ABA, ABC, and TTG. Vq and Vapp are relative to the chargeneutrality potential. Taken together, these data reveal that flat electronic bands result in a more significant fraction of Vapp partitioning into Vdl nearthe charge neutrality potential. (C) Dependence of the ET rate constant, k0, on the trilayer graphene stacking type (ABA, ABC) and θm for M-t-BTTG. Each marker denotes the mean of measurements made on samples within a standard deviation of the mean twist angle. The horizontal andvertical error bars represent the standard deviations of θm and the standard error of k0. The inset shows comparison of k0 values for M-t-B, B-t-M,and A-t-A TTG at θm = 0.82 ± 0.05°.ACS Central Science http://pubs.acs.org/journal/acscii Research Articlehttps://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−11281121https://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig3&ref=pdfhttp://pubs.acs.org/journal/acscii?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asMaterials and Methods and Supporting Information) providescompelling evidence that it is the moire ́ flat bands that drivethe observed angle-dependent electrokinetic modulation inTTG, as in TBG.25An unexpected observation of the factors controllinginterfacial ET is made by comparing the electrochemicalresponses of TTG polytypes. A-t-A TTG, on the basis of itsmassive DOS (SI Figure 1 and Figure 1D) and giant Cq−whichexceeds that of M-t-B (Figure 3A)−should be expected to yieldthe highest ET rates. However, while an effect of θm on k0 isalso observed in A-t-A samples (see Supporting InformationTable 1), this variant of TTG displays consistently lower k0than M-t-B at similar θm values (Figure 3C, inset).Furthermore, B-t-M heterostructures, which consist of a Bernalbilayer placed with a twist atop a monolayer (i.e., flippedversions of M-t-B), display markedly lower k0 values than thecorresponding M-t-B electrodes, notwithstanding an ostensiblyidentical overall electronic structure. These striking observa-tions point clearly to effects governing the interfacial ETkinetics beyond simply the ensemble DOS.To fully understand these θm dependencies as well as thedisparities among the interfacial electron transfer kinetics of M-t-B, B-t-M, and A-t-A, we used STM (room temperature,constant current) to evaluate the role of lattice relaxation incontrolling the area fraction of stacking domains in M-t-B andA-t-A TTG. In Figure 4A, a representative STM map of small-angle (θm = 0.14°) M-t-B shows a clear contrast among thevarious stacking domains. Regions with higher local DOSappear brighter than those with lower DOS since a larger tip−sample distance is required to maintain a constant current.38ABC domains, therefore, appear brighter than ABA domainsowing to the native flat band of the ABC stacking type (SIFigure 1). These ABA and ABC domains (black and redregions, respectively) form alternating triangular patterns whilethe AAB region forms small circles of diameter ∼11 nm, whichappear with the brightest contrast owing to the localization ofthe moire ́ flat band and associated large DOS on these AABsites as shown in Figure 1C and SI Figure S2 (this is analogousto the localization of moire ́ flat bands on AA sites in TBG24).For θm = 0.78° (Figure 4B), while the triangular ABA/ABCpatterns have shrunk in size compared to those in Figure 4A,the diameters of AAB regions remained largely unchanged. ForA-t-A, AAA domains are visible as bright spots (Figure 4D,E),consistent with the localization of the large DOS on theseregions (Figure 1D and SI Figure 2),42 with degenerate ABAand BAB regions requiring smaller tip−sample distances (darkregions) to sustain a constant STM current because of a lowerlocal DOS.The measured area distribution of stacking domains in TTG,therefore, differs significantly from those of rigid moire ́structures. Both structures relax as depicted schematically inFigure 4C,F minimizing (maximizing) high (low) energydomains in a manner that is conceptually analogous to thatreported for TBG.24,43,44 To support these experiments, wealso performed finite element method (FEM) simulations tomodel relaxation in TTG (see SI Figure 3 and SupportingInformation), finding results that lie in good agreement withour STM and dark-field transmission electron microscopy (SIFigure 4) data. Importantly, these structural measurements andcalculations permit a quantitative determination of the areafractions in TTG after reconstruction as a function of θm asplotted in Figure 4G (see also SI Figure 5 and SupportingInformation Table 2).These area fraction distributions after structural relaxationexplain the origin of the kinetic modulation observed in Figure3C at θm < 2° as being driven by θm-dependent area fractionsof the “topological defect”45,46 AAB and AAA sites. Ourrelaxation simulations (SI Figure 2) also show that at θm ≤ 0.3°the relaxation of these moire ́ superlattices reestablishes nearlycommensurate ABA, BAB, and/or ABC domains with localDOS that should not deviate substantially from those offreestanding ABA and ABC trilayers. This observation is in linewith previous experimental38,43,44,46 and theoretical studies46,47of lattice relaxation in bilayer analogues. Therefore, byconsidering k0 variations at θm < 1° in Figure 3C (which arealso within the range of kinetically resolvable k0), we canextract the local rate constant associated with the AAB andAAA stacking domains through eqs 1 and 2 where βi and κi0Figure 4. Lattice relaxation and stacking area fractions in TTG. (A, B, D, E) Constant-current STM images representative M-t-B (A, B) and A-t-A(D, E) samples. Scale bars: 50 nm. (C, D) Qualitative illustrations of different stacking domains in rigid and relaxed M-t-B (C) and A-t-A (F) moire ́unit cells. (G) Extracted area fraction of different stacking domains in M-t-B TTG. The horizontal and vertical error bars represent the standarddeviations of θm and the standard error of the area fraction, respectively.ACS Central Science http://pubs.acs.org/journal/acscii Research Articlehttps://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−11281122https://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig4&ref=pdfhttp://pubs.acs.org/journal/acscii?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asrepresent the area fraction and local standard heterogeneousET rate constant, respectively, for stacking domain i.= + + +kMtB AAB AAB ABC ABC ABA ABA SP SP0 0 0 0 0(1)= + + +kAtA AAA AAA ABA ABA BAB BAB SP SP0 0 0 0 0(2)As a result of the lattice relaxation effect discussed above, wecan determine κABA and κABC from independent measurementsof freestanding Bernal and rhombohedral trilayers (Figures 2Cand 3C). In addition, we can assume that κSP0 ≈ κABA0 , which isjustified on the basis of the STM images and calculated localDOS (see SI Figure 2). This analysis allows us to extractstandard electron-transfer rate constants for the AAB (M-t-B),ABB (B-t-M), and AAA (A-t-A) topological defects.Combined with previous electrochemical measurements atTBG surfaces,25 we compare the ET kinetics of Ru(NH3)63+/2+among a wide array of stacking configurations from monolayerto trilayer graphene in Figure 5A. For atomic stacking ordersnaturally found in bulk graphite, we observed a gradualenhancement as the number of layers increases from amonolayer to a Bernal trilayer. This can be explained by amodest increase in DOS close to the Fermi level as the numberof layers increases.16 ABC graphene displays a pronouncedaugmentation in k0 from that of ABA graphene due to theintrinsic flat band of the rhombohedral system (SI Figure 1).Most notably, “artificial” high-energy stacking (AA, AAA, AAB,and ABB) topological defects created by moire ́ superlatticesexhibit extraordinarily high k0 values, with that of AABexceeding 3 cm/s, which is greater than that measured on bulkplatinum electrodes (0.85−1.2 cm/s),48 notwithstandingconsisting of only three atomic layers (see also SupportingInformation Table 2).Figure 5A also shows the unexpected result that AAA sitesdisplay lower ET rates than AAB notwithstanding the higherDOS and Cq of AAA than those of AAB (SI Figure 1 andFigure 3A). Strikingly, we also find that ABB sites yield slowerET kinetics than both AAB (despite identical overall DOS)and AA (despite higher overall DOS). Thus, while in-planeelectronic localization and structural relaxation effects explainthe dependence of k0 on θm in TTG, the relative interfacial ETrates of AAB (M-t-B), ABB (B-t-M), and AAA (A-t-A) (Figure3C inset and Figure 5A) appear not to correlate with DOS.To explain these trends, Figure 5C−E shows layer-isolatedlocal DOS(ϵ) and Cq(ϵ) profiles (Figure 5C,E) at thetopological defects (AAB/ABB, AAA) along with calculatedreal-space DOS maps (insets in Figure 5C,E). SupportingInformation Figure 6 contains layer-dependent DOS at othertwist angles. These calculations show how the DOS enhance-ments at AAB sites are distinctly localized on the top twolayers of M-t-B structures (i.e., the “AA” portions of AAB).49 Incontrast, the DOSs at AAA sites are most strongly localized onthe middle layer of A-t-A. This three-dimensional electroniclocalization (within a thickness of only three atomic layers)arising from different symmetries of these topological defectsunveils the fundamental basis for the unexpected trends in ETrate constants at AAB, ABB, and AAA (Figures 3C and 5A):though the electrodes are only three atomic layers thick, ETrate constants are correlated only with the electronic propertiesprecisely at the electrode−electrolyte interface.Figure 5. ET rates of few-layer graphene and layer-dependent DOS localization. (A) Local standard Ru(NH3)63+/2+ ET rate constants at few-layergraphene in different stacking configurations. “Artificial” moire-́derived stacking domains are labeled with an asterisk. Each bar is the mean local rateeither measured (for natural stacking) or calculated (for aritifical stacking) for small twist angle samples. The error bars represent the standarderrors for the rates. (B) Schematic of M-t-B/B-t-M graphene layers. (C) Layer-dependent DOS profile (see Materials and Methods and SupportingInformation Text) for AAB stacking domains in M-t-B and B-t-M graphene at θm = 1.2°. Insets show real space DOS maps of each layer at ϵ = −3meV. (D) Schematic of the A-t-A layers. (E) Layer-dependent DOS profile for AAA stacking domains in A-t-A graphene at θm = 1.2°. The insetsshow real space DOS maps of each layer at ϵ = −1 meV for θm = 1.2°.ACS Central Science http://pubs.acs.org/journal/acscii Research Articlehttps://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−11281123https://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?fig=fig5&ref=pdfhttp://pubs.acs.org/journal/acscii?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asThese observations strongly hint at the role of interfacialelectronic coupling (between the localized states on theelectrode and the electron donor/acceptor in solution), electricdouble-layer effects, and/or interfacial reorganization energy aseven more crucial than the overall DOS alone. Indeed,theoretical calculations based on the MHC model thataccounts only for the θm-dependent DOS but with a couplingstrength, ν, and reorganization energy, λ, that are invariant withθm (see Supporting Information text and SI Figure 7) vastlyunderestimate the dependence of k0 on θm. These MHCcalculations also likewise predict identical interfacial ET ratesfor M-t-B and B-t-M, which is clearly at odds with theexperiment. Our experimental results, therefore, now motivatefuture theoretical work to adapt these MHC models toconsider how electronic localization, which is deterministicallytuned here by varying θm or TTG structure, modifies ν50 and/or λ51 to bridge the gap between theory and experiment andextend our microscopic understanding of interfacial ET.■ CONCLUSIONSControlling stacking geometries and twist angles in few-layergraphene, therefore, enables the manipulation of standard ETrate constants over 3 orders of magnitude. In particular,energetically unfavorable topological defects (AAA and AABstacking domains), which are attainable only through theconstruction of a moire ́ superlattice, exhibit extraordinarilyhigh standard rate constants. This electrochemical behaviorarises from the moire-́derived flat bands that are localized inthese topological defects. In addition to the effects of in-planestructural relaxation and electronic localization, the out-of-plane localization of the electron wave function on specificlayers of twisted trilayer graphene results in measurabledifferences in ET rates at topological defects possessingdifferent symmetries.These results provide a powerful demonstration of thesensitivity of interfacial ET kinetics to the three-dimensionallocalization of electronic states at electrochemical surfaces andraise the question of whether traditional measurements of ETrates at macroscopic electrodes might severely underestimatethe true local rate constant, which may be mediated by atomicdefects that strongly localize electronic DOS at theseinterfaces. In turn, SECCM measurements are shown to bepowerful tools for probing layer-dependent electronic local-ization in atomic heterostructure electrodes.Future experimental and theoretical work is needed to shedmore light on the microscopic origin of these electron-transfermodulations in the context of reorganization energy, electroniccoupling, and even the electric double-layer structure. Thiswork also heralds the use of moire ́ materials as a versatile andsystematically tunable experimental platform for theoreticaladaptations of the MHC framework applied to interfaces withlocalized electronic states, which are representative of defectivesurfaces that are ubiquitous to nearly all real electrochemicalsystems. In an applied context, twistronics is shown to be apowerful pathway for engineering pristine 2D material surfacesto execute charge-transfer processes with facile kinetics,holding implications for electrocatalysis52,53 and other energyconversion device schemes that could benefit from ultrathin,flexible, and/or transparent electrodes that retain highelectron-transfer kinetics.■ MATERIALS AND METHODSChemicals. Natural Kish graphite crystals were purchasedfrom Graphene Supermarket. Si/SiO2 wafers (0.5 mm thickwith 285 nm SiO2 or 90 nm SiO2) were purchased fromNOVA Electronic Materials. Polydimethylsiloxane (PDMS)stamps were purchased from MTI Corporation. Sn/In alloywas purchased from Custom Thermoelectric. Poly(bisphenolA carbonate) (Mw 45 000), dichlorodimethylsilane (>99.5%),hexaammineruthenium(III) chloride (98%), cobalt(II) chlor-ide hexahydrate (98%), 1,10-phenanthroline (>99%), calciumchloride (>93%), and potassium chloride (>99%) werepurchased from Sigma-Aldrich and used as received. Allaqueous electrolyte solutions were prepared with type I water(EMD Millipore, 18.2 MΩ cm resistivity). The 2 mM solutionsof tris(1,10-phenanthroline)cobalt(II) were prepared bydissolving 1:3 molar ratios of solid cobalt(II) chloride and1,10-phenanthroline in water. In both Ru(NH3)63+/2+ andCo(phen)33+ solutions, 0.1 M KCl was added as a supportingelectrolyte.Sample Fabrication. Graphite and hexagonal boronnitride (hBN) were exfoliated from the bulk crystals withScotch tape. Exfoliated films were surveyed with an opticalmicroscope (Laxco LMC-5000). Monolayer, bilayer, andtrilayer graphene were identified with their characteristicoptical contrasts of 7, 12, and 18%, respectively, in the greenchannel.54 Trilayer graphene films were further confirmed byRaman spectroscopy (HORIBA LabRAM Evo) of the 2D peak(around 2600−2700 cm−1).39 The 2D peak was used todistinguish different stacking domains (ABC/ABA) as ABCtrilayer graphene exhibits an enhanced shoulder at around2640 cm−1 (see Supporting Information text). Trilayergraphene and twisted trilayer graphene samples were fabricatedby the well-established “cut and stack” dry transfer method.25All transfers were carried out on a temperature-controlledheating stage (Instec), an optical microscope (MitutoyoFS70), and a micromanipulator (MP-285, Sutter Instrument).For monolayer twist bilayer or bilayer twist monolayersamples, graphene flakes with both bilayer and monolayerparts were carefully selected. The monolayer section wassevered from the bilayer with a scanning tunneling microscopy(STM) tip. For a-twist-a samples, a large piece of graphene(>50 μm by 20 μm) was cut evenly into three pieces. A thinpiece of poly(bisphenol A carbonate) (PC) film (∼3 × 3 mm2)attached to a PDMS chunk (∼7 × 7 mm2) was used to pick upan hBN (∼10−20 nm) from the SiO2/Si substrate at 120 °C.This hBN was carefully aligned with the bottom layer of thegraphene stack and lowered to pick up that piece. The stagewas rotated (usually to a slightly larger angle than the desiredtwist), and the second piece of graphene was overlapped by thealready picked-up graphene and thus delaminated from thesubstrate. For a-twist-a samples, a third piece of graphene waspicked up after the stage was rotated back to the originalorientation. A piece of graphite (∼20 nm, >50 μm × 50 μm)was then picked up such that it was connected to the graphene.The PC film was carefully removed from the PDMS and placedonto a clean SiO2/Si. In/Sn was painted onto the graphite viamicrosoldering55 to a metallic plate which is attached beneaththe SiO2/Si.Finite Element Simulation and Cyclic Voltammo-grams Fitting. All finite element simulations of electrontransport were performed on a COMSOL Multiphysics v5.6(COMSOL) to capture the effects of quantum capacitanceACS Central Science http://pubs.acs.org/journal/acscii Research Articlehttps://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−11281124https://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttp://pubs.acs.org/journal/acscii?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-as(see Supporting Information Text). The fitting of the CVs wasachieved by statistical analysis of the experimental andsimulated CVs (SI Figures 8 and 9).Raman Mapping. Confocal Raman spectra were collectedby recording from 2550−2800 cm−1 with a 532 nm laser at 3.2mW. Raman maps were generated by collecting the spectrumacross the trilayer films with a step size of 2 μm. The spectrumwas fitted with single Lorentzian functions. The full-width athalf maxima of the fitted functions were used to differentiateABA and ABC trilayers (see Supporting Information text).PFM Measurements. PFMs were performed on an AIST-NT OmegaScope Reflection. Ti/Ir-coated silicon probes fromthe Nanosensor with a force constant of 2.8 N m−1 and aresonance frequency of 75 kHz were used. A 2 V AC bias withresonance frequencies at 820 kHz was used, and the force wasset to 25 nN.STM Measurements. STM measurements were conductedusing a Park NX10 STM module (Park Systems) at roomtemperature and atmospheric pressure. Pt−Ir tips wereprepared by electrochemical etching of 0.25 mm Pt−Ir wires(Nanosurf) in 1.5 M CaCl2 solutions.56 The scanned imageswere taken with a 0.2 V tip−sample bias and a 100 pA currentset point. More STM images of various samples can be foundin SI Figure 10. Twist angles of various samples weredetermined using Delaunay triangulation on the Gaussiancenters.24,25Electron Microscopy Measurements. The transmissionelectron microscopy images of the nanopipettes (SI Figure 11)were obtained with a JEOL 1200EX transmission electronmicroscope operated at 100 keV. The top ∼1 mm portion ofthe pipette was attached to the grid (PELCO Hole Grids) suchthat the pipette tip was positioned in the center hole, and therest of the pipette was broken off. Selected-area electrondiffraction patterns were collected on an FEI Tecnai T20 S-TWIN transmission electron microscope with a LaB6 filamentoperated at 200 kV. Selected area electron diffraction was usedto resolve the twist angles for samples with twist angles largerthan 3° (SI Figure 12). To obtain the diffraction patterns, thefabricated TLG/hBN samples were transferred onto a holeysilicon nitride membrane after electrochemical measurements.Dark-field images shown in SI Figure 4 of TLG/hBN sampleswere measured at the National Center for Electron Microscopyfacility in the Molecular Foundry at Lawrence BerkeleyNational Laboratory. Low-magnification DF-TEM imageswere acquired using a Gatan UltraScan camera on a ThermoFisher Scientific Titan-class microscope operated at 60 kV.Calculation of Band Structure and DOS. The DOS fortrilayer graphene structures was calculated as a function of θmusing the ab initio perturbation continuum model developedpreviously.57 The low-energy electronic structure is based on amomentum expansion about the valley K point of the supercellBrillouin zone, allowing a smooth dependence of bands on thetwist angle. It has been shown that the perturbation continuummodel exactly reproduces the results of the more expensive abinitio tight-binding model, and both are in good agreementwith full density functional theory (DFT) calculations.57−60The energy range of integration for the DOS was fixed at ±0.5eV around the charge neutrality point (CNP). For evaluationof the LDOS, the normalized moire ́ supercell was divided intoa 90 × 90 grid in real space and sampled over 36 k points inthe Brillouin zone. We kept the sublattice symmetry intact andassumed no extra screening of the interlayer couplingconstants.Quantum Capacitance Calculation. Quantum capaci-tance (Cq) describes the variation of electrical charges withrespect to the chemical potential (Vq). Theoretical Cq valueswith respect to Vq were calculated based on the followingequation61=+C e D F eV( ) ( )dq q2T (3)=F k T k T( ) (4 ) sech ( /2 )T B1 2B (4)where D(ϵ) is the density of states, which we center at theCNP, FT(ϵ) is the thermal broadening function, and kB isBoltzmann’s constant. We assumed T = 300 K for ourexperimental conditions. The total electric double-layercapacitance is governed by the compact layer capacitance.Hence, we used a constant Cdl = 10 μF cm−2 to simplify thecalculation.62 We solved the self-consistent equations relatingVapp, Vq, Vdl, Cq, and Cdl using Simpson integration andnonlinear least squares= +V V Vapp d ql (5)=VVCCdlqqdl (6)to obtain Cq vs Vq and Vdl/Vapp vs Vapp as shown in Figure 3.SECCM Measurements. The SECCM nanopipettes werefabricated from single-channel quartz capillaries (inner andouter diameters of 0.7 mm and 1.0 mm from SutterInstrument) in a laser nanopipet puller (Sutter Instrumentmodel 2000). The program was set to heat 700, filament 4,velocity 20, delay 127, and pull 140 to generate pipettes ofdiameters around 200 nm, as later confirmed with bright-fieldTEM25 (see SI Figure 11). The outer surfaces of the pipetteswere silanized by dipping them into dichlorodimethylsilane forless than 1 s when nitrogen was flowed through the inside ofthe pipettes. They were then filled with either Ru(NH3)63+ orCo(phen)33+ solutions through a microsyringe. The pipetteswere gently tapped, and a gentle string of nitrogen was used toeliminate the bubbles. The pipettes were then inserted with aAg/AgCl wire as a quasi-counter reference electrode (QCRE).The pipettes carefully approached (0.2 μm/s) the locations ofinterest while a −0.5 V (0.5 V for Co(phen)33+) bias wasapplied. The meniscus achieved contact when a current oflarger than 2 pA (or smaller than −2 pA) was observed. Thepipette was allowed to stabilize for 30 s. Cyclic voltammograms(CVs) were then conducted by sweeping the potential at 100mV s−1 between −0.6 and 0 V (0 to 0.8 V for Co(phen)33+/2+)for five cycles. Multiple CVs were collected for each sample,and for small twist samples (θ ≤ 0.15°) with moire ́wavelengths of more than 80 nm, only CVs recorded withnanopipettes of more than 200 nm in diameter were includedto ensure that they surveyed multiple stacking domains. Tosurvey electrochemical activities across a large sample, thepipette was retracted by 1 μm after CVs were measured andhorizontally moved to a new location for a new approach.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326.Raman maps of ABA and ABC graphene, calculations ofthe areal fraction from STM and dark-field images, finiteACS Central Science http://pubs.acs.org/journal/acscii Research Articlehttps://doi.org/10.1021/acscentsci.3c00326ACS Cent. Sci. 2023, 9, 1119−11281125https://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acscentsci.3c00326/suppl_file/oc3c00326_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acscentsci.3c00326?goto=supporting-infohttp://pubs.acs.org/journal/acscii?ref=pdfhttps://doi.org/10.1021/acscentsci.3c00326?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-aselement simulation of cyclic voltammagrams, Marcus−Hush−Chidsey calculations, area fraction determina-tions based on rigid and relaxed moire,́ calculations ofrelaxation and the local twist angle of TTL, Supple-mentary Figures 1−19, and Supplementary Tables 1−3(PDF)■ AUTHOR INFORMATIONCorresponding AuthorD. Kwabena Bediako − Department of Chemistry, Universityof California, Berkeley, California 94720, United States;Chemical Sciences Division, Lawrence Berkeley NationalLaboratory, Berkeley, California 94720, United States;orcid.org/0000-0003-0064-9814; Email: bediako@berkeley.eduAuthorsKaidi Zhang − Department of Chemistry, University ofCalifornia, Berkeley, California 94720, United StatesYun Yu − Department of Chemistry, University of California,Berkeley, California 94720, United States; PresentAddress: Current affiliation: Department of Chemistryand Biochemistry, George Mason University, Fairfax, VA22030, United StatesStephen Carr − Brown Theoretical Physics Center, BrownUniversity, Providence, Rhode Island 02912, United StatesMohammad Babar − Department of Mechanical Engineering,Carnegie Mellon University, Pittsburgh, Pennsylvania 15213,United States; orcid.org/0000-0001-6779-3859Ziyan Zhu − SLAC National Accelerator Laboratory, MenloPark, California 94025, United StatesBryan Junsuh Kim − Department of Chemistry, University ofCalifornia, Berkeley, California 94720, United StatesCatherine Groschner − Department of Chemistry, Universityof California, Berkeley, California 94720, United StatesNikta Khaloo − Department of Chemistry, University ofCalifornia, Berkeley, California 94720, United StatesTakashi Taniguchi − International Center for MaterialsNanoarchitectonics, National Institute for Materials Science,305-0044 Tsukuba, Japan; orcid.org/0000-0002-1467-3105Kenji Watanabe − Research Center for Functional Materials,National Institute for Materials Science, 305-0044 Tsukuba,Japan; orcid.org/0000-0003-3701-8119Venkatasubramanian Viswanathan − Department ofMechanical Engineering, Carnegie Mellon University,Pittsburgh, Pennsylvania 15213, United States; orcid.org/0000-0003-1060-5495Complete contact information is available at:https://pubs.acs.org/10.1021/acscentsci.3c00326Author ContributionsK.Z., Y.Y., and D.K.B. conceived the study. K.Z., B.J.K., C.G.,and N.K. performed the experiments. K.Z. performed theCOMSOL simulations. M.B., S.C., and V.V. carried out thetheoretical calculations. K.Z. performed the quantum capaci-tance calculations. K.Z. and B.J.K. performed STM imageanalysis. T.T. and K.W. provided the hBN crystals. K.Z., Y.Y.,and D.K.B. analyzed the data. K.Z. and D.K.B. wrote themanuscript with input from all coauthors.NotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThis material is based upon work supported by the U.S.Department of Energy, Office of Science, Office of BasicEnergy Sciences, under award no. DE-SC0021049 (exper-imental studies by K.Z., Y.Y., B.J.K., N.K., and D.K.B.) and theOffice of Naval Research under award no. N00014-180-S-F009(computational work by M.B. and V.V.). S.C. acknowledgessupport from the National Science Foundation under grant no.OIA-1921199. C.G. was supported by a grant from the W. M.Keck Foundation (award no. 993922). Experimental work atthe Molecular Foundry, LBNL was supported by the Office ofScience, Office of Basic Energy Sciences, the U.S. Departmentof Energy under contract no. DE-AC02-05CH11231. ConfocalRaman spectroscopy was supported by a Defense UniversityResearch Instrumentation Program grant through the Office ofNaval Research under award no. N00014-20-1-2599 (D.K.B.).Other instrumentation used in this work was supported bygrants from the Canadian Institute for Advanced Research(CIFAR−Azrieli Global Scholar, award no. GS21-011), theGordon and Betty Moore Foundation EPiQS Initiative (awardno. 10637), and the 3M Foundation through the 3M Non-Tenured Faculty Award (no. 67507585). K.W. and T.T.acknowledge support from JSPS KAKENHI (grant numbers19H05790, 20H00354, and 21H05233). We thank Isaac M.Craig for the helpful discussion regarding STM analysis.■ REFERENCES(1) Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.;Nørskov, J. K.; Jaramillo, T. F. 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