Establishing reaction networks in the 16-electron sulfur reduction reaction.

The sulfur reduction reaction (SRR) plays a central role in high-capacity lithium sulfur (Li-S) batteries. The SRR involves an intricate, 16-electron conversion process featuring multiple lithium polysulfide intermediates and reaction branches1-3. Establishing the complex reaction network is essential for rational tailoring of the SRR for improved Li-S batteries, but represents a daunting challenge4-6. Herein we systematically investigate the electrocatalytic SRR to decipher its network using the nitrogen, sulfur, dual-doped holey graphene framework as a model electrode to understand the role of electrocatalysts in acceleration of conversion kinetics. Combining cyclic voltammetry, in situ Raman spectroscopy and density functional theory calculations, we identify and directly profile the key intermediates (S8, Li2S8, Li2S6, Li2S4 and Li2S) at varying potentials and elucidate their conversion pathways. Li2S4 and Li2S6 were predominantly observed, in which Li2S4 represents the key electrochemical intermediate dictating the overall SRR kinetics. Li2S6, generated (consumed) through a comproportionation (disproportionation) reaction, does not directly participate in electrochemical reactions but significantly contributes to the polysulfide shuttling process. We found that the nitrogen, sulfur dual-doped holey graphene framework catalyst could help accelerate polysulfide conversion kinetics, leading to faster depletion of soluble lithium polysulfides at higher potential and hence mitigating the polysulfide shuttling effect and boosting output potential. These results highlight the electrocatalytic approach as a promising strategy for tackling the fundamental challenges regarding Li-S batteries.

Unconventional superconductivity in chiral molecule-TaS2 hybrid superlattices.

Chiral superconductors, a unique class of unconventional superconductors in which the complex superconducting order parameter winds clockwise or anticlockwise in the momentum space1, represent a topologically non-trivial system with intrinsic time-reversal symmetry breaking (TRSB) and direct implications for topological quantum computing2,3. Intrinsic chiral superconductors are extremely rare, with only a few arguable examples, including UTe2, UPt3 and Sr2RuO4 (refs. 4-7). It has been suggested that chiral superconductivity may exist in non-centrosymmetric superconductors8,9, although such non-centrosymmetry is uncommon in typical solid-state superconductors. Alternatively, chiral molecules with neither mirror nor inversion symmetry have been widely investigated. We suggest that an incorporation of chiral molecules into conventional superconductor lattices could introduce non-centrosymmetry and help realize chiral superconductivity10. Here we explore unconventional superconductivity in chiral molecule intercalated TaS2 hybrid superlattices. Our studies reveal an exceptionally large in-plane upper critical field Bc2,|| well beyond the Pauli paramagnetic limit, a robust π-phase shift in Little-Parks measurements and a field-free superconducting diode effect (SDE). These experimental signatures of unconventional superconductivity suggest that the intriguing interplay between crystalline atomic layers and the self-assembled chiral molecular layers may lead to exotic topological materials. Our study highlights that the hybrid superlattices could lay a versatile path to artificial quantum materials by combining a vast library of layered crystals of rich physical properties with the nearly infinite variations of molecules of designable structural motifs and functional groups11.

Hypocrystalline ceramic aerogels for thermal insulation at extreme conditions.

Thermal insulation under extreme conditions requires materials that can withstand complex thermomechanical stress and retain excellent thermal insulation properties at temperatures exceeding 1,000 degrees Celsius1-3. Ceramic aerogels are attractive thermal insulating materials; however, at very high temperatures, they often show considerably increased thermal conductivity and limited thermomechanical stability that can lead to catastrophic failure4-6. Here we report a multiscale design of hypocrystalline zircon nanofibrous aerogels with a zig-zag architecture that leads to exceptional thermomechanical stability and ultralow thermal conductivity at high temperatures. The aerogels show a near-zero Poisson's ratio (3.3 × 10-4) and a near-zero thermal expansion coefficient (1.2 × 10-7 per degree Celsius), which ensures excellent structural flexibility and thermomechanical properties. They show high thermal stability with ultralow strength degradation (less than 1 per cent) after sharp thermal shocks, and a high working temperature (up to 1,300 degrees Celsius). By deliberately entrapping residue carbon species in the constituent hypocrystalline zircon fibres, we substantially reduce the thermal radiation heat transfer and achieve one of the lowest high-temperature thermal conductivities among ceramic aerogels so far-104 milliwatts per metre per kelvin at 1,000 degrees Celsius. The combined thermomechanical and thermal insulating properties offer an attractive material system for robust thermal insulation under extreme conditions.

Chiral molecular intercalation superlattices.

The discovery of chiral-induced spin selectivity (CISS) opens up the possibility to manipulate spin orientation without external magnetic fields and enables new spintronic device designs1-4. Although many approaches have been explored for introducing CISS into solid-state materials and devices, the resulting systems so far are often plagued by high inhomogeneity, low spin selectivity or limited stability, and have difficulties in forming robust spintronic devices5-8. Here we report a new class of chiral molecular intercalation superlattices (CMIS) as a robust solid-state chiral material platform for exploring CISS. The CMIS were prepared by intercalating layered two-dimensional atomic crystals (2DACs) (such as TaS2 and TiS2) with selected chiral molecules (such as R-α-methylbenzylamine and S-α-methylbenzylamine). The X-ray diffraction and transmission electron microscopy studies demonstrate highly ordered superlattice structures with alternating crystalline atomic layers and self-assembled chiral molecular layers. Circular dichroism studies show clear chirality-dependent signals between right-handed (R-) and left-handed (S-) CMIS. Furthermore, by using the resulting CMIS as the spin-filtering layer, we create spin-selective tunnelling junctions with a distinct chirality-dependent tunnelling current, achieving a tunnelling magnetoresistance ratio of more than 300 per cent and a spin polarization ratio of more than 60 per cent. With a large family of 2DACs of widely tunable electronic properties and a vast selection of chiral molecules of designable structural motifs, the CMIS define a rich family of artificial chiral materials for investigating the CISS effect and capturing its potential for new spintronic devices.

Promises and prospects of two-dimensional transistors.

Two-dimensional (2D) semiconductors have attracted tremendous interest as atomically thin channels that could facilitate continued transistor scaling. However, despite many proof-of-concept demonstrations, the full potential of 2D transistors has yet to be determined. To this end, the fundamental merits and technological limits of 2D transistors need a critical assessment and objective projection. Here we review the promise and current status of 2D transistors, and emphasize that widely used device parameters (such as carrier mobility and contact resistance) could be frequently misestimated or misinterpreted, and may not be the most reliable performance metrics for benchmarking 2D transistors. We suggest that the saturation or on-state current density, especially in the short-channel limit, could provide a more reliable measure for assessing the potential of diverse 2D semiconductors, and should be applied for cross-checking different studies, especially when milestone performance metrics are claimed. We also summarize the key technical challenges in optimizing the channels, contacts, dielectrics and substrates and outline potential pathways to push the performance limit of 2D transistors. We conclude with an overview of the critical technical targets, the key technological obstacles to the 'lab-to-fab' transition and the potential opportunities arising from the use of these atomically thin semiconductors.

Approaching the intrinsic exciton physics limit in two-dimensional semiconductor diodes.

Two-dimensional (2D) semiconductors have attracted intense interest for their unique photophysical properties, including large exciton binding energies and strong gate tunability, which arise from their reduced dimensionality1-5. Despite considerable efforts, a disconnect persists between the fundamental photophysics in pristine 2D semiconductors and the practical device performances, which are often plagued by many extrinsic factors, including chemical disorder at the semiconductor-contact interface. Here, by using van der Waals contacts with minimal interfacial disorder, we suppress contact-induced Shockley-Read-Hall recombination and realize nearly intrinsic photophysics-dictated device performance in 2D semiconductor diodes. Using an electrostatic field in a split-gate geometry to independently modulate electron and hole doping in tungsten diselenide diodes, we discover an unusual peak in the short-circuit photocurrent at low charge densities. Time-resolved photoluminescence reveals a substantial decrease of the exciton lifetime from around 800 picoseconds in the charge-neutral regime to around 50 picoseconds at high doping densities owing to increased exciton-charge Auger recombination. Taken together, we show that an exciton-diffusion-limited model well explains the charge-density-dependent short-circuit photocurrent, a result further confirmed by scanning photocurrent microscopy. We thus demonstrate the fundamental role of exciton diffusion and two-body exciton-charge Auger recombination in 2D devices and highlight that the intrinsic photophysics of 2D semiconductors can be used to create more efficient optoelectronic devices.

High-order superlattices by rolling up van der Waals heterostructures.

Two-dimensional (2D) materials1,2 and the associated van der Waals (vdW) heterostructures3-7 have provided great flexibility for integrating distinct atomic layers beyond the traditional limits of lattice-matching requirements, through layer-by-layer mechanical restacking or sequential synthesis. However, the 2D vdW heterostructures explored so far have been usually limited to relatively simple heterostructures with a small number of blocks8-18. The preparation of high-order vdW superlattices with larger number of alternating units is exponentially more difficult, owing to the limited yield and material damage associated with each sequential restacking or synthesis step8-29. Here we report a straightforward approach to realizing high-order vdW superlattices by rolling up vdW heterostructures. We show that a capillary-force-driven rolling-up process can be used to delaminate synthetic SnS2/WSe2 vdW heterostructures from the growth substrate and produce SnS2/WSe2 roll-ups with alternating monolayers of WSe2 and SnS2, thus forming high-order SnS2/WSe2 vdW superlattices. The formation of these superlattices modulates the electronic band structure and the dimensionality, resulting in a transition of the transport characteristics from semiconducting to metallic, from 2D to one-dimensional (1D), with an angle-dependent linear magnetoresistance. This strategy can be extended to create diverse 2D/2D vdW superlattices, more complex 2D/2D/2D vdW superlattices, and beyond-2D materials, including three-dimensional (3D) thin-film materials and 1D nanowires, to generate mixed-dimensional vdW superlattices, such as 3D/2D, 3D/2D/2D, 1D/2D and 1D/3D/2D vdW superlattices. This study demonstrates a general approach to producing high-order vdW superlattices with widely variable material compositions, dimensions, chirality and topology, and defines a rich material platform for both fundamental studies and technological applications.

Solution-Processable and Printable Two-Dimensional Transition Metal Dichalcogenide Inks.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) with layered crystal structures have been attracting enormous research interest for their atomic thickness, mechanical flexibility, and excellent electronic/optoelectronic properties for applications in diverse technological areas. Solution-processable 2D TMD inks are promising for large-scale production of functional thin films at an affordable cost, using high-throughput solution-based processing techniques such as printing and roll-to-roll fabrications. This paper provides a comprehensive review of the chemical synthesis of solution-processable and printable 2D TMD ink materials and the subsequent assembly into thin films for diverse applications. We start with the chemical principles and protocols of various synthesis methods for 2D TMD nanosheet crystals in the solution phase. The solution-based techniques for depositing ink materials into solid-state thin films are discussed. Then, we review the applications of these solution-processable thin films in diverse technological areas including electronics, optoelectronics, and others. To conclude, a summary of the key scientific/technical challenges and future research opportunities of solution-processable TMD inks is provided.

General synthesis of two-dimensional van der Waals heterostructure arrays.

Two-dimensional van der Waals heterostructures (vdWHs) have attracted considerable interest1-4. However, most vdWHs reported so far  are created by an arduous micromechanical exfoliation and manual restacking process5, which-although versatile for proof-of-concept demonstrations6-16 and fundamental studies17-30-is clearly not scalable for practical technologies. Here we report a general synthetic strategy for two-dimensional vdWH arrays between metallic transition-metal dichalcogenides (m-TMDs) and semiconducting TMDs (s-TMDs). By selectively patterning nucleation sites on monolayer or bilayer s-TMDs, we precisely control the nucleation and growth of diverse m-TMDs with designable periodic arrangements and tunable lateral dimensions at the predesignated spatial locations, producing a series of vdWH arrays, including VSe2/WSe2, NiTe2/WSe2, CoTe2/WSe2, NbTe2/WSe2, VS2/WSe2, VSe2/MoS2 and VSe2/WS2. Systematic scanning transmission electron microscopy studies reveal nearly ideal vdW interfaces with widely tunable moiré superlattices. With the atomically clean vdW interface, we further show that the m-TMDs function as highly reliable synthetic vdW contacts for the underlying WSe2 with excellent device performance and yield, delivering a high ON-current density of up to 900 microamperes per micrometre in bilayer WSe2 transistors. This general synthesis of diverse two-dimensional vdWH arrays provides a versatile material platform for exploring exotic physics and promises a scalable pathway to high-performance devices.

Towards the scalable synthesis of two-dimensional heterostructures and superlattices beyond exfoliation and restacking.

Two-dimensional transition metal dichalcogenides, which feature atomically thin geometry and dangling-bond-free surfaces, have attracted intense interest for diverse technology applications, including ultra-miniaturized transistors towards the subnanometre scale. A straightforward exfoliation-and-restacking approach has been widely used for nearly arbitrary assembly of diverse two-dimensional (2D) heterostructures, superlattices and moiré superlattices, providing a versatile materials platform for fundamental investigations of exotic physical phenomena and proof-of-concept device demonstrations. While this approach has contributed importantly to the recent flourishing of 2D materials research, it is clearly unsuitable for practical technologies. Capturing the full potential of 2D transition metal dichalcogenides requires robust and scalable synthesis of these atomically thin materials and their heterostructures with designable spatial modulation of chemical compositions and electronic structures. The extreme aspect ratio, lack of intrinsic substrate and highly delicate nature of the atomically thin crystals present fundamental difficulties in material synthesis. Here we summarize the key challenges, highlight current advances and outline opportunities in the scalable synthesis of transition metal dichalcogenide-based heterostructures, superlattices and moiré superlattices.

Van der Waals integration before and beyond two-dimensional materials.

Material integration strategies, such as epitaxial growth, usually involve strong chemical bonds and are typically limited to materials with strict structure matching and processing compatibility. Van der Waals integration, in which pre-fabricated building blocks are physically assembled together through weak van der Waals interactions, offers an alternative bond-free integration strategy without lattice and processing limitations, as exemplified by two-dimensional van der Waals heterostructures. Here we review the development, challenges and opportunities of this emerging approach, generalizing it for flexible integration of diverse material systems beyond two dimensions, and discuss its potential for creating artificial heterostructures or superlattices beyond the reach of existing materials.

Determining the hydronium pK[Formula: see text] at platinum surfaces and the effect on pH-dependent hydrogen evolution reaction kinetics.

Electrocatalytic hydrogen evolution reaction (HER) is critical for green hydrogen generation and exhibits distinct pH-dependent kinetics that have been elusive to understand. A molecular-level understanding of the electrochemical interfaces is essential for developing more efficient electrochemical processes. Here we exploit an exclusively surface-specific electrical transport spectroscopy (ETS) approach to probe the Pt-surface water protonation status and experimentally determine the surface hydronium pKa [Formula: see text] 4.3. Quantum mechanics (QM) and reactive dynamics using a reactive force field (ReaxFF) molecular dynamics (RMD) calculations confirm the enrichment of hydroniums (H3O[Formula: see text]) near Pt surface and predict a surface hydronium pKa of 2.5 to 4.4, corroborating the experimental results. Importantly, the observed Pt-surface hydronium pKa correlates well with the pH-dependent HER kinetics, with the protonated surface state at lower pH favoring fast Tafel kinetics with a Tafel slope of 30 mV per decade and the deprotonated surface state at higher pH following Volmer-step limited kinetics with a much higher Tafel slope of 120 mV per decade, offering a robust and precise interpretation of the pH-dependent HER kinetics. These insights may help design improved electrocatalysts for renewable energy conversion.

Highly Robust Room-Temperature Interfacial Ferromagnetism in Ultrathin Co2Si Nanoplates.

The reduced dimensionality and interfacial effects in magnetic nanostructures open the feasibility to tailor magnetic ordering. Here, we report the synthesis of ultrathin metallic Co2Si nanoplates with a total thickness that is tunable to 2.2 nm. The interfacial magnetism coupled with the highly anisotropic nanoplate geometry leads to strong perpendicular magnetic anisotropy and robust hard ferromagnetism at room temperature, with a Curie temperature (TC) exceeding 950 K and a coercive field (HC) > 4.0 T at 3 K and 8750 Oe at 300 K. Theoretical calculations suggest that ferromagnetism originates from symmetry breaking and undercoordinated Co atoms at the Co2Si and SiO2 interface. With protection by the self-limiting intrinsic oxide, the interfacial ferromagnetism of the Co2Si nanoplates exhibits excellent environmental stability. The controllable growth of ambient stable Co2Si nanoplates as 2D hard ferromagnets could open exciting opportunities for fundamental studies and applications in Si-based spintronic devices.

Platinum Surface Water Orientation Dictates Hydrogen Evolution Reaction Kinetics in Alkaline Media.

The fundamental understanding of sluggish hydrogen evolution reaction (HER) kinetics on a platinum (Pt) surface in alkaline media is a topic of considerable debate. Herein, we combine cyclic voltammetry (CV) and electrical transport spectroscopy (ETS) approaches to probe the Pt surface at different pH values and develop molecular-level insights into the pH-dependent HER kinetics in alkaline media. The change in HER Tafel slope from ∼110 mV/decade in pH 7-10 to ∼53 mV/decade in pH 11-13 suggests considerably enhanced kinetics at higher pH. The ETS studies reveal a similar pH-dependent switch in the ETS conductance signal at around pH 10, suggesting a notable change of surface adsorbates. Fixed-potential calculations and chemical bonding analysis suggest that this switch is attributed to a change in interfacial water orientation, shifting from primarily an O-down configuration below pH 10 to a H-down configuration above pH 10. This reorientation weakens the O-H bond in the interfacial water molecules and modifies the reaction pathway, leading to considerably accelerated HER kinetics at higher pH. Our integrated studies provide an unprecedented molecular-level understanding of the nontrivial pH-dependent HER kinetics in alkaline media.

Element Screening of High-Entropy Silicon Anodes for Superior Li-Storage Performance of Li-Ion Batteries.

The high-entropy silicon anodes are attractive for enhancing electronic and Li-ionic conductivity while mitigating volume effects for advanced Li-ion batteries (LIBs), but are plagued by the complicated elements screening process. Inspired by the resemblances in the structure between sphalerite and diamond, we have selected sphalerite-structured SiP with metallic conductivity as the parent phase for exploring the element screening of high-entropy silicon-based anodes. The inclusion of the Zn in the sphalerite structure is crucial for improving the structural stability and Li-storage capacity. Within the same group, Li-storage performance is significantly improved with increasing atomic number in the order of BZnSiP3 < AlZnSiP3 < GaZnSiP3 < InZnSiP3. Thus, InZnSiP3-based electrodes achieved a high capacity of 719 mA h g-1 even after 1,500 cycles at 2,000 mA g-1, and a high-rate capacity of 725 mA h g-1 at 10,000 mA g-1, owing to its superior lithium-ion affinity, faster electronic conduction and lithium-ion diffusion, higher Li-storage capacity and reversibility, and mechanical integrity than others. Additionally, the incorporation of elements with larger atomic sizes leads to greater lattice distortion and more defects, further facilitating mass and charge transport. Following these screening rules, high-entropy disordered-cation silicon-based compounds such as GaCuSnInZnSiP6, GaCu(or Sn)InZnSiP5, and CuSnInZnSiP5, as well as high-entropy compounds with mixed-cation and -anion compositions, such as InZnSiPSeTe and InZnSiP2Se(or Te), are synthesized, demonstrating improved Li-storage performance with metallic conductivity. The phase formation mechanism of these compounds is attributed to the negative formation energies arising from elevated entropy.

Solid-State Electrocatalysis in Heteroatom-Doped Alloy Anode Enables Ultrafast Charge Lithium-Ion Batteries.

Electrocatalysis is generally confined to dynamic liquid-solid and gas-solid interfaces and is rarely applicable in solid-state reactions. Here, we report a paradigm shift strategy to exploit electrocatalysis to accelerate solid-state reactions in the context of lithium-ion batteries (LIBs). We employ heteroatom doping, specifically boron for silicon and sulfur for phosphorus, to catalyze electrochemical Li-alloying reactions in solid-state electrode materials. The preferential cleavage of polar dopant-host chemical bonds upon lithiation triggers chemical bond breaking of the host material. This solid-state catalysis, distinct from liquid and gas phases, requires a critical doping concentration for optimal performance. Beyond a critical concentration of ∼1 atom %, boron and sulfur doping drastically reduces activation energies and accelerates redox kinetics during lithiation/delithiation processes, leading to markedly enhanced rate performance in boron-doped silicon and sulfur-doped black/red phosphorus anode. Notably, a sulfur-doped black phosphorus anode coupled with a lithium cobalt oxide cathode achieves an ultrafast-charging battery, recharging 80% energy of a battery in 302 Wh kg-1 in 9 min, surpassing the thus far reported LIBs.

Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction.

In analogy to natural enzymes, an elaborated design of catalytic systems with a specifically tailored local chemical environment could substantially improve reaction kinetics, effectively combat catalyst poisoning effect and boost catalyst lifetime under unfavourable reaction conditions. Here we report a unique design of 'Ni(OH)2-clothed Pt-tetrapods' with an amorphous Ni(OH)2 shell as a water dissociation catalyst and a proton conductive encapsulation layer to isolate the Pt core from bulk alkaline electrolyte while ensuring efficient proton supply to the active Pt sites. This design creates a favourable local chemical environment to result in acidic-like hydrogen evolution reaction kinetics with a lowest Tafel slope of 27 mV per decade and a record-high specific activity and mass activity in alkaline electrolyte. The proton conductive Ni(OH)2 shell can also effectively reject impurity ions and retard the Oswald ripening, endowing a high tolerance to solution impurities and exceptional long-term durability that is difficult to achieve in the naked Pt catalysts. The markedly improved hydrogen evolution reaction activity and durability in an alkaline medium promise an attractive catalyst material for alkaline water electrolysers and renewable chemical fuel generation.

2D Heterostructures for Ubiquitous Electronics and Optoelectronics: Principles, Opportunities, and Challenges.

A grand family of two-dimensional (2D) materials and their heterostructures have been discovered through the extensive experimental and theoretical efforts of chemists, material scientists, physicists, and technologists. These pioneering works contribute to realizing the fundamental platforms to explore and analyze new physical/chemical properties and technological phenomena at the micro-nano-pico scales. Engineering 2D van der Waals (vdW) materials and their heterostructures via chemical and physical methods with a suitable choice of stacking order, thickness, and interlayer interactions enable exotic carrier dynamics, showing potential in high-frequency electronics, broadband optoelectronics, low-power neuromorphic computing, and ubiquitous electronics. This comprehensive review addresses recent advances in terms of representative 2D materials, the general fabrication methods, and characterization techniques and the vital role of the physical parameters affecting the quality of 2D heterostructures. The main emphasis is on 2D heterostructures and 3D-bulk (3D) hybrid systems exhibiting intrinsic quantum mechanical responses in the optical, valley, and topological states. Finally, we discuss the universality of 2D heterostructures with representative applications and trends for future electronics and optoelectronics (FEO) under the challenges and opportunities from physical, nanotechnological, and material synthesis perspectives.

Approaching the Schottky-Mott limit in van der Waals metal-semiconductor junctions.

The junctions formed at the contact between metallic electrodes and semiconductor materials are crucial components of electronic and optoelectronic devices 1 . Metal-semiconductor junctions are characterized by an energy barrier known as the Schottky barrier, whose height can, in the ideal case, be predicted by the Schottky-Mott rule2-4 on the basis of the relative alignment of energy levels. Such ideal physics has rarely been experimentally realized, however, because of the inevitable chemical disorder and Fermi-level pinning at typical metal-semiconductor interfaces2,5-12. Here we report the creation of van der Waals metal-semiconductor junctions in which atomically flat metal thin films are laminated onto two-dimensional semiconductors without direct chemical bonding, creating an interface that is essentially free from chemical disorder and Fermi-level pinning. The Schottky barrier height, which approaches the Schottky-Mott limit, is dictated by the work function of the metal and is thus highly tunable. By transferring metal films (silver or platinum) with a work function that matches the conduction band or valence band edges of molybdenum sulfide, we achieve transistors with a two-terminal electron mobility at room temperature of 260 centimetres squared per volt per second and a hole mobility of 175 centimetres squared per volt per second. Furthermore, by using asymmetric contact pairs with different work functions, we demonstrate a silver/molybdenum sulfide/platinum photodiode with an open-circuit voltage of 1.02 volts. Our study not only experimentally validates the fundamental limit of ideal metal-semiconductor junctions but also defines a highly efficient and damage-free strategy for metal integration that could be used in high-performance electronics and optoelectronics.

Gate-tunable frequency combs in graphene-nitride microresonators.

Optical frequency combs, which emit pulses of light at discrete, equally spaced frequencies, are cornerstones of modern-day frequency metrology, precision spectroscopy, astronomical observations, ultrafast optics and quantum information1-7. Chip-scale frequency combs, based on the Kerr and Raman nonlinearities in monolithic microresonators with ultrahigh quality factors8-10, have recently led to progress in optical clockwork and observations of temporal cavity solitons11-14. But the chromatic dispersion within a laser cavity, which determines the comb formation15,16, is usually difficult to tune with an electric field, whether in microcavities or fibre cavities. Such electrically dynamic control could bridge optical frequency combs and optoelectronics, enabling diverse comb outputs in one resonator with fast and convenient tunability. Arising from its exceptional Fermi-Dirac tunability and ultrafast carrier mobility17-19, graphene has a complex optical dispersion determined by its optical conductivity, which can be tuned through a gate voltage20,21. This has brought about optoelectronic advances such as modulators22,23, photodetectors 24 and controllable plasmonics25,26. Here we demonstrate the gated intracavity tunability of graphene-based optical frequency combs, by coupling the gate-tunable optical conductivity to a silicon nitride photonic microresonator, thus modulating its second- and higher-order chromatic dispersions by altering the Fermi level. Preserving cavity quality factors up to 106 in the graphene-based comb, we implement a dual-layer ion-gel-gated transistor to tune the Fermi level of graphene across the range 0.45-0.65 electronvolts, under single-volt-level control. We use this to produce charge-tunable primary comb lines from 2.3 terahertz to 7.2 terahertz, coherent Kerr frequency combs, controllable Cherenkov radiation and controllable soliton states, all in a single microcavity. We further demonstrate voltage-tunable transitions from periodic soliton crystals to crystals with defects, mapped by our ultrafast second-harmonic optical autocorrelation. This heterogeneous graphene microcavity, which combines single-atomic-layer nanoscience and ultrafast optoelectronics, will help to improve our understanding of dynamical frequency combs and ultrafast optics.