Electrochemical Detection of Nucleic Acids Using Three-Dimensional Graphene Screen-Printed Electrodes.

Electrochemical approaches, along with miniaturization of electrodes, are increasingly being employed to detect and quantify nucleic acid biomarkers. Miniaturization of the electrodes is achieved through the use of screen-printed electrodes (SPEs), which consist of one to a few dozen sets of electrodes, or by utilizing printed circuit boards. Electrode materials used in SPEs include glassy carbon (Chiang H-C, Wang Y, Zhang Q, Levon K, Biosensors (Basel) 9:2-11, 2019), platinum, carbon, and graphene (Cheng FF, He TT, Miao HT, Shi JJ, Jiang LP, Zhu JJ, ACS Appl Mater Interfaces 7:2979-2985, 2015). There are numerous modifications to the electrode surfaces as well (Cheng FF, He TT, Miao HT, Shi JJ, Jiang LP, Zhu JJ, ACS Appl Mater Interfaces 7:2979-2985, 2015). These approaches offer distinct advantages, primarily due to their demonstrated superior limit of detection without amplification. Using the SPEs and potentiostats, we can detect cells, proteins, DNA, and RNA concentrations in the nanomolar (nM) to attomolar (aM) range. The focus of this chapter is to describe the basic approach adopted for the use of SPEs for nucleic acid measurement.

A self-powered theranostic DNA nanodevice for amplification of both intracellular microRNA imaging and photodynamic therapy.

While numerous methods exist for diagnosing tumors through the detection of miRNA within tumor cells, few can simultaneously achieve both tumor diagnosis and treatment. In this study, a novel graphene oxide (GO)-based DNA nanodevice (DND), initiated by miRNA, was developed for fluorescence signal amplification imaging and photodynamic therapy in tumor cells. After entering the cells, tumor-associated miRNA drives DND to Catalyzed hairpin self-assembly (CHA). The CHA reaction generated a multitude of DNA Y-type structures, resulting in a substantial amplification of Ce6 fluorescence release and the generation of numerous singlet oxygen (1O2) species induced by laser irradiation, consequently inducing cell apoptosis. In solution, DND exhibited high selectivity and sensitivity to miRNA-21, with a detection limit of 11.47 pM. Furthermore, DND discriminated between normal and tumor cells via fluorescence imaging and specifically generated O21 species in tumor cells upon laser irradiation, resulting in tumor cells apoptosis. The DND offer a new approach for the early diagnosis and timely treatment of malignant tumors.

Chemical reduction-induced defect-rich bismuth oxide-reduced graphene oxide anode for high-performance supercapacitors.

We prepare bismuth oxide-reduced graphene oxide (Bi2O3-rGO) composite anode using a one-step chemical precipitation/reduction method. Under a reducing atmosphere, oxygen atoms on the surface of Bi2O3 are gradually removed and neighboring oxygen atoms migrate to the surface, leaving oxygen vacancies. Defective Bi2O3 enhances the number of active sites, providing additional pseudocapacitive performance. The transition metal oxide-based Bi2O3 acts as an anode, providing capacitive performance that far exceeds that of conventional carbon materials. Moreover, the introduction of rGO forms a conductive network for Bi2O3, improving capacitive contribution and ion diffusion capabilities for the electrode. The Bi2O3-rGO-100 (GO added at 100 mg) exhibits a high specific capacitance of 1053F/g at 1 A/g, significantly higher than that of Bi2O3 (866F/g). The Bi2O3-rGO-100 anode and Ni3Co2-rGO cathode are assembled into a battery-type supercapacitor. The coin-cell device achieves an energy density of 88.2 Wh kg-1 at a power density of 850 W kg-1. The Ni3Co2-rGO//Bi2O3-rGO-100 pouch-cell device demonstrates an extremely low Rct of 0.77 Ω. At a power density of 850 W kg-1, the energy density reaches 118.5 Wh kg-1, and remains 67.4 Wh kg-1 at 8500 W kg-1.

Wide-temperature-range pressure sensing by an aramid nanofibers/reduced graphene oxide flakes composite aerogel.

Aerogel-based conductive materials have emerged as a major candidate for piezoresistive pressure sensors due to their excellent mechanical and electrical performance besides light-weighted and low-cost characteristics, showing great potential for applications in electronic skins, biomedicine, robot controlling and intelligent recognition. However, it remains a grand challenge for these piezoresistive sensors to achieve a high sensitivity across a wide working temperature range. Herein, we report a highly flexible and ultra-light composite aerogel consisting of aramid nanofibers (ANFs) and reduced graphene oxide flakes (rGOFs) for application as a high-performance pressure sensing material in a wide temperature range. By controlling the orientations of pores in the composite framework, the aerogel promotes pressure transfer by aligning its conductive channels. As a result, the ANFs/rGOFs aerogel-based piezoresistive sensor exhibits a high sensitivity of up to 7.10 kPa-1, an excellent stability over 12,000 cycles, and an ultra-wide working temperature range from -196 to 200 °C. It is anticipated that the ANFs/rGOFs composite aerogel can be used as reliable sensing materials in extreme environments.

A highly sensitive electrochemical sensor based on poly(3-aminobenzoic acid)/graphene oxide-gold nanoparticles modified screen printed carbon electrode for paraquat detection.

Herein, a modified screen printed carbon electrode (SPCE) based on a composite material, graphene oxide-gold nanoparticles (GO-AuNPs), and poly(3-aminobenzoic acid)(P3ABA) for the detection of paraquat (PQ) is introduced. The modified electrode was fabricated by drop casting of the GO-AuNPs, followed by electropolymerization of 3-aminobenzoic acid to achieve SPCE/GO-AuNPs/P3ABA. The morphology and microstructural characteristics of the modified electrodes were revealed by scanning electron microscopy (SEM) for each step of modification. The composite GO-AuNPs can provide high surface area and enhance electroconductivity of the electrode. In addition, the presence of negatively charged P3ABA notably improved PQ adsorption and electron transfer rate, which stimulate redox reaction on the modified electrode, thus improving the sensitivity of PQ analysis. The SPCE/GO-AuNPs/P3ABA offered a wide linear range of PQ determination (10-9-10-4 mol/L) and low limit of detection (LOD) of 0.45 × 10-9 mol/L or 0.116 µg/L, which is far below international safety regulations. The modified electrode showed minimum interference effect with percent recovery ranging from 96.5% to 116.1% after addition of other herbicides, pesticides, metal ions, and additives. The stability of the SPCE/GO-AuNPs/P3ABA was evaluated, and the results indicated negligible changes in the detection signal over 9 weeks. Moreover, this modified electrode was successfully implemented for PQ analysis in both natural and tapped water with high accuracy.

Effect of surface species on the alcohol-acid adsorption from FTS wastewater on graphene: A structure-capacity study.

Fischer-Tropsch synthesis (FTS) wastewater retaining low-carbon alcohols and acids are organic pollutants as a limiting factor for FTS industrialization. In this work, the structure-capacity relationships between alcohol-acid adsorption and surface species on graphene were reported, shedding light into their intricate interactions. The graphene oxide (GO) and reduced graphene oxide (rGO) were synthesized via improved Hummers method with flake graphite (G). The physicochemical properties of samples were characterized via SEM, XRD, XPS, FT-IR, and Raman. The alcohol-acid adsorption behaviors and adsorption quantities on G, GO, and rGO were measured via theoretical and experimental method. It was revealed that the presence of COOH, C=O and CO species on graphene occupy the adsorption sites and increase the interactions of water with graphene, which are unfavorable for alcohol-acid adsorption. The equilibrium adsorption quantities of alcohols and acids grow in pace with carbon number. The monolayer adsorption occurs on graphene was verified via model fitting. rGO has the highest FTS modeling wastewater adsorption quantity (110 mg/g) due to the reduction of oxygen species. These novel findings provide a foundation for the alcohol-acid wastewater treatment, as well as the design and development of high-performance carbon-based adsorbent materials.

Impact of Graphene Oxide Nanoparticles on In Vitro Development of a Mouse Preimplantation Embryo and Interaction With the Zona Pellucida.

The development of assisted reproductive technologies increases the likelihood of nanoparticles' (NPs) direct contact with gametes and embryos in in vitro conditions. Analyzing the influence of nanomaterials on the early mammalian embryo becomes increasingly relevant. This work is devoted to the effect of graphene oxide (GO) NPs on the in vitro development of mammalian embryos. Mouse 2-cell embryos were preincubated with GO NPs. The interaction of GO with the Zona Pellucida (ZP) of the embryo was investigated using fluorescence lifetime imaging with two-photon excitation (2p-FLIM). During embryo development, the NPs penetration into ZP (blastocyst stage) and perivitelline space (blastocyst hatching stage) was observed. Despite this, GO did not affect the embryo's ability to develop till late and hatching blastocysts. The mechanism of the NPs getting into the perivitelline space and the consequences of NP-embryo direct contact are discussed. The 2p-FLIM efficiency for studying NP interaction with mammalian embryos is evaluated.

Visible Light-Triggered Catalytic Performance of Reduced Graphene Oxide Decorated With Copper Oxide Nanocomposite for Degradation of Rhodamine B Dye and Kinetics Studies.

Herein, novel nanocomposites based on reduced graphene oxide decorated copper oxide nanoparticles (rGO/CuO) were prepared by the in situ co-precipitation method. The structural, morphological, and optical characterization of as-prepared nanocomposites was performed by powdered x-ray diffraction (p-XRD), scanning electron microscopy (SEM), and Fourier-transform infrared (FTIR), Raman, and ultraviolet-visible (UV-Vis) spectroscopy, respectively. The as-prepared nanocomposites exhibited better photocatalytic activity of rhodamine B dye with maximum ~94% degradation in 120 min with a rate constant of 0.2353 min-1 under optimized conditions. Furthermore, the effects of solution pH and catalyst loading are studied on the degradation process. Therefore, this state-of-the-art strategy for the decoration of CuO nanoparticles onto the surface of rGO nanosheets could be an ideal platform for fabricating highly efficient photocatalysts.

A Versatile Metal-Organic-Framework Pillared Interlayer Design for High-Capacity and Long-Life Lithium-Sulfur Batteries.

Developing high-performance lithium-sulfur batteries is a promising way to attain higher energy density at lower cost beyond the state-of-the-art lithium-ion battery technology. However, the major issues blocking their practical application are the sluggish kinetics and parasitic shuttling reactions for sulfur and polysulfides. Here, pillaring multilayer graphene with the metal-organic framework (MOF) demonstrates the substantial impact of a versatile interlayer design in tackling those issues. Unlike regular composite separators reported so far, the participation of tri-metallic Ni-Co-Mn MOF (NCM-MOF) as pillars supports the construction of an ion-channel interconnected interlayer structure, unexpectedly balancing the interfacial concentration polarization, spatially confining the soluble polysulfides and vastly affording lithiophilic sites for highly efficient polysulfide sieving/conversion. As a demonstration, we show that the MOF-pillared interlayer structure enables outstanding capacity (1634 mAh g-1 at 0.1C) and longevity (average capacity decay of 0.034% per cycle in 2000 cycles) of lithium-sulfur batteries. Besides, the multilayer separator can be readily integrated into the high-nickel cathode (LiNi0.91Mn0.03Co0.06O2)-based lithium-ion batteries, which efficiently suppresses the undesired phase evolution upon cycling. These findings suggest the potential of "gap-filling" materials in fabricating multi-functional separators, bring forward the pillared interlayer structure for energy-storage applications.

Effectively Sieving Alkali Metal Ions Using Functionalized Graphene Oxide Membranes by Exploiting Water-Repellent Interactions.

Sieving membranes capable of discerning different alkali metal ions are important for many technologies, such as energy, environment, and life science. Recently, two-dimensional (2D) materials have been extensively explored for the creation of sieving membranes with angstrom-scale channels. However, because of the same charge and similar hydrated sizes, mostly laminated membranes typically show low selectivity (<10). Herein, we report a facile and scalable method for functionalizing graphene oxide (GO) laminates by dually grafting cations and water-repellent dimethylsiloxane (DMDMS) molecules to achieve high selectivities of ∼50 and ∼20 toward the transport of Cs+/Li+ and K+/Li+ ion pairs, surpassing many of the state-of-the-art laminated membranes. The enhanced selectivity for alkali metal ions can be credited to a dual impact: (i) strong hydrophobic interactions between the incident cations' hydration shells and the water-repellent DMDMS; (ii) the efficient screening of electrostatic interactions that hamper selectivity.

Humidity Sensing Properties of Different Atomic Layers of Graphene on the SiO2/Si Substrate.

Graphene has great potential to be used for humidity sensing due to its ultrahigh surface area and conductivity. However, the impact of different atomic layers of graphene on the SiO2/Si substrate on humidity sensing has not been studied yet. In this paper, we fabricated three types of humidity sensors on the SiO2/Si substrate based on one to three atomic layers of graphene, in which the sensing areas of graphene are 75 µm × 72 µm and 45 µm × 72 µm, respectively. We studied the impact of both the number of atomic layers of graphene and the sensing areas of graphene on the responsivity and response/recovery time of the prepared graphene-based humidity sensors. We found that the relative resistance change of the prepared devices decreased with the increase of number of atomic layers of graphene under the same change of relative humidity. Further, devices based on tri-layer graphene showed the fastest response/recovery time, while devices based on double-layer graphene showed the slowest response/recovery time. Finally, we chose devices based on double-layer graphene that have relatively good responsivity and stability for application in respiration monitoring and contact-free finger monitoring.

Unraveling the Spin-to-Charge Current Conversion Mechanism and Charge Transfer Dynamics at the Interface of Graphene/WS2 Heterostructures at Room Temperature.

We report experimental investigations of spin-to-charge current conversion and charge transfer (CT) dynamics at the interface of the graphene/WS2 van der Waals heterostructure. Pure spin current was produced by the spin precession in the microwave-driven ferromagnetic resonance of a permalloy film (Py=Ni81Fe19) and injected into the graphene/WS2 heterostructure through a spin pumping process. The observed spin-to-charge current conversion in the heterostructure is attributed to the inverse Rashba-Edelstein effect (IREE) at the graphene/WS2 interface. Interfacial CT dynamics in this heterostructure was investigated based on the framework of the core-hole clock (CHC) approach. The results obtained from spin pumping and CHC studies show that the spin-to-charge current conversion and charge transfer processes are more efficient in the graphene/WS2 heterostructure compared to isolated WS2 and graphene films. The results show that the presence of WS2 flakes improves the current conversion efficiency. These experimental results are corroborated by density functional theory (DFT) calculations, which reveal (i) Rashba spin-orbit splitting of graphene orbitals and (ii) electronic coupling between graphene and WS2 orbitals. This study provides valuable insights for optimizing the design and performance of spintronic devices.

Graphene Oxide Quantum Dots-Preactivated Dental Pulp Stem Cells/GelMA Facilitates Mitophagy-Regulated Bone Regeneration.

Background: In bone tissue engineering (BTE), cell-laden scaffolds offer a promising strategy for repairing bone defects, particularly when host cell regeneration is insufficient due to age or disease. Exogenous stem cell-based BTE requires bioactive factors to activate these cells. Graphene oxide quantum dots (GOQDs), zero-dimensional derivatives of graphene oxide, have emerged as potential osteogenic nanomedicines. However, constructing biological scaffolds with GOQDs and elucidating their biological mechanisms remain critical challenges. Methods: We utilized GOQDs with a particle size of 10 nm, characterized by a surface rich in C-O-H and C-O-C functional groups. We developed a gelatin methacryloyl (GelMA) hydrogel incorporated with GOQDs-treated dental pulp stem cells (DPSCs). These constructs were transplanted into rat calvarial bone defects to estimate the effectiveness of GOQDs-induced DPSCs in repairing bone defects while also investigating the molecular mechanism underlying GOQDs-induced osteogenesis in DPSCs. Results: GOQDs at 5 µg/mL significantly enhanced the osteogenic differentiation of DPSCs without toxicity. The GOQDs-induced DPSCs showed active osteogenic potential in three-dimensional cell culture system. In vivo, transplantation of GOQDs-preactivated DPSCs/GelMA composite effectively facilitated calvarial bone regeneration. Mechanistically, GOQDs stimulated mitophagy flux through the phosphatase-and-tensin homolog-induced putative kinase 1 (PINK1)/Parkin E3 ubiquitin ligase (PRKN) pathway. Notably, inhibiting mitophagy with cyclosporin A prevented the osteogenic activity of GOQDs. Conclusion: This research presents a well-designed bionic GOQDs/DPSCs/GelMA composite scaffold and demonstrated its ability to promote bone regeneration by enhancing mitophagy. These findings highlight the significant potential of this composite for application in BTE and underscore the crucial role of mitophagy in promoting the osteogenic differentiation of GOQDs-induced stem cells.

The Construction of Face-to-Face Combination between NiFe-layered Double Hydroxide Nanosheets and Monolayer rGO for Efficient Water Splitting and Oxygen Reduction.

Developing cost-effective and efficient electrocatalysts is essential for advancing a green energy future. Herein, a NiFe-layered double hydroxide loaded on reduced graphene oxide (NiFe-LDHs@rGO) hybrid was synthesized using a straightforward three-step process involving exfoliation tearing, electrostatic self-assembly, and chemical reduction. The face-to-face packing and ultrathin exfoliation enable strong heterogeneous interactions, fully harnessing the potential of these complementary two-dimensional counterparts. Consequently, the resultant catalyst displays outstanding oxygen evolution reaction (OER) catalytic activity and stability, whose overpotential is as low as 241 mV at 30 mA cm-2 and 255 mV at 50 mA cm-2 with a low Tafel slope of 62.1 mV dec-1. Both the experimental results and density functional theory (DFT) calculations reveal that the face-to-face assembly strengthens the electronic interactions between NiFe-LDHs and rGO, which effectively modulates the d-band center of Ni and Fesites and improves the reaction kinetics for OER. Moreover, the resultant NiFe-LDHs@rGO hybrids exhibit excellent multifunctional catalytic performance. Its hydrogen evolution reaction (HER) activity is endowed by Fe-site of NiFe-LDHs and defect states rGO and achieves a low voltage of 1.68 V to drive a current density of 10 mA cm-2 for overall water splitting. The face-to-face heteroassembly also imparts NiFe-LDHs@rGO with superior oxygen reduction reaction (ORR) activity, with a half-wave potential of 0.70 V and a limiting current density of 4.2 mA cm-2. Its ORR primarily follows a four-electron transfer pathway with a minor contribution from a two-electron process. This study establishes the groundwork for optimizing two-dimensional heterogeneous interfaces in LDH@carbon-based materials for advanced energy conversion.

Ultra-efficient Heat Transport across a "2.5D" All-carbon sp2/sp3 Hybrid Interface.

Single- and few-layer graphene-based thermal interface materials (TIMs) with extraordinary high-temperature resistance and ultra-high thermal conductivity are very essential to develop the next-generation integrated circuits. However, the function of the as-prepared graphene-based TIMs would undergo severe degradation when being transferred to chips, as the interface between the TIMs and chips possesses a very small interfacial thermal conductance. Here, a "2.5D" all-carbon interface containing rich covalent bonding, namely a sp2/sp3 hybrid interfaces is designed and realized by a plasma-assisted chemical vapor deposition with a function of ultra-rapid quenching. The interfacial thermal conductance of the 2.5D interface is excitingly very high, up to 110-117 MWm-2K-1 at graphene thickness of 12-25 nm, which is even more than 30% higher than various metal/diamond contacts, and orders of magnitude higher than the existing all-carbon contacts. Atomic-level simulation confirm the key role of the efficient heat conduction via covalent C-C bonds, and reveal that the covalent-based heat transport could contribute 85% to the total interfacial conduction at a hybridization degree of 22 at%. This study provides an efficient strategy to design and construct 2.5D all-carbon interfaces, which can be used to develop high performance all-carbon devices and circuits.

Flexible epidermal wearable sensor for Athlete's sweat biomarkers monitoring.

Wearable sweat sensors hold great promise for the monitoring of athletic sweat biomarkers that are reflective of physical status and the inimitable feature of wearable sensors to conduct dynamic sweat analysis in situ. However, the preparative methods of wearable patches for monitoring athlete's biomarkers are often complicated. Here, we demonstrate the first example of "sports lab-on-skin" as a fully integrated epidermal sweat sensor through simple laser engraving and laser cutting methods, which enables on-body and wirelessly measuring sweat Na+, sweat K+, sweat lactate, and initial sweat rate for physical status assessment. We test the performance of the "sports lab-on-skin" in both physically trained and un-trained groups under the same exercise intensity. We also validate the influence of different scenarios (water intake, breakfast, and exercise intensity) on dehydration time, sweat K+ level, sweat lactate level, and initial sweat rate.

Assessment of Edge Modification of Nanographene.

Carboxy groups on the edges of nanographene (NG) enable functionalization for realizing NG-organic hybrid materials. Therefore, assessment of the edge-functionalization of the electronic structures of NGs is valuable for the rational design of functional carbon materials. In this study, the structures of model NGs comprising 174 carbon atoms with armchair edges and various functional groups at the edges were computed. To achieve the greatest possible similarity between the computed structure and the real one, the carbon framework was designed based on experimental observations. The functional groups can be accessed via suitable chemical reactions. The computations predicted that although the conversion of carboxyl groups with electron-withdrawing/donating groups influences the orbital energies, the HOMO-LUMO (H-L) gap is not significantly affected, except in a few cases. Among the evaluated examples, π-extension had the greatest influence on the H-L gap. Interestingly, for the Pd2+-coordinated NG, the participation of the low-lying LUMO localized on Pd2+ in the surface-to-metal transitions seemingly narrowed the H-L gap, and a surface-to-ligand transition was observed.

Is Low Polydispersity Always Beneficial? Exploring the Impact of Size Polydispersity on the Microstructure and Rheological Properties of Graphene Oxide.

Graphene oxide (GO) is a promising material widely utilized in advanced materials engineering, such as in the development of soft robotics, sensors, and flexible devices. Considering that GOs are often processed using solution-based methods, a comprehensive understanding of the fundamental characteristics of GO in dispersion states becomes crucial given their significant influence on the ultimate properties of the device. GOs inherently exhibit polydispersity in solution, which plays a critical role in determining the mechanical behavior and flowability. However, research in the domain of 2D colloids concerning the effects of GO's polydispersity on its rheological properties and microstructure is relatively scant. Consequently, gaining a comprehensive understanding of how GO's polydispersity affects these critical aspects remains a pressing concern. In this study, we aim to investigate the dispersions and structure of GOs and clarify the effect of polydispersity on the rheological properties and yielding behavior. Using a rheometer, polarized optical microscopy, and small-angle X-ray scattering, we found that higher polydispersity in the same average size leads to overall improved rheological properties and higher flowability during yielding. Thus, our study can be beneficial in the employment of polydispersity in the processing of GO such as 3D printing and fiber spinning.

Fabrication of Self-Assembled Graphene Oxide Film and Its Application in Aqueous Zinc Metal Batteries.

Fabrication of well-dispersed thin graphene oxide (GO) films (GOFs) has always been a challenge. Herein, a quick preparation method for GOFs was developed using our homemade GO with a large lateral size. The film can be prepared in less than 2 h via a metal framework-induced self-assembly process. The thickness of the films can be as thin as ∼15.5 µm, which will be thinner with compression. When it is used as a flexible modification layer on the Zn metal for aqueous Zn-ion batteries, Zn can grow along the [010] direction in plane and stack orderly along the [002] direction even on the Cu substrate with GOF through epitaxial plating owing to negligible lattice mismatch between the (002) plane of Zn and the hexagonal ring [also (002) plane for graphite] of GO. Meanwhile, the rich O groups on the GO film can provide abundant zincophilic points and promote uniform distribution of Zn2+ around the anode. Finally, dendrite-free and dense Zn stripping/plating can be achieved and well remained. The GOF@Zn symmetric cell reveals long cyclic stability of 1300 h at 1 mA cm-2 and 1 mA h cm-2. It still can remain at 350 h even at a very high current density of 10 mA cm-2 accompanied by a high areal capacity of 10 mA h cm-2. With the same plating amount of 5 mA h cm-2, the thickness of the plated Zn is only ∼10 µm with GOF modification, very close to the theoretical value of 8.54 µm, much thinner than that without GOF (∼18 µm), indicating very dense deposition. Full cells assembled with the GOF@Zn anode and the MnO2 cathode exhibit a capacity retention rate of 71% over 1000 cycles at 0.7 A g-1, showing much better cycling performance than that using bare Zn.

Graphene Chainmail-Enabled Moderate Precatalyst Phase Evolution for Sustainable Polysulfide Electrocatalysis in Li─S Batteries.

The rational design of polysulfide electrocatalysts is of vital importance to achieve longevous Li─S batteries. Notwithstanding fruitful advances made in elevating electrocatalytic activity, efforts to regulate precatalyst phase evolution and protect active sites are still lacking. Herein, an in situ graphene-encapsulated bimetallic model catalyst (CoNi@G) is developed for striking a balance between electrocatalytic activity and stability for sulfur electrochemistry. The layer numbers of directly grown graphene can be dictated by tuning the synthetic duration. Exhaustive experimental and theoretical analysis comprehensively reveals that the tailored graphene chainmail boosts catalytic durability while guaranteeing moderate phase evolution, accordingly attaining a decorated surface sulfidation with advanced catalytic essence. Benefiting from the sustainable polysulfide electrocatalysis, CoNi@G enabled sulfur electrodes to harvest a capacity output of 1276.2 mAh g-1 at 0.2 C and a negligible capacity decay of 0.055% per cycle after 1000 cycles at 1.0 C. Such a maneuver can be readily extended to other metallic catalysts including NiFe, CoFe, or Co. The work elucidates the precatalyst phase evolution mechanism through a controllable graphene-armored strategy, offering meaningful guidance to realize durable electrocatalysts in Li─S batteries.