Pyrolysis Of Precursors Research Articles

Endowing turbostratically porous carbon with rich edge nitrogen active sites for efficient capacitive removal of phosphate

The mitigation of phosphate in water is a pivotal concern for the prevention of eutrophication and enhancement of water quality. Capacitance deionization (CDI) technique possesses the merits of high removal efficacy, facile operation, and environmental friendliness, rendering it a promising strategy for phosphate elimination. Herein, the nitrogen-rich laminar porous carbon composites (NTPCs) prepared by direct pyrolysis of supermolecular precursor were utilized as phosphate capture electrodes. The resulting NTPC800 features a high nitrogen content turbostratically amorphous carbon framework, which facilitates efficient ion diffusion pathways and electron transfer. The abundant presence of edge nitrogen (pyridine and pyrrole nitrogen) optimizes the electronic structure of the carbon system and provides more active sites, thus leading to the boosted electrochemical activity and dephosphorization efficiency. Consequently, NTPC800 demonstrates a rapid phosphate removal capacity, achieving 73.51 mg g−1 within a mere 10 min at 1.2 V condition, which is nearly 6 times more efficient than that of the commercial activated carbon electrode. Moreover, it exhibited consistent phosphate removal efficiency across various pH ranges, coexisting ion interferences, and cyclic stability assessments. This study provides theoretical support for the utilization of edge nitrogen decorated carbonaceous electrodes to enhance charge transfer and provide additional active sites for efficient capacitive dephosphorization.

Nonthermal plasma coupled with Mn/N-doped carbon catalysts for highly efficient removal of toluene

In order to ensure the excellent performance of a nonthermal plasma (NTP)-catalysis system, a highly efficient catalyst is generally required. In this study, nitrogen-enriched hollow hybrid carbon (N-C) catalysts were designed, synthesized through facile pyrolysis of a zeolitic imidazolate framework precursor, and used as a support on which to disperse Mn species. Notably, the coupling of NTP with the Mn/N-C catalysts resulted in strong activity. Mn loading of 6 % was found to remove almost all toluene (98 % efficiency) and to have COx selectivity (82.1 %) when the specific energy density (SED) value was 252 J·L−1; when the SED value was 102 J·L−1, the energy yield was 10.6 g·kWh−1. The performances of the developed Mn/N-C catalysts were related to their highly dispersed nature and strong ability to activate oxygen and dissociate O3. Hereafter, the toluene decomposition pathway is described. The present findings demonstrate the potential applications of porous N-C-supported metal oxide catalysts in the removal of volatile organic compounds through a catalyzed NTP process.

Co-ZIF-derived dual Co and Co3S4 nanoparticles encapsulated in N-doped carbon matrix for efficient photocatalytic CO2 reduction

In this study, a novel N-doped carbon-coated dual Co and Co3S4 nanoparticles composite (Co-Co3S4@NC) has been developed by pyrolysis of an ideal flower-like Co-ZIF precursor followed via subsequent hydrothermal sulfidation. Under visible-light irradiation, the Co-Co3S4@NC exhibits outstanding performances for CO2 reduction with H2O vapor into CO (23.14 μmol g−1 h−1) and CH4 (0.62 μmol g−1 h−1) in a continuous flow system, significantly outperforming the single Co@NC photocatalyst. The experimental results demonstrate that the energy band structure in Co-Co3S4@NC can provide a more favorable reduction potential for the effective reduction of CO2. Moreover, the presence of Co3S4 is beneficial for the rapid separation and transfer of charges, thereby enhancing the utilization of photogenerated charge carriers. Thanks to its unique composition, Co-Co3S4@NC possesses abundant active sites for chemisorption and activation of CO2, which facilitates CO2 photoreduction. The reaction mechanism is revealed in detail by analyzing the key intermediate species obtained through in situ DRIFTS. The current work offers a facile route for the construction of MOF-derived composites for promising photocatalytic reactions.

Optimizing capacitance performance: Solar pyrolysis of lignocellulosic biomass for homogeneous porosity in carbon production

This work compares the effect of using a solar reactor against a conventional electrical furnace to obtain carbon materials by pyrolysis of a lignocellulosic precursor. The solar reactor is directly irradiated and includes modifications to improve the control of the process and the reproducibility of solar experiments. A bagasse of agave creole was selected as the lignocellulosic precursor or biomass to obtain carbon materials at temperatures of 700 °C. Comparing carbons produced by conventional and solar pyrolysis, higher crystallinity and lower hydrophilicity are evident in the former. Moreover, conventional pyrolysis tends to promote a more homogeneous porous structure in comparison to solar pyrolysis. However, within the spectrum of solar carbons produced, the morphology of biomass plays a crucial role in influencing the chemical composition and porosity properties. Specifically, the use of fibers instead of powders to produce carbons through solar pyrolysis results in a more homogeneous porosity, attributed to an enhanced volumetric absorption of solar radiation. This modification leads to a significant improvement in capacitance, increasing from 125 F/g to 175 F/g at 5 mV/s in aqueous electrolytes. The carbons from the solar furnace are reproducible, underlying the potential of the proposed process towards a sustainable alternative. To achieve a theoretical reference, the pyrolysis process was mimic trough Reactive Molecular Dynamics calculations modeling the initial structural conditions of agave biomass with its corresponding lignocellulosic components and considering analogous thermal conditions. The resulting carbon structures at the end of the simulations showed structural properties that are consistent with those observed in the pair distribution functions obtained from XRD and the pore size distribution from physisorption analyses. This combined experimental–theoretical approach offers the potential to elucidate porous carbon structures derived from pyrolysis processes powered by solar radiation . This method can help in the design and identification of lignocellulosic structures in biomass, with the resulting carbon materials suitable for energy storage applications.

Hollow Fiber Carbon Molecular Sieve Membranes for Gas Separation: A Mini Review

Abstract: Owing to the advantages of rapid adsorption and desorption characteristics, excellent gas separation performance, as well as good thermal and chemical resistance, carbon molecular sieve (CMS) membranes have been developed as a promising gas separation tool. Over the past 30 years, hollow fiber carbon molecular sieve (HFCMS) membranes have become the preferred choice for industrial applications due to their high surface area-to-volume ratio and the ability to assemble lightweight membrane modules. The gas transport mechanism behind the HFCMS is dominated by molecular sieving function. They can be prepared by pyrolysis of the polymeric hollow fiber precursors. Post-treatments can tailor the ultramicropores structure to improve the separation performance. This paper aims to review the recent progress in the preparation of HFCMS membranes from aspects of precursor selection, pyrolysis conditions and post-treatment. Moreover, a brief perspective in terms of future investigation of HFCMS membrane is also proposed.

Hybrid HfC‐SiCN matrix for improved oxidation resistance of carbon fiber–reinforced mini‐composites

AbstractHafnium carbide (HfC) is an ultrahigh‐temperature ceramic with high melting point, chemical stability, hardness, and wear resistance. However, its low fracture toughness and poor thermal shock resistance limit its structural applications in extreme environments. In this study, co‐curing of liquid precursors was carried out prior to complete pyrolysis of individual polymeric precursors. First, HfC preceramic polymer precursor was cured, followed by silicon carbonitride (SiCN) precursor curing on a 2D carbon fiber (CF) cloth using the drop‐coating process. The infiltrated CFs were pyrolyzed at 800°C to achieve CF/HfC‐SiCN ceramic mini‐composites. The cross‐linked precursor‐to‐ceramic yield was observed to be as high as 65% when the procedure was carried out in an inert environment. Although stable up to 1200°C, CF/HfC‐SiCN samples demonstrated susceptibility to oxidation at 1500°C in ambient air. The oxidation of HfC in the presence of SiC leads to the formation of a hafnium‐containing silicate (HfxSiyOz) along with hafnia (HfO2). This compound of silicate and hafnia limits oxygen diffusion better than SiO2 and HfO2 individually. The incorporation of SiCN in HfC ceramic led to improved phase stability compared to a neat HfC system. The results of this study also show that the use of liquid‐phase precursors for HfC and SiCN in the polymer‐infiltrated pyrolysis method is a promising approach to fabricating high‐temperature structural ceramic matrix composites with good oxidation resistance.

High pressure induced formation of carbon nanorods from tetracosane

Morphology control of carbon structures is essential for improving their performance in many applications. Direct pyrolysis of organic precursors, however, usually yields bulk amorphous carbon. Therefore, traditional methods for controlling the morphology of carbon structures involve multistep processes and complex precursor molecules. While various methods have been developed under ambient pressure, the impact of pressure on the morphology of the resulting carbon structures remains unexplored. Herein, we present the synthesis of carbon nanorods by direct pyrolysis of the low-cost aliphatic hydrocarbon tetracosane under high pressure conditions. The diameters of the carbon nanorods are adjusted by simply varying the synthetic pressures. High pressure allows controlling both the nanorod morphology as well as the degree of order, and local conductivity of the thus prepared nanorods has been confirmed by conductive atomic force microscopy measurements. Our method promises a convenient strategy to synthesize carbon structures with controlled morphology and high ordered chemical structure, which opens opportunities for potential electronic and electrochemical applications.

Effect of BN interfacial layer on the mechanical behavior of SiC fiber reinforced SiC ceramic matrix composites

AbstractBoron nitride (BN) interfacial layer with controlled thickness and structure was prepared on the surface of near stoichiometric ratio SiC fiber preforms by a chemical vapor deposition process, and the SiC/SiC composites were obtained by polymer precursor infiltration and pyrolysis process. The microstructure of the BN interfacial layer and SiC/SiC composites was tested by scanning electron microscopy, and the mechanical behavior of SiC/SiC composites was characterized by a mechanical properties test. Results showed that BN interfacial layer was evenly distributed in the fiber preforms with excellent thickness consistency. As the thickness of the BN interfacial layer increased, the deflection path of the crack increased gradually, resulting in the flexural strength first increasing and then decreasing. The mechanical behavior mentioned above was mainly attributed to the dual effects of load transfer and crack propagation of the BN interfacial layer; that was, the crack propagation of ceramic matrix under external load lengthened the path of load transfer and formed a large number of fibers bridging and pulling out successively, which contributed to the energy dissipation mechanism.

The effect of the pyrolysis temperature and biomass type on the biocarbons characteristics.

The conversion of biomass and natural wastes into carbon-based materials for various applications such as catalysts and energy-related materials is a fascinating and sustainable approach emerged during recent years. Precursor nature and characteristics are complex, hence, their effect on the properties of resulting materials is still unclear. In this work, we have investigated the effect of different precursors and pyrolysis temperature on the properties of produced carbon materials and their potential application as negative electrode materials in Li-ion batteries. Three biomasses, lignocellulosic brewery spent grain from a local brewery, catechol-rich lignin and tannins, were selected for investigations. We show that such end-product carbon characteristic as functional and elemental composition, porosity, specific surface area, defectiveness level, and morphology strictly depend on the precursor composition, chemical structure, and pyrolysis temperature. The electrochemical characteristics of produced carbon materials correlate with the characteristics of the produced materials. A higher pyrolysis temperature is shown to be favourable for production of carbon material for the Li-ion battery application in terms of both specific capacity and long-term cycling stability.

Microstructure evolution and ablation mechanisms of Csf/ZrB2-SiC composites at different heat fluxes under air plasma flame

In this study, short carbon fibre (Csf) reinforced ZrB2-SiC composites were fabricated via direct ink writing followed by precursor infiltration and pyrolysis. The ablation behaviour of the composites was investigated at heat fluxes of 4–6 MW/m2 under an air plasma flame, which revealed excellent ablation resistance with negative linear ablation rates of − 0.1 to − 0.5 µm/s. The results showed that ZrO2-SiO2 oxide layer was formed on the ablation surface after ablation, which provided effective protection to the internal materials. With an increase in heat flux, ZrO2 precipitated from the SiO2 melt first in the form of nano-tetragonal ZrO2 (t-ZrO2), owing to the vaporisation of SiO2. During cooling, the nano t-ZrO2 particles were retained, and some of them reacted with SiO2 to form ZrSiO4, thus improving the thermal stability of the SiO2-ZrO2 oxide layer. In contrast, t-ZrO2 agglomerated and grew owing to capillary force and finally transformed into monoclinic ZrO2 (m-ZrO2). Moreover, a higher heat flux led to the size of precipitation ZrO2 increases, meanwhile increasing the content of t-ZrO2 and ZrSiO4 in the oxide layer.

Microarchitected Compliant Scaffolds of Pyrolytic Carbon for 3D Muscle Cell Growth.

The integration of additive manufacturing technologies with the pyrolysis of polymeric precursors enables the design-controlled fabrication of architected 3D pyrolytic carbon (PyC) structures with complex architectural details. Despite great promise, their use in cellular interaction remains unexplored. This study pioneers the utilization of microarchitected 3D PyC structures as biocompatible scaffolds for the colonization of muscle cells in a 3D environment. PyC scaffolds are fabricated using micro-stereolithography, followed by pyrolysis. Furthermore, an innovative design strategy using revolute joints is employed to obtain novel, compliant structures of architected PyC. The pyrolysis process results in a pyrolysis temperature- and design-geometry-dependent shrinkage of up to 73%, enabling the geometrical features of microarchitected compatible with skeletal muscle cells. The stiffness of architected PyC varies with the pyrolysis temperature, with the highest value of 29.57±0.78GPa for 900°C. The PyC scaffolds exhibit excellent biocompatibility and yield 3D cell colonization while culturing skeletal muscle C2C12 cells. They further induce good actin fiber alignment along the compliant PyC construction. However, no conclusive myogenic differentiation is observed here. Nevertheless, these results are highly promising for architected PyC scaffolds as multifunctional tissue implants and encourage more investigations in employing compliant architected PyC structures for high-performance tissue engineeringapplications.

Embedding Pd into SnO2 drastically enhances gas sensing.

Combustion aerosol processes can uniquely embed noble metals into semiconducting particles. Here, monocrystalline SnO2 particles embedded with Pd and/or PdOx were made by flame spray pyrolysis (FSP) of appropriate precursors through microexplosions by droplet-to-particle conversion as the crystal size was proportional to the cube root of precursor solution concentration, C. These particles were air-annealed and leached with nitric acid for removal of metallic Pd from their surface. The SnO2 crystal size varied from 11 to 24 nm and was in close agreement with the primary particle size determined by nitrogen adsorption. The embedded fraction of Pd ranged from about 30 to 80% of the nominal Pd-content. This was achieved by judiciously varying the C, Pd content and the ratio of precursor solution to dispersion oxygen flowrates during FSP. The response of sensors made by doctor blading films of such particles to 1 ppm of acetone and CO was evaluated at 350 °C and 50% relative humidity. Embedding Pd/PdOx into SnO2 significantly increased the sensor response: 2-6 times over that of pure or conventionally-made Pd-containing SnO2 sensors at low nominal Pd-contents (0.2 mol%). For higher ones (i.e. 1 mol% Pd), the sensor response was enhanced by up to two orders of magnitude. This is attributed to Pd atoms in the SnO2 lattice near the particle surface and/or Pd/PdOx clusters acting as nanoelectrodes into SnO2 films and altering their transducing properties as shown by high resolution electron microscopy, XPS and baseline resistance measurements of pure and Pd-embedded SnO2 sensing films.

Porous layered ZnV2O4@C synthesized based on a bimetallic MOF as a stable cathode material for aqueous zinc ion batteries.

Vanadium-based oxides are considered potential cathode materials for aqueous zinc ion batteries (AZIBs) due to their distinctive layered (or tunnel) structure suitable for zinc ion storage. However, the structural instability and sluggish kinetics of vanadium-based oxides have limited their capacity and cycling stability for large-scale applications. To overcome these shortcomings, here a porous vanadium-based oxide doped with zinc ions and carbon with the molecular formula ZnV2O4@C (ZVO@C) as the cathode material is synthesized by the pyrolysis of a bimetallic MOF precursor containing Zn/V. This electrode demonstrates a remarkable specific capacity of 425 mA h g-1 at 0.5 A g-1 and excellent cycling stability with about 97% capacity retention after 1000 cycles at 10 A g-1. The excellent electrochemical performance of ZVO@C can be attributed to more reaction active sites and the faster reaction kinetics for zinc ion diffusion and storage brought about by the porous layered spinel-type tunnel structure with high surface area and massive mesoporosity, as well as the enhanced electron transport efficiency and more stable channel structure achieved from the doped conductive carbon. The reaction mechanism and structural evolution of the ZVO@C electrode are analyzed using X-ray diffraction and X-ray photoelectron spectroscopy, revealing the formation of a new phase of ZnxV2O5·nH2O during the first charge, which participates in reversible cycling together with ZVO@C during the charging and discharging processes. Moreover, the energy storage mechanism is revealed, in which zinc ions and hydrogen ions jointly participate in intercalation and extraction. The present study demonstrates that constructing composite vanadium-based oxides based on bimetallic organic frameworks as precursor templates is an effective strategy for the development of high-performance cathode materials for AZIBs.

Hexamethyldisiloxane pyrolysis: Probing H-atom initiation by femtosecond two-photon LIF

Previous experiments have led to the hypothesis that pyrolysis of silica nanoparticle precursors carried in an inert central gas jet surrounded by a laminar flame is initiated not by thermal decomposition (the measured jet temperatures are too low for pyrolysis), but by reactions with H-atoms diffusing from the surrounding flame into the jet. The current work tests this hypothesis using femtosecond two-photon laser-induced fluorescence (fs-TPLIF) to image H-atom concentrations in the same flame configuration as the previous experiments. Methane flames (ϕ = 0.83, 1.01 and 1.13) were generated using a multi-element diffusion (Hencken) burner equipped with a central tube through which the N2 jet was introduced. The fs-TPLIF line imaging showed significant concentrations of H-atoms in the nitrogen jets at heights above the burner (HAB) close to the methane flame front. The measurements indicate radial diffusion of the H atoms from the flame to the jet is significant. The H-atom concentrations in the jet increased with increasing stoichiometry of the methane flame. Additional experiments were performed with hexamethyldisiloxane entrained in the central jet flow. In each case, a diffusion flame producing silica nanoparticles was established at the boundaries between the central jet and the methane flames. The 2D H-atom images showed a transition from over-ventilated diffusion flames to under-ventilated diffusion flames with increasing equivalence ratio. Furthermore, the fs-TPLIF profiles show a significant production of H-atoms within the jet when the surrounding flame is lean. This knowledge contributes to a deeper understanding of the underlying mechanisms governing these synthesis flame systems and opens avenues for advancing silica nanoparticle synthesis techniques.

Nanoarchitectonics of ultrafine molybdenum carbide nanocrystals into three-dimensional nitrogen-doped carbon framework for capacitive deionization.

Molybdenum carbide (MoC) has emerged as a promising material for capacitive deionization (CDI), but the poor electrochemical kinetics in conventional MoC owing to the bulk structure and low electric conductivity limit its CDI performance. To address this challenge, herein, we develop a novel strategy to synthesize ultrafine MoC nanocrystals that are embedded within a three-dimensional nitrogen-doped carbon framework (NC/MoC). This synthesis method involves the space-confined pyrolysis of molybdate precursors within metal-organic frameworks (MOFs). In this process, molybdates are confined into the MOF crystalline structure, where MOFs provide a confined reactor and carbon source. The resulting NC/MoC with the uniformly distributed MoC nanocrystals provides sufficient active sites for the electrosorption of salt ions, while the MOF-derived NC matrix facilitates charge transfer and provides the space-confined effect for preventing the possible aggregations of MoC nanocrystals during the CDI process. The NC/MoC exhibits an impressive salt adsorption capacity (SAC, 84.2 mg g-1, 1.2 V), rapid desalination rate, and high cycling stability (91.4% SAC retention after 200 cycles), better than those of most previously reported carbon-based CDI materials. Besides, the possible mechanisms are systematically investigated by ex situ characterization and density functional theory calculations. This study opens up new avenues for the construction of metal carbide-based nanocrystals for CDI and other electrochemical applications.

Cf/SiC Ceramic Matrix Composites with Extraordinary Thermomechanical Properties up to 2000 °C.

The thermomechanical properties of carbon fiber reinforced silicon carbide ceramic matrix composites (Cf/SiC CMCs) were studied up to 2000 °C using high-temperature in situ flexural testing in argon. The CMC specimens were fabricated using an ultrahigh concentration (66 vol%) aqueous slurry containing nano-sized silicon carbide powder. The SiC powder compacts were obtained by drying the slurry and were densified using the precursor impregnation and pyrolysis (PIP) method with field assisted sintering technology/spark plasma sintering (FAST/SPS). The high relative density of the SiC green body (77.6%) enabled densification within 2.5 days using four PIP cycles. In contrast, conventional PIP processes take over 7 days. The in situ flexural strength of the Cf/SiC CMC was 434 MPa at 1750 °C, which was 84% higher than the room temperature value. The value further increased to 542 MPa at 2000 °C. Possible mechanisms to explain the excellent strength of the CMC at elevated temperatures are discussed.

Preparation of polymer-derived SiOC-Cu ceramic composites and their tribological performance

Cu-containing silicon oxycarbide (SiOC) ceramic composites have been prepared by thermal pyrolysis of polymeric precursors and subsequent spark plasma sintering at 1600 °C. The resulting composites consist of SiO2, SiC, free carbon, and Cu-Si alloys. The microstructure of the composites has been identified via optical microscope and SEM. The mechanical properties, including the Vickers hardness, nano-indentation hardness, and Young’s modulus, of the SiOC composites have been assessed via indentation methods. The effects of Cu content on the tribological properties of the composites have additionally been investigated under different sliding frequencies against Al2O3 spheres at room temperature. It is shown that the introduction of the Cu-Si alloys is effective in reducing the friction coefficient of the material system, which decreases linearly from 0.27 of monolithic SiOC to 0.15 of SiOC with 7 wt% Cu content at 1 Hz. Raman spectroscopy has highlighted the friction-driven evolution of the free carbon phase in the SiOC ceramics. Finally, a correlation between the sliding frequency, Cu-Si content, and tribological properties of SiOC is established.

Numerical analysis of particle radial distribution during spray pyrolysis of dual-solute precursor

This study investigates the droplet-to-particle formation process in spray pyrolysis, focusing on interactions between low-solubility precursor A (KNO3) and high-solubility precursor B (NaNO3). A numerical model simulates evaporation, multi-component transport, and precipitation in droplets, and is validated with experimental data. The numerical results reveal that the preferential precipitation of KNO3 near the surface hinders NaNO3, lowering its surface molar concentration. The radial distribution of NaNO3 varies with parameters, exhibiting monotonic or non-monotonic trends. The presence of a small amount of low-solubility KNO3 decreases NaNO3 near the surface, while a higher KNO3 proportion forms a shell layer, increasing NaNO3 from the center to the surface. The results also show that environmental factors influence particle size and component structure. Adjusting the precipitation rate of KNO3, along with reduced temperature and droplet size, leads to smaller particles, enhancing NaNO3 accumulation inside and decreasing surface concentration. This work deepens understanding of pyrolysis droplet evolution, supporting customizable particle design for improved droplet-based technologies.

Polymer-derived W-doping (Zr, Hf, Nb, Ta)C high entropy ceramics: Preparation, Properties and DFT calculation

(Zr, Hf, Nb, Ta, W)C high entropy carbides nano-powders (average particle size less than 65 nm) with low oxygen content (0.2–1.4 wt%) were synthesized through pyrolysis of polymer precursors. Bulk ceramics were fabricated through the process of hot-pressing, and their characteristics were studied by both computational and experimental methods. Density functional theory was carried out to analyze the effects of defects and the W element on the melting point, hardness, modulus, and toughness of ceramics. The results showed that W content had limited influence on the melting points and the aforementioned mechanical properties of ceramics, while carbon vacancies lead to a significant decrease in melting point, hardness and modulus, with slight increases in toughness. Experimental results indicated that the grain size, grain boundary strength, and lattice distortion of ceramic bulks increased with the increase of W content, which affected the mechanical properties consequently. Ceramics with W content of 5 mol% exhibited the best experimental comprehensive performances, with the Vickers hardness, fracture toughness and flexural strength of 23.82 ± 0.49 GPa, 5.66 ± 0.22 MPa·m1/2 and 593.95 ± 15.71 MPa, respectively.

Synthesis and pyrolysis of Hf–N–B backbone polymer precursor for HfC/HfB2 composite ceramics

AbstractMetallopolymers containing refractory metal in the main chain are highly desired but rarely reported as oxygen‐free single‐source precursors for preparing ultrahigh‐temperature ceramics. Herein, a novel single‐source precursor of poly‐hafnium‐borocarbosilane (PHBCNS) with an Hf–N–B backbone molecular structure was synthesized through the dehalogenation reaction between HfCl4 and B(NHCH3)3. The polymeric Hf–N–B chain with large bond angle and conjugated molecular structure endowed the PHBCNS precursor to be relatively stable, dissolvable, and meltable. Subsequent precursor pyrolysis up to 1800°C resulted in an HfC/HfB2 nanocomposite comprising an Hf content of 87.54 wt%, with the average grain size of HfC and HfB2 to be 34.9 and 74.1 nm, respectively. The ceramization mechanism and phase evolution from the PHBCNS precursor to HfC/HfB2 composite ceramics were thoroughly investigated. This work not only highlights a novel Hf–N–B backbone polymer with high metal content and good shaping properties but also provides fresh insights of designing single‐source precursors for ultrahigh‐temperature composite ceramics.