Search arXiv⌕ Search
Home/Archive/arXiv

arXiv · 2603.14314

Carbon black and hydrogen production from methane pyrolysis: measured and modeled insights from integrated gas and particle diagnostics in shock tubes

Gibson Clark·Mohammad Adib·Chengze Li·Taylor M. Rault·Jesse W. Streicher·Enoch Dames·M. Reza Kholghy·Ronald K. Hanson
View original source ↗Read source document ↗Export metadata ↓

Abstract

Methane (CH4) pyrolysis is a promising route to co-produce hydrogen (H2) and carbon black (CB) while avoiding emissions associated with steam-methane reforming and furnace black processes. Model development of pyrolytic CB synthesis requires experimental observations of concurrent gas chemistry, particulate formation, and morphology. This work presents a combined experimental and modeling study of CH4 pyrolysis behind reflected shock waves in 5% CH4/Argon mixtures at post-reflected shock temperatures (T5) of 1850-2450 K and P5 around 4.5 atm. Laser absorption diagnostics quantified CH4, C2H4, and C2H2 mole fractions, while multiwavelength extinction (633 and 1064 nm) resolved time-dependent particle formation and the temperature-dependent evolution of optical maturity. Simulations reproduce small-molecule speciation well, but large variations in predicted polycyclic aromatic hydrocarbons (PAHs) persist among models. Coupled gas-particle simulations capture accurate volume fraction (fv) trends and the influence of gas dynamics but underpredict induction times at high T5. Samples collected at the shock tube endwall were analyzed by transmission electron microscopy (TEM) to quantify primary particle size distributions and nanostructure arrangement. Image segmentation and manual measurements showed reduced primary particle size growth (dp) with increasing T5, while graphitic nanostructure generally increased. This study provides an integrated benchmark for improving models of CB and H2 production from CH4 pyrolysis by constraining gas-phase kinetics, PAH-driven inception, particle dynamics, and particle maturity. The results highlight that accurate partitioning of mass between particle number and particle size is an important constraint for further model development.

Explore related subjects

physics.chem-ph

Keep this discovery

Explore connections, maps & timelines

BibTeXRIS

Gibson Clark, Mohammad Adib, Chengze Li, Taylor M. Rault, Jesse W. Streicher, Enoch Dames, M. Reza Kholghy, Ronald K. Hanson. 2026-03-15. Carbon black and hydrogen production from methane pyrolysis: measured and modeled insights from integrated gas and particle diagnostics in shock tubes. https://arxiv.org/abs/2603.14314

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Charge Transfer with a Spin. I: A Variational Constrained-CASSCF Framework for Investigating Charge Transfer in the Presence of Spin-Orbit Coupling

Charge transfer in open-shell molecular systems can involve a delicate interplay between charge localization, orbital relaxation, and spin-orbit coupling (SOC), particularly near ground-excited state crossings. Here, we introduce a very inexpensive variational framework for treating these effects in odd-electron systems by extending the electron/hole-transfer Dynamically-weighted State-Averaged Constrained CASSCF (eDSC/hDSC) method to include SOC. Our method incorporates the SOC Hamiltonian directly into the variational orbital optimization through complex-valued spinor orbitals, allowing orbital and spin degrees of freedom to relax self-consistently while preserving the time-reversal symmetry of doublet states. The method achieves smooth potential energy surfaces and rapid self-consistent field (SCF) convergence; moreover, from physically small to artificially large SOC strengths, the calculation can be converged to very tight thresholds across the whole potential energy surface. While the results presented here are for systems with two charge centers, as shown in the appendix, the theory is quite general and can be adapted to either a system of $N$ charge centers or a metal-molecule surface with a continuum of states, so that charge transport (and not just charge transfer) can also be studied. The approach therefore provides a route towards ab initio studies of spin-dependent charge transfer and charge transport in molecular systems with nontrivial spin degrees of freedom.

physics.chem-ph↗
arXiv2026

Charge Transfer with a Spin. II: A Framework for Diabatization which Localizes Charge and Spin

We investigate a diabatization procedure that localizes charges (in real space) and localizes spins (in spin space) for open-shell systems that exhibit charge transfer in the presence of spin-orbit coupling. The procedure is applied to a two-state crossing between pairs of Kramers-restricted doublet states (which can also be considered effectively a four-state crossing). To generate the relevant diabatic states, we employ a two-step optimization over complex-unitary rotations that sequentially maximizes dipole and spin moments through iterative Jacobi sweeps; the resulting update rules are effectively equivalent to those of approximate joint diagonalization (AJD) applied to charge and spin. The method converges rapidly and yields smooth diabatic potential energy surfaces that preserve dipole and spin properties (e.g., a smoothly varying spin quantization axis) along the reaction coordinate while maintaining time-reversal symmetry.

physics.chem-ph↗
arXiv2026

Fixed-Dimensional Latent Flow for Generating Variable-Size 3D Molecules

Molecular size is coupled to composition, structure, and function, yet most 3D molecular generators require a predefined atom count. We introduce Equivariant-Free Transformer-Autoencoded Latent Flow Matching, a two-stage framework that samples a fixed-dimensional latent vector using flow matching and uses an autoregressive Transformer to determine molecular size, atom types, coordinates, and chemical attributes. Canonical atom ordering and rigid-pose alignment enable Transformers without equivariant layers, while decoded attributes guide bond reconstruction. On PCQM4Mv2, unconditional generation yields 87.9\% unique, novel molecules passing sanitization and PoseBusters checks, exceeding baselines with lower end-to-end training and sampling time and higher end-to-end throughput. Across ten target HOMO-LUMO gaps, internal ranking retains 30\% of screened candidates and increases the density functional theory-verified hit rate within 0.1 eV from 25.0\% to 52.4\%, while largely preserving novelty and diversity. These results demonstrate fixed-dimensional latent generation with autoregressive decoding as a practical approach to molecular design without prespecifying size.

physics.chem-ph↗