A kinetic model for the kraft pulping delignification of Eucalyptus globulus is proposed. This model is discriminated among some kinetic expressions often used in the literature, and the kinetic parameters are determined by fitting of experimental results. A total of 25 isothermal experiments at liquor-to-wood ratios of 50 and 5 L kg -1 have been carried out. Initial, bulk, and residual delignification stages have been observed during the lignin removal, the transitions being, referring to the lignin initial content, about 82 and 3%. Carbohydrate removal and effective alkali-metal and hydrosulfide consumption have been related with the lignin removal by means of effective stoichiometric coefficients for each stage, coefficients also being calculated by fitting of the experimental data. The kinetic model chosen has been used to simulate typical kraft pulping experiments carried out at nonisothermal conditions, using a temperature ramp. The model yields simulated values close to those obtained experimentally for the wood studied and also ably reproduces the trends of the literature data.

On-surface chemistry in ultrahigh vacuum offers complementary routes for synthesizing molecular complexes that cannot be accessed through standard solution chemistry. The presence of a surface not only imposes spatial two-dimensional restraints but also frequently acts as a source of adatoms actively participating in the chemical reactions. Here we demonstrate the formation of gold porphyrin derivatives via thermally induced chemical transformations of a fluorinated free-base porphyrin, 2H-4FTPP, on a Au(111) surface, which can rarely be accessed via standard solution chemistry protocols. We also provide an accurate description of the mechanisms of on-surface reactions and self-assembly processes, including structural and electronic characterization of intermediates and products using high-resolution scanning probe microscopy with a CO tip supported by a computational study. An initial annealing step at 500 K induces planarization of the adsorbed free base via dehydrogenation and ring-closing reactions that preserve the integrity of the C–F bonds. A second annealing step at 575 K enables metalation, producing unprecedented surface-supported gold-coordinated planarized porphyrins. A final annealing step at 625 K induces C–F and C–H activation, leading to intermolecular C–C coupling between phenyl termini to form planarized porphyrin oligomers. These results open new avenues for engineering in a stepwise manner thermally sensitive on-surface chemical reactions and metal–organic compounds that cannot be accessed in solution chemistry.

Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy‐carboxylate metal–organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X‐ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface‐supported metal–organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in‐plane easy magnetization axis despite the out‐of‐plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal–organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces.

The design of antiferromagnetic nanomaterials preserving large orbital magnetic moments is important to protect their functionalities against magnetic perturbations. Here, we exploit an archetype H 6 HOTP species for conductive metal−organic frameworks to design a Co-HOTP one-atom-thick metal−organic architecture on a Au(111) surface. Our multidisciplinary scanning probe microscopy, X-ray absorption spectroscopy, X-ray linear dichroism, and X-ray magnetic circular dichroism study, combined with density functional theory simulations, reveals the formation of a unique network design based on threefold Co +2 coordination with deprotonated ligands, which displays a large orbital magnetic moment with an orbital to effective spin moment ratio of 0.8, an in-plane easy axis of magnetization, and large magnetic anisotropy. Our simulations suggest an antiferromagnetic ground state, which is compatible with the experimental findings. Such a Co-HOTP metal−organic network exemplifies how on-surface chemistry can enable the design of field-robust antiferromagnetic materials.

The design of lanthanide multinuclear networks is an emerging field of research due to the potential of such materials for nanomagnetism, spintronics, and quantum information. Therefore, controlling their electronic and magnetic properties is of paramount importance to tailor the envisioned functionalities. In this work, a multidisciplinary study is presented combining scanning tunneling microscopy, scanning tunneling spectroscopy, X‐ray absorption spectroscopy, X‐ray linear dichroism, X‐ray magnetic circular dichroism, density functional theory, and multiplet calculations, about the supramolecular assembly, electronic and magnetic properties of periodic dinuclear 2D networks based on lanthanide‐pyridyl interactions on Au(111). Er‐ and Dy‐directed assemblies feature identical structural architectures stabilized by metal–organic coordination. Notably, despite exhibiting the same +3 oxidation state, there is a shift of the energy level alignment of the unoccupied molecular orbitals between Er‐ and Dy‐directed networks. In addition, there is a reorientation of the easy axis of magnetization and an increment of the magnetic anisotropy when the metallic center is changed from Er to Dy. Thus, the results show that it is feasible to tune the energy level alignment and magnetic anisotropy of a lanthanide‐based metal‐organic architecture by metal exchange, while preserving the network design.