Sample preparation under turbulent flow with renewable sorbent.

Turbulent flow chromatography is an online solid phase extraction mode that achieves the extraordinary effect of proxying an upper molecular weight cutoff for the retained molecules, based on loading the sample at high linear velocities. Despite the potential of being a universal sample preparation technique prior to inductively coupled plasma mass spectrometry and liquid chromatography mass spectrometry, it employs specific hardware and expensive consumables. In the present work we apply this technique using off-the-shelf fluidic components and the niche "bead injection" methodology. For the first time, this procedure has been executed with a pressure of approximately 20 bar, compared to the low pressure of the classic setup, achieving a sample throughput >285 h-1 for the SPE/TFC procedure, or 20 h-1 if the procedure involves renewing the sorbent, using no more than 4 mg of sorbent for every µ-SPE. Another novelty is that sorbent packing and unpacking has been controlled with a smart method using real-time pressure feedback as quality control for truly unattended operation. Finally, the turbulent flow chromatography principle has been comprehensively characterized, providing similar performance to that demonstrated in earlier literature, and the ancillary sample preparation capabilities, e.g., in-valve acidification, have been demonstrated by the fractionation of gadolinium in surface waters prior to ICP-MS, an element of increasing surface water concern due to its use as a magnetic resonance contrast agent.

Combined orbital tomography study of multi-configurational molecular adsorbate systems.

Molecular reactivity is determined by the energy levels and spatial extent of the frontier orbitals. Orbital tomography based on angle-resolved photoelectron spectroscopy is an elegant method to study the electronic structure of organic adsorbates, however, it is conventionally restricted to systems with one single rotational domain. In this work, we extend orbital tomography to systems with multiple rotational domains. We characterise the hydrogen evolution catalyst Co-pyrphyrin on an Ag(110) substrate and compare it with the empty pyrphyrin ligand. In combination with low-energy electron diffraction and DFT simulations, we fully determine adsorption geometry and both energetics and spatial distributions of the valence electronic states. We find two states close to the Fermi level in Co-pyrphyrin with Co [Formula: see text] character that are not present in the empty ligand. In addition, we identify several energetically nearly equivalent adsorption geometries that are important for the understanding of the electronic structure. The ability to disentangle and fully elucidate multi-configurational systems renders orbital tomography much more useful to study realistic catalytic systems.

Ranking the Stability of Transition-Metal Complexes by On-Surface Atom Exchange.

Surface-adsorbed macrocycles exhibit a number of interesting physical and chemical properties; many of them are determined by their transition-metal centers. The hierarchical exchange of the central metal atom in such surface-adsorbed complexes is demonstrated, specifically in the porphyrin-like macrocycle pyrphyrin adsorbed on Cu(111). Using scanning tunneling microscopy and X-ray photoelectron spectroscopy, we show that Cu as central metal atom is easily exchanged with Ni or Fe atoms supplied in trace amounts to the surface. Atom exchange of Ni centers with Fe atoms also occurs, with moderate yield. These results allow ranking the stability of the surface-adsorbed Cu, Ni, and Fe complexes. The fact that the atom exchange occurs at 423 K shows that surface-adsorbed macrocycles can be surprisingly easily transformed.

Structure-Activity and Stability Relationships for Cobalt Polypyridyl-Based Hydrogen-Evolving Catalysts in Water.

A series of eight new and three known cobalt polypyridyl-based hydrogen-evolving catalysts (HECs) with distinct electronic and structural differences are benchmarked in photocatalytic runs in water. Methylene-bridged bis-bipyridyl is the preferred scaffold, both in terms of stability and rate. For a cobalt complex of the tetradentate methanol-bridged bispyridyl-bipyridyl complex [CoII Br(tpy)]Br, a detailed mechanistic picture is obtained by combining electrochemistry, spectroscopy, and photocatalysis. In the acidic branch, a proton-coupled electron transfer, assigned to formation of CoIII -H, is found upon reduction of CoII , in line with a pKa (CoIII -H) of approximately 7.25. Subsequent reduction (-0.94 V vs. NHE) and protonation close the catalytic cycle. Methoxy substitution on the bipyridyl scaffold results in the expected cathodic shift of the reduction, but fails to change the pKa (CoIII -H). An analysis of the outcome of the benchmarking in view of this postulated mechanism is given along with an outlook for design criteria for new generations of catalysts.

Atomically Resolved Band Bending Effects in a p-n Heterojunction of Cu2O and a Cobalt Macrocycle.

We present a hetero junction based on macrocyclic hydrogen evolution catalysts (HEC) physisorbed on a single crystalline Cu2O(111) surface. Angle-resolved X-ray photoelectron spectroscopy (ARXPS) provides the spatial resolution of the band bending within the first nanometer of the subsurface region. Oxygen vacancies on the Cu2O(111) surface cause a downward band bending which is conserved upon adsorption of HEC layers of various thicknesses. This allows photoexcited electrons to be directed toward the surface where they can be made available for the reduction of protons by the HEC. Furthermore, Poisson's equation relates more subtle changes in the measured ARXPS spectra to the local charge density profile within the first 7 Å away from the surface and with atomic resolution. All observations are consistent with a polarization of the molecular layer in response to the electrical field at the oxide surface, which should be a general phenomenon at such organic-oxide heterointerfaces.

The impact of metalation on adsorption geometry, electronic level alignment and UV-stability of organic macrocycles on TiO2(110).

Metal complexes of the tetradentate bipyridine based macrocycle pyrphyrin (Pyr) have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on stoichiometric TiO2(110) is investigated in ultrahigh vacuum by means of scanning tunneling microscopy, photoelectron spectroscopy, low-energy electron diffraction, and density functional theory. In a joint experimental and computational effort, the local adsorption geometry at low coverage, the long-range molecular ordering at higher coverage and the electronic structure have been determined for both the bare ligand and the cobalt-metalated Pyr molecule on TiO2. The energy level alignment of CoPyr/TiO2 supports electron injection into TiO2 upon photoexcitation of the CoPyr complex and thus renders it a potential sensitizer dye. Importantly, Co-incorporation is found to stabilize the Pyr molecule against photo-induced degradation, while the bare ligand is decomposed rapidly under continuous UV-irradiation. This interesting phenomenon is discussed in terms of additional de-excitation channels for electronically highly excited molecular states.

From porphyrins to pyrphyrins: adsorption study and metalation of a molecular catalyst on Au(111).

The molecular ligand pyrphyrin, a tetradentate bipyridine based macrocycle, represents an interesting but widely unexplored class of molecules. It resembles the well-known porphyrin, but consists of pyridyl subunits instead of pyrroles. Metal complexes based on pyrphyrin ligands have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on a single crystalline Au(111) surface is investigated in an ultrahigh vacuum by means of scanning tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy and density functional theory. Pyrphyrin coverages of approximately one monolayer and less are obtained by sublimation of the molecules on the substrate kept at room temperature. The molecules self-assemble in two distinct phases of long-range molecular ordering depending on the surface coverage. The deposition of cobalt metal and subsequent annealing lead to the formation of Co-ligated pyrphyrin molecules accompanied by a pronounced change of the molecular self-assembly. Electronic structure calculations taking the herringbone reconstruction of Au(111) into account show that the molecules are physisorbed, but preferred adsorption sites are identified where Co and the N atoms of the two terminal cyano groups are optimally coordinated to the surface Au atoms. An intermediate state of the metalation reaction is observed and the reaction steps for the Co metalation of pyrphyrin molecules on Au(111) are established in a joint experimental and computational effort.