Klaus Attenkofer

Isolated Ni single atoms in graphene nanosheets for high-performance CO2 reduction

Single-atom catalysts have emerged as an exciting paradigm with intriguing properties different from their nanocrystal counterparts. Here we report Ni single atoms dispersed into graphene nanosheets, without Ni nanoparticles involved, as active sites for the electrocatalytic CO2 reduction reaction (CO2RR) to CO. While Ni metal catalyzes the hydrogen evolution reaction (HER) exclusively under CO2RR conditions, Ni single atomic sites present a high CO selectivity of 95% under an overpotential of 550 mV in water, and an excellent stability over 20 hours’ continuous electrolysis. The current density can be scaled up to more than 50 mA cm−2 with a CO evolution turnover frequency of 2.1 × 105 h−1 while maintaining 97% CO selectivity using an anion membrane electrode assembly. Different Ni sites in graphene vacancies, with or without neighboring N coordination, were identified by in situ X-ray absorption spectroscopy and density functional theory calculations. Theoretical analysis of Ni and Co sites suggests completely different reaction pathways towards the CO2RR or HER, in agreement with experimental observations.

Direct observation of bi-alkali antimonide photocathodes growth via in operando x-ray diffraction studies

Alkali antimonides have a long history as visible-light-sensitive photocathodes. This work focuses on the process of fabrication of the bi-alkali photocathodes, K2CsSb. In-situ synchrotron x-ray diffraction and photoresponse measurements were used to monitor phase evolution during sequential photocathode growth mode on Si(100) substrates. The amorphous-to-crystalline transition for the initial antimony layer was observed at a film thickness of 40 A . The antimony crystalline structure dissolved upon potassium deposition, eventually recrystallizing upon further deposition into K-Sb crystalline modifications. This transition, as well as the conversion of potassium antimonide to K2CsSb upon cesium deposition, is correlated with changes in the quantum efficiency.

Experimental proof of the bifunctional mechanism for the hydrogen oxidation in alkaline media

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data, which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo-PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shape enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.

Bi-alkali antimonide photocathode growth: An X-ray diffraction study

Bi-alkali antimonide photocathodes are one of the best known sources of electrons for high current and/or high bunch charge applications like Energy Recovery Linacs or Free Electron Lasers. Despite their high quantum efficiency in visible light and low intrinsic emittance, the surface roughness of these photocathodes prohibits their use as low emittance cathodes in high accelerating gradient superconducting and normal conducting radio frequency photoguns and limits the minimum possible intrinsic emittance near the threshold. Also, the growth process for these materials is largely based on recipes obtained by trial and error and is very unreliable. In this paper, using X-ray diffraction, we investigate the different structural and chemical changes that take place during the growth process of the bi-alkali antimonide material K2CsSb. Our measurements give us a deeper understanding of the growth process of alkali-antimonide photocathodes allowing us to optimize it with the goal of minimizing the surface roughness to preserve the intrinsic emittance at high electric fields and increasing its reproducibility.

Diamond sensors and polycapillary lenses for X-ray absorption spectroscopy

Diamond sensors are evaluated as incident beam monitors for X-ray absorption spectroscopy experiments. These single crystal devices pose a challenge for an energy-scanning experiment using hard X-rays due to the effect of diffraction from the crystalline sensor at energies which meet the Bragg condition. This problem is eliminated by combination with polycapillary lenses. The convergence angle of the beam exiting the lens is large compared to rocking curve widths of the diamond. A ray exiting one capillary from the lens meets the Bragg condition for any reflection at a different energy from the rays exiting adjacent capillaries. This serves to broaden each diffraction peak over a wide energy range, allowing linear measurement of incident intensity over the range of the energy scan. Extended X-ray absorption fine structure data are measured with a combination of a polycapillary lens and a diamond incident beam monitor. These data are of comparable quality to data measured without a lens and with an ionization chamber monitoring the incident beam intensity.

Real time evolution of antimony deposition for high performance alkali photocathode development

The development of X-ray techniques opens new opportunities for real-time in-situ study of photocathode growth process in details. The initial ultra thin Sb films during photocathode process were investigated on multiple substrates based on different applications. The real-time X-ray scattering and post-growth X-ray reflectivity and diffraction measurement were performed and analyzed. Experiment results indicate that Sb deposition performs a phase change from amorphous to crystalline, the critical thicknesses are different on B33 float glass, Si and Mo. Two methods were applied for film thickness calculation from X-ray scattering data, and they agree well with thickness monitor result. Sb films deposited on different substrates show similar final film roughnesses. The real time x-ray study indicates that the initial Sb layer deposition process on different substrate has different structure during deposition, the optimized thickness of the initial Sb layer may varies depends on the substrate. This study also paved the road for further study of the more complex alkali metal vapor diffusion process in photocathode growth.

Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery

Conductive metal sulfides are promising multi-functional additives for future lithium-sulfur (Li-S) batteries. These can increase the sulfur cathode’s electrical conductivity to improve the battery’s power capability, as well as contribute to the overall cell-discharge capacity. This multi-functional electrode design showed initial promise; however, complicated interactions at the system level are accompanied by some detrimental side effects. The metal sulfide additives with a chemical conversion as the reaction mechanism, e.g., CuS and FeS2, can increase the theoretical capacity of the Li-S system. However, these additives may cause undesired parasitic reactions, such as the dissolution of the additive in the electrolyte. Studying such complex reactions presents a challenge because it requires experimental methods that can track the chemical and structural evolution of the system during an electrochemical process. To address the fundamental mechanisms in these systems, we employed an operando multimodal x-ray characterization approach to study the structural and chemical evolution of the metal sulfide—utilizing powder diffraction and fluorescence imaging to resolve the former and absorption spectroscopy the latter—during lithiation and de-lithiation of a Li-S battery with CuS as the multi-functional cathode additive. The resulting elucidation of the structural and chemical evolution of the system leads to a new description of the reaction mechanism.

Synchrotron X-Ray Topography for Encapsulation Stress/Strain and Crack Detection in Crystalline Silicon Modules

In this paper, we present the first experiment to prove the capabilities of X-ray topography for the direct imaging and analysis of defects, stress, and strain affecting the cell within the laminated photovoltaic (PV) module. Cracks originating from grain boundaries structures have been detected, developing along the cleavage planes of the crystal. The strain affecting the cell is clearly visualized through the bending of the metallization line images and can be easily mapped. While the recording conditions need to be optimized to maximize image contrast, this experiment demonstrates how synchrotron facilities can enable PV industry and research to characterize full PV modules. Appropriate development of the technique could also lead to future use of laboratory-level X-ray sources.

Development of polycapillary x-ray optics for synchrotron spectroscopy

A new spectrometer design that will result in a highly efficient, easy to handle, low-cost, high-resolution spectroscopy system with excellent background suppression is being developed for the NSLS-II Inner-Shell Spectroscopy beamline. This system utilizes non-diffractive optics comprised of fused and directed glass capillary tubes that will be used to collect and pre-collimate fluorescence photons. There are several advantages enabled by this design; a large energy range is accessible without modifying the s-stem, a large collection angle is achieved per detection unit: 4-5% of the full solid angle, easy integration in complex and harsh environments is enabled due to the use of a pre-collimation system as a secondary source for the spectrometer, and background from a complex sample environment can be easily and efficiently suppressed. The polycapillary X-ray focusing optics segment of this application has been under development. This includes improvement in manufacturing methods of polycapillary structure for x-ray optics, forming the polycapillary structure to produce X-ray optics to achieve the required solid angle collection and transmission efficiency, and measurement of X-ray focusing properties of the optics using an X-ray source. Two promising advances are large open area ratios of 80% or more, and the possibility of adding coatings in the capillaries using Atomic Layer Deposition techniques to improve reflection efficiency.