More Like this

1. Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction

   https://doi.org/10.1073/pnas.1900761116  

   Li, Jingyi ; Li, Xiang ; Gunathunge, Charuni M. ; Waegele, Matthias M. ( April 2019 , Proceedings of the National Academy of Sciences)

   The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surface-adsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (${\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$,${\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$,${\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{p}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$, and${\mathrm{b}\mathrm{u}\mathrm{t}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of${\mathrm{m}\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$and${\mathrm{e}\mathrm{t}\mathrm{h}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$cations, whereas this product is not synthesized in${\mathrm{p}\mathrm{r}\mathrm{o}\mathrm{p}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$- and${\mathrm{b}\mathrm{u}\mathrm{t}\mathrm{y}\mathrm{l}}_4{\mathrm{N}}^{+}$-containing electrolytes. Surface-enhanced infrared absorption spectroscopy (SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.

    

   more » « less
2. Utilizing adaptive optics to mitigate intra-modal-group power coupling of graded-index few-mode fiber in a 200-Gbit/s mode-division-multiplexed link

   https://doi.org/10.1364/OL.394307  

   Zhang, Runzhou ; Song, Hao ; Song, Haoqian ; Zhao, Zhe ; Milione, Giovanni ; Pang, Kai ; Du, Jing ; Li, Long ; Zou, Kaiheng ; Zhou, Huibin ; et al ( June 2020 , Optics Letters)

   We experimentally demonstrate the utilization of adaptive optics (AO) to mitigate intra-group power coupling among linearly polarized (LP) modes in a graded-index few-mode fiber (GI FMF). Generally, in this fiber, the coupling between degenerate modes inside a modal group tends to be stronger than between modes belonging to different groups. In our approach, the coupling inside the${\mathrm{L}\mathrm{P}}_{11}$group can be represented by a combination of orbital-angular-momentum (OAM) modes, such that reducing power coupling in OAM set tends to indicate the capability to reduce the coupling inside the${\mathrm{L}\mathrm{P}}_{11}$group. We employ two output OAM modes$l=+1$and$l=-<\#comment/>1$as resultant linear combinations of degenerate${\mathrm{L}\mathrm{P}}_{11\mathrm{a}}$and${\mathrm{L}\mathrm{P}}_{11\mathrm{b}}$modes inside the${\mathrm{L}\mathrm{P}}_{11}$group of a$\sim <\#comment/>0.6\text{-}\mathrm{k}\mathrm{m}$GI FMF. The power coupling is mitigated by shaping the amplitude and phase of the distorted OAM modes. Each OAM mode carries an independent 20-, 40-, or 100-Gbit/s quadrature-phase-shift-keying data stream. We measure the transmission matrix (TM) in the OAM basis within${\mathrm{L}\mathrm{P}}_{11}$group, which is a subset of the full LP TM of the FMF-based system. An inverse TM is subsequently implemented before the receiver by a spatial light modulator to mitigate the intra-modal-group power coupling. With AO mitigation, the experimental results for$l=+1$and$l=-<\#comment/>1$modes show, respectively, that (i) intra-modal-group crosstalk is reduced by$><\#comment/>5.8\mathrm{d}\mathrm{B}$and$><\#comment/>5.6\mathrm{d}\mathrm{B}$and (ii) near-error-free bit-error-rate performance is achieved with a penalty of$\sim <\#comment/>0.6\mathrm{d}\mathrm{B}$and$\sim <\#comment/>3.8\mathrm{d}\mathrm{B}$, respectively.

    

   more » « less
3. Large H 2 O solubility in dense silica and its implications for the interiors of water-rich planets

   https://doi.org/10.1073/pnas.1917448117  

   Nisr, Carole ; Chen, Huawei ; Leinenweber, Kurt ; Chizmeshya, Andrew ; Prakapenka, Vitali B. ; Prescher, Clemens ; Tkachev, Sergey N. ; Meng, Yue ; Liu, Zhenxian ; Shim, Sang-Heon ( April 2020 , Proceedings of the National Academy of Sciences)

   Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in${\mathrm{H}}_2$O-rich setting at high pressures and temperatures ($P-T$) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between${\mathrm{S}\mathrm{i}\mathrm{O}}_2$and${\mathrm{H}}_2$O as archetypal materials for rock and ice, respectively, at high$P-T$. We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the${\mathrm{C}\mathrm{a}\mathrm{C}\mathrm{l}}_2$-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of (${\mathrm{S}\mathrm{i}}_{1-x}{\mathrm{H}}_{4x}$)${\mathrm{O}}_2\hspace{0.17em}\left(x=0.12\right)$. At pressures above 60 GPa,${\mathrm{H}}_2$O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could be the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

    

   more » « less
4. Growth and characterization of Sc 2 O 3 doped Ta 2 O 5 thin films

   https://doi.org/10.1364/AO.59.00A106  

   Fazio, Mariana ; Yang, Le ; Markosyan, Ashot ; Bassiri, Riccardo ; Fejer, Martin_M ; Menoni, Carmen_S ( December 2019 , Applied Optics)

   We present the optical and structural characterization of films of${\mathrm{T}\mathrm{a}}_2{\mathrm{O}}_5$,${\mathrm{S}\mathrm{c}}_2{\mathrm{O}}_3$, and${\mathrm{S}\mathrm{c}}_2{\mathrm{O}}_3$doped${\mathrm{T}\mathrm{a}}_2{\mathrm{O}}_5$with a cation ratio around 0.1 grown by reactive sputtering. The addition of${\mathrm{S}\mathrm{c}}_2{\mathrm{O}}_3$as a dopant induces the formation of tantalum suboxide due to the “oxygen getter” property of scandium. The presence of tantalum suboxide greatly affects the optical properties of the coating, resulting in higher absorption loss at$\mathrm{\lambda <\#comment/>}=1064\mathrm{n}\mathrm{m}$. The refractive index and optical band gap of the mixed film do not correspond to those of a mixture of${\mathrm{T}\mathrm{a}}_2{\mathrm{O}}_5$and${\mathrm{S}\mathrm{c}}_2{\mathrm{O}}_3$, given the profound structural modifications induced by the dopant.

    

   more » « less
5. On-chip spin-orbit locking of quantum emitters in 2D materials for chiral emission

   https://doi.org/10.1364/OPTICA.463481  

   Ma, Yichen ; Zhao, Haoqi ; Liu, Na ; Gao, Zihe ; Mohajerani, Seyed_Sepehr ; Xiao, Licheng ; Hone, James ; Feng, Liang ; Strauf, Stefan ( August 2022 , Optica)

   Light carries both spin angular momentum (SAM) and orbital angular momentum (OAM), which can be used as potential degrees of freedom for quantum information processing. Quantum emitters are ideal candidates towards on-chip control and manipulation of the full SAM–OAM state space. Here, we show coupling of a spin-polarized quantum emitter in a monolayer${\mathrm{W}\mathrm{S}\mathrm{e}}_2$with the whispering gallery mode of a${\mathrm{S}\mathrm{i}}_3{\mathrm{N}}_4$ring resonator. The cavity mode carries a transverse SAM of$\mathrm{\sigma <\#comment/>}=\pm <\#comment/>1$in the evanescent regions, with the sign depending on the orbital power flow direction of the light. By tailoring the cavity–emitter interaction, we couple the intrinsic spin state of the quantum emitter to the SAM and propagation direction of the cavity mode, which leads to spin–orbit locking and subsequent chiral single-photon emission. Furthermore, by engineering how light is scattered from the WGM, we create a high-order Bessel beam which opens up the possibility to generate optical vortex carrying OAM states.

    

   more » « less