Brookhaven National Laboratory Research Articles

Performance of laser ion source LION operated at Brookhaven National Laboratory

LION is a laser ion source that has been in operation at Brookhaven National Laboratory (BNL) to provide heavy ions for NASA Space Radiation Laboratory (NSRL) and Relativistic Heavy Ion Collider (RHIC). It is the first laser ion source to supply stable ion beams for a long-term operation for users at a large accelerator facility in the world. LION is located at the upstream end of the heavy ion accelerator complex at BNL and supplies singly charged ion beams of various ion species. LION has been in operation since 2014 and is planned to be upgraded in 2024. This paper summarizes the operational performance achieved by LION.

Progress of the laser ion source upgrade (LION2) for RHIC and NSRL program at Brookhaven National Laboratory

At Brookhaven National Laboratory (BNL), the LION2 ion source is being constructed to replace an existing laser ion ablation ion source (LIS) at the EBIS facility, which provides heavy ion beams of multiple ion species for the operation of NASA Space Radiation Laboratory (NSRL) and Relativistic Heavy Ion Collider (RHIC). The LION1 ion source currently provides singly charged ions of Li, B, C, O, Al, Si, Ca, Ti, Fe, Cu, Zr, Nb, Ag, Tb, Ta, W, Au, Bi, and Th with a rapid-species-change capability. An electron beam ion source, Extended-EBIS captures, confines, and ionizes the ions to high charge state, suitable for injection and acceleration by an RFQ accelerator. Typically, single pulses of the LIS ion species for NSRL are changed sequentially during Galactic Cosmic Ray experiments, while multiple pulses of a given ion beam are provided quasi-simultaneously for RHIC. LION2 will have the same capability of the rapid-species-change with improved beam performance and reliability. LION2 is being constructed in a remote assembly location and is expected to finish in December 2023. The removal of LION1 and installation of LION2 is planned during the December 2023 or summer 2024 shutdown.

Time-resolved synchrotron light source X-ray detection with Low-Gain Avalanche Diodes

Low Gain Avalanche Diodes (LGADs) represent the state-of-the-art in timing measurements and will instrument future timing detectors at the High Luminosity Large Hadron Collider (HL-LHC) experiments. While conceived as a sensor for charged particles, the intrinsic gain of LGADs makes it possible to detect low energy X-rays with good energy resolution and excellent timing (tens of picoseconds). Using the Stanford Synchrotron Radiation Lightsource (SSRL) at SLAC, several LGADs designs were characterized with energies from 5 to 35 keV. The SSRL provides 10 ps pulsed X-ray bunches separated by 2.1ns intervals, and with an energy dispersion (ΔE/E) of 1 × 10-4. LGADs fabricated by Hamamatsu Photonics (HPK) and Brookhaven National Laboratory (BNL) with different thicknesses ranging from 20µm to 50µm and different gain layer designs were read out a two stage fast amplification circuit and digitized with a high bandwidth, high sampling rate oscilloscope. PIN devices from HPK were characterized as well. A systematic and detailed characterization of the devices’ energy linearity, resolution and timing resolution as a function of X-ray energy was performed for different biasing voltages at room temperature.

Francis James Macdonald Farley. 13 October 1920—16 July 2018

Francis Farley was a British experimental physicist who worked for much of his career at CERN. He was a clever designer and builder of particle beams, and a team leader and player who inspired, advised, amused and regaled others. In the middle of his career he worked on the first four experiments to measure g − 2, one of the most important numbers in particle physics. Three of these were conducted while he was at CERN, and one at Brookhaven National Laboratory in New York. Later he studied the problem of extracting energy from water waves, attempting to build proof of concept models as well as to study the problems that might stand in the way of commercial application. Farley had the rare ability to synthesize both theoretical and experimental knowledge of a subject, to collaborate in solving problems and to pass on what he knew to others. He was also articulate about the wonder and awe that he found in science.

X-Ray Fluorescence Analysis of Historic Art Paint Pigments

X-Ray Fluorescence Analysis of Historic Art Paint Pigments

Personnel dosimetry for the mixed beta (Kr-85)/photon (gamma, X-ray) beams using Harshaw 8814 TL dosimeters: Performance Test Applicability Study

Performance of Harshaw 8814 TL dosimeters was evaluated in the mixture of low energy beta (Kr-85, average energy 251 keV) and X-ray/gamma photon beams, when many doses obtained using existing dose calculation algorithms show a high bias. 264 TLDs were exposed at the Radiological and Environmental Sciences Laboratory to the pure Kr-85 energy beam as well as to different combinations of beta and photon beams of various energies (including Cs-137 and Co-60 gamma sources and M50, M200 and H300 X-ray beams). The TLDs were irradiated to different beta-to-photon dose ratios; 22 different combinations of radiation energy beams and beam dose ratios were tested. After exposure, the TLDs were readout at Brookhaven National Laboratory facility using a Harshaw 8800 reader. The doses were determined with the Harshaw Combined DOELAP dose calculation algorithm and compared to the known values. The results showed a significant deviation from the corresponding nominal values for some of the tested TLDs exposed to pure Kr-85 or a combination of Kr-85 and photon beam mixed energies. The different ratios of TL signals from chips 1–4 of the 8814 TL cards were analyzed, and an algorithm was proposed to identify the radiation beam energy to which each individual TLD was irradiated to. Finally, correction coefficients were developed which improves the performance of TL dosimetry dose calculation algorithm in the cases of exposure to a low energy beta beam and to a mixture of such beam with photons.

The high-performance DIRC for the ePIC detector at the EIC

The next-generation nuclear physics facility in the United States will be the Electron-Ion Collider (EIC), scheduled to be built at Brookhaven National Laboratory (BNL). Excellent particle identification (PID) is one of the key requirements for the EIC central detector called ePIC. Identification of the hadrons in the final state is critical to study how different quark flavors contribute to nucleon properties. A detector using the Detection of Internally Reflected Cherenkov light (DIRC) principle, with a radial size of only 7-8 cm, was chosen as the PID system for the ePIC barrel region. Within the framework of the EIC R&D programs, the development of a high-performance DIRC (hpDIRC) detector was undertaken with the aim of significantly advancing state-of-the-art performance. Key components of the hpDIRC detector are a 3-layer compound lens and small pixel-size photo sensors. Currently, the hpDIRC R&D program is focused on developing and validating the radiation hard 3-layer lens, quality assurance of the BaBar DIRC radiation bars, and the early stage of the hpDIRC prototype program with Cosmic Ray Telescope at Stony Brook University, in preparation for beam tests at Fermilab in 2024.

Emission Ghost Imaging: reconstruction with data augmentation.

Ghost Imaging enables 2D reconstruction of an object even though particles transmitted or emitted by the object of interest are detected with a single pixel detector without spatial resolution. This is possible because for the particular implementation of ghost imaging presented here, the incident beam is spatially modulated with a non-configurable attenuating mask whose orientation is varied (e.g. via transverse displacement or rotation) in the course of the ghost imaging experiment. Each orientation yields a distinct spatial pattern in the attenuated beam. In many cases, ghost imaging reconstructions can be dramatically improved by factoring the measurement matrix which consists of measured attenuated incident radiation for each of many orientations of the mask at each pixel to be reconstructed as the product of an orthonormal matrix and an upper triangular matrix provided that the number of orientations of the mask () is greater than or equal to the number of pixels () reconstructed. For the case, we present a data augmentation method that enables QR factorization of the measurement matrix. To suppress noise in the reconstruction, we determine the Moore-Penrose pseudoinverse of the measurement matrix with a truncated singular value decomposition approach. Since the resulting reconstruction is still noisy, we denoise it with the Adaptive Weights Smoothing method. In simulation experiments, our method outperforms a modification of an existing alternative orthogonalization method where rows of the measurement matrix are orthogonalized by the Gram-Schmidt method. We apply our ghost imaging methods to experimental X-ray fluorescence data acquired at Brookhaven National Laboratory.

Numerical Evaluation of Sodium Droplet Swarm Combustion and Its Modeling Optimization

Because of its superior thermal-hydraulic qualities, liquid sodium has been applied to a variety of industries, including energy storage, solar energy, sodium-cooled fast reactors, and aerospace. However, fires brought on by sodium leaks at high pressure can have major thermodynamic repercussions and put employees and equipment in use at risk directly or indirectly. As a result, a realistic and accurate forecast of the combustion behavior of sodium droplet swarm can offer technical backing for the use of liquid sodium in engineering as well as a way of sodium fire prevention and control. Spray dynamics (droplet settling, droplet particle size distribution, etc.), combustion kinetics (premixed combustion, gas phase combustion, etc.), sodium aerosol diffusion, and other specialized phenomena all contribute to the complex process of sodium droplet swarm combustion. The NACOM code created by Brookhaven National Laboratory for sodium droplet swarm combustion is utilized in this paper as a framework. The code is first validated using the benchmark of the sodium droplet swarm combustion tests carried out by prestigious institutions. The validation results demonstrate that the code’s drag model, droplet combustion model, and heat transfer model are to blame for the significantly overestimated thermodynamic effects of sodium droplet swarm combustion. NACOM is subsequently developed twice for the authors’ previously developed vapor-liquid two-layer-structure drag model, chemical kinetic combustion model, and suitable heat transfer coefficient. It is then thoroughly assessed for the separate-effects tests and integral-effects test. The evaluation results demonstrate that the optimized drag model accelerates the settling of sodium droplets due to the consideration of the sodium-vapor drag reduction effect, reducing the thermodynamic effects of liquid sodium combustion; the optimized premixed combustion model can accurately predict the low-temperature sodium droplet swarm combustion conditions, resolving the issue of serious misvaluation of the original version of NACOM. The associated research findings can serve as valuable resources and tools for deeper comprehension of the combustion effects and mechanisms of sodium droplet swarm under various operating settings (such as leakage rate and oxygen concentration).

Federated Access from DOE Labs to Distributed Storage in the EIC Era of Computing

The Electron Ion Collider (EIC) collaboration and future experiment is a unique scientific ecosystem within Nuclear Physics as the experiment starts right off as a crosscollaboration between Brookhaven National Lab (BNL) & Jefferson Lab (JLab). As a result, this muti-lab computing model tries at best to provide services accessible from anywhere by anyone who is part of the collaboration. While the computing model for the EIC is not finalized, it is anticipated that the computational and storage resources will be made accessible to a wide range of collaborators across the world. The use of federated ID seems to be a critical element to the strategy of providing such services, allowing seamless access to each lab site computing resources. However, providing Federated access to a Federated storage is not a trivial matter and has its share of technical challenges. In this contribution, we focus on the steps we took towards the deployment of a distributed object storage system that integrates with Amazon S3 and Federated ID. We will first cover for and explain the first stage storage solutions provided to the EIC during the detector design phase. Our initial test deployment consisted of Lustre storage using MinIO, hence providing an S3 interface. High Availability load balancers were added later to provide the initial scalability it lacked. Performance of that system will be shown. While this embryonic solution worked well, it had many limitations. Looking ahead, the Ceph object storage is considered a top-of-the-line solution in the storage community - since the Ceph Object Gateway is compatible with the Amazon S3 API out of the box, our next phase will use a native S3 storage. Our Ceph deployment will consist of erasure coded storage nodes to maximize storage potential along with multiple Ceph Object Gateways for redundant access. We will compare performance of our next stage implementations. Finally, we will present how to leverage OpenID Connect with the Ceph Object Gateway’s to enable Federated ID access. We hope this contribution will serve the community needs as we move forward with cross-lab collaborations and the need for Federated ID access to distributed compute facilities.

The Creation and Evolution of the US ATLAS Shared Analysis Facilities

Prior to the start of the LHC Run 3, the US ATLAS Software and Computing operations program established three shared Tier 3 Analysis Facilities (AFs). The newest AF was established at the University of Chicago in the past year, joining the existing AFs at Brookhaven National Lab and SLAC National Accelerator Lab. In this paper, we will describe both the common and unique aspects of these three AFs, and the resulting distributed facility from the user’s perspective, including how we monitor and measure the AFs. The common elements include enabling easy access via Federated ID, file sharing via EOS, provisioning of similar Jupyter environments using common Jupyter kernels and containerization, and efforts to centralize documentation and user support channels. The unique components we will cover are driven in turn by the requirements, expertise and resources at each individual site. Finally, we will highlight how the US AFs are collaborating with other ATLAS and LHC wide (IRIS-HEP and HSF) user analysis support activities, evaluating tools like ServiceX and Coffea-Casa.

Simulated galactic cosmic ray exposure activates dose-dependent DNA repair response and down regulates glucosinolate pathways in arabidopsis seedlings.

Outside the protection of Earth's magnetic field, organisms are constantly exposed to space radiation consisting of energetic protons and other heavier charged particles. With the goal of crewed Mars exploration, the production of fresh food during long duration space missions is critical for meeting astronauts' nutritional and psychological needs. However, the biological effects of space radiation on plants have not been sufficiently investigated and characterized. To that end, 10-day-old Arabidopsis seedlings were exposed to simulated Galactic Cosmic Rays (GCR) and assessed for transcriptomic changes. The simulated GCR irradiation was carried out in the NASA Space Radiation Laboratory (NSRL) at Brookhaven National Lab (BNL). The exposures were conducted acutely for two dose points at 40 cGy or 80 cGy, with sequential delivery of proton, helium, oxygen, silicon, and iron ions. Control and irradiated seedlings were then harvested and preserved in RNAlater at 3 hrs post irradiation. Total RNA was isolated for transcriptomic analyses using RNAseq. The data revealed that the transcriptomic responses were dose-dependent, with significant upregulation of DNA repair pathways and downregulation of glucosinolate biosynthetic pathways. Glucosinolates are important for plant pathogen defense and for the taste of a plant, which are both relevant to growing plants for spaceflight. These findings fill in knowledge gaps of how plants respond to radiation in beyond-Earth environments.

Three-pole wigglers at NSLS-II

The National Synchrotron Light Source-II (NSLS-II) at Brookhaven National Lab (BNL) is a third-generation medium-energy storage ring with 3 GeV and sub-nm-rad horizontal emittance, equipped with a top-off capability of 500 mA. It is designed to deliver an extremely intense photon beam across a wide spectral range, from the far-infrared to the very hard X-ray region. This outstanding performance is achieved through a combination of bending magnets (BM), three-pole wigglers (3 PW), and advanced insertion device (ID) sources. Six three-pole wigglers have been constructed at the NSLS-II IDs Lab. These devices are used to produce broadband radiation with lower angular power density and to monitor the electron beam emittance and energy spread. This paper describes the R&D activities focused on developing the required magnetic and mechanical designs, along with magnetic field optimization and the final magnetic measurement results. It also covers the spectral brightness, flux, power density, spatial and angular output properties of the 3 PWs, including their commissioning results and their effects on the performance of the NSLS-II storage ring.

High figure of merit spin polarized electron sources grown via MOCVD

Spin polarized photocathodes are key to the future operation of electron accelerators such as the ones at Thomas Jefferson National Accelerator Facility and Brookhaven National Laboratory. Currently, these photocathodes come in short supply due to limited production by molecular beam epitaxy. By developing a process to implement similar structures using metal organic chemical vapor deposition, the availability of these devices can be increased. In this paper, we detail the implementation of recent photocathode advancements via metal organic chemical vapor deposition process and show an improvement in both polarization and quantum efficiency of our devices compared to those fabricated via molecular beam epitaxy, with devices reaching 82% polarization and 2.9% quantum efficiency.

Hardware acceleration of complex HEP algorithms with HLS and FPGAs: Methodology and preliminary implementation

The amount of data coming from modern acquisition systems, especially working in extreme experimental conditions, is significantly rising over the years. Combined with complex algorithms, the computation time and power consumption are considerably increasing. The issue usually occurs in many world laboratories, such as CERN, Brookhaven National Laboratory, GSI Helmholtzzentrum für Schwerionenforschung, and tokamak devices (JET, WEST, MAST, and more). Often well verified, but legacy codes are used as a main computational engine, resulting in weak performance unsuitable for current needs. The paper presents a methodology to appropriately adapt the legacy C/C++ high-energy physics (HEP) algorithms for computation acceleration using FPGAs, which may improve the designing of real-time systems based on verified codes. The main idea is to separate the HLS-FPGA code work areas between groups of experts: physicists and electronics. The methodology consists of several parts: interfacing, storage, verification methods, defining the algorithm and data structures, program refactoring in the scope of CPU and FPGA, performance and results analysis, FPGA verification methods, FPGA performance estimation, and automatization of the process. The methodology has been successfully tested by implementing a legacy, complex HEP algorithm for femtoscopy correlations in the HLS framework for FPGA. It works with extensive input data from international experiments, like STAR at RHIC. The implementation and verification were done successfully on the FPGA hardware platform. Following the methodology results in a clearer to analyze and debug HEP code than a machine-generated version by tools. We also confirmed that it is possible to make a working, HLS-compliant program designed by non-FPGA experts. Using the modern implementation tools, FPGA resource usage is low despite unoptimized syntax. It gives a large field for further significant optimizations and good performance. The proposed approach should be interesting to introduce in devices like tokamaks, synchrotrons, and similar, where the real-time monitoring of the experimental processes is essential.

Synchrotron light source X-ray detection with Low-Gain Avalanche Diodes

Low Gain Avalanche Diodes (LGADs) represent the state-of-the-art in timing measurements and will instrument the future Timing Detectors of ATLAS and CMS for the High-Luminosity LHC. While initially conceived as a sensor for charged particles, the intrinsic gain of LGADs makes it possible to detect low-energy X-rays with good energy resolution and excellent time resolution (tens of picoseconds). Using the Stanford Synchrotron Radiation Lightsource (SSRL) at SLAC, several LGADs designs were characterized with energies from 5 to 70 keV. The SSRL provides 10 ps pulsed X-ray bunches separated by 2 ns intervals with an energy dispersion (ΔE/E) of 10-4. LGADs from Hamamatsu Photonics (HPK) and Brookhaven National Laboratory (BNL) with different thicknesses ranging from 20 μm to 50 μm and different gain layer designs were read out using fast amplification boards and digitized with a high bandwidth and high sampling rate oscilloscope. PIN devices from HPK and AC-LGADs from BNL were characterized as well. A systematic and detailed characterization of the devices' energy linearity, resolution, and time resolution as a function of X-ray energy was performed for different biasing voltages at room temperature and are reported in this work. The charge collection and multiplication mechanism were simulated using Geant4 and TCAD Sentaurus, providing an important handle for interpreting the data.

The potential of a TeV-scale muon-ion collider

We propose the development of a novel muon-proton and muon-nucleus collider facility at the TeV scale that is capable of performing precision deep inelastic scattering measurements in new regimes and providing a rich program in nuclear and particle physics. Such a facility could seed, or leverage, the development of a muon-antimuon collider and make use of the existing hadron accelerator infrastructure when sited at a facility such as Brookhaven National Laboratory, Fermilab, or CERN. We discuss the possible energy and luminosity design parameters for several collider configurations, and illustrate the science potential with several studies on deep inelastic scattering kinematics, Higgs and vector boson production, top quark production, and beyond Standard Model leptoquark production. Detector design considerations and a possible road map toward development are also given.

Operando EXAFS to Determine the Mechanism of Bi Dopant at Low Concentration in Rechargeable MnO2 Cathodes

The rechargeable Zn-MnO2 battery system is one few systems in development capable of meeting the extreme cost requirements needed for global integration of battery storage in the power grid. Doping the MnO2 cathode with Bi allows it to cycle reversibly between layered Mn oxides 𝛿-MnO2 and Mn(OH)2, without detrimental formation of Mn3O4. This provides a cathode capacity of 617 mAh/g, which modeling has shown to enable costs below $50/kWh. However, to achieve commercial adoption, cycling stability must be improved. The mechanism through which the Bi dopant improves rechargeability remains largely unknown, and this must be clarified to rationally improve the system. Our previous work has established that the mechanism involves structurally disordered intermediates, and thus characterization techniques based on short-range order need to be used. This talk will demonstrate rapidly collected, operando extended x-ray absorption fine-structure (EXAFS) data collected on MnO2 cathodes with and without Bi dopant. Operando techniques are scientifically powerful as they reduce experimental uncertainty resulting from destructive preparation of samples for ex-situ analysis. In addition, rapid EXAFS collection allows for analysis of the kinetics of Mn coordination changes.Previously, the formation of a disordered 𝛿-MnO2 phase with no diffraction signal was identified during the first charge of Bi-modified MnO2 cathodes.1 In this work, operando X-Ray Absorption Spectroscopy (XAS) was employed to further compare Mn coordination environments in standard and Bi-modified cathodes at points of interest throughout cycling (pristine, intermediate, discharge, intermediate, charged). Specifically, the EXAFS region of the data was used to visualize the dynamic first shell (Mn-O) and second shell (Mn-Mn) interatomic distances during the first cycle. The values throughout cycling were compared with interatomic distances of Mn oxides that have been reported in literature, allowing the data to be used both for “fingerprinting” as a method of identifying the same pristine, intermediate, and discharged phases in both cases. Rapid EXAFS data collection allows for precise analysis of the potentials and states of charge at which these compounds form in each cathode. This portion of the analysis allows for observation of the faster kinetics of changes in Mn coordination in the Bi-modified MnO2 cathode. Furthmore, analysis of the first charge shows that deformation of the Mn(OH)2 discharge product is observed at the same potential energy in both cases, demonstrating that the thermodynamic stability of Mn(OH)2 is not improved in the first cycle of Bi-modified MnO2 cathodes, despite improved capacity. These findings suggest that Bi dopant may primarily act to improve kinetics within the MnO2 electrode rather than enhancing the thermodynamic stability to prevent degradation into Mn3O4. References Andrea M. Bruck et al 2020 Electrochem. Soc. 167 Acknowledgements We acknowledge financial support from the National Science Foundation under Award Number CBET-ES-2044602. This research used resources of beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.

Li-Ion and Na-Ion Intercalation in Layered MnO2 Cathodes Enabled by Using Bismuth as a Cation Pillar

Rechargeability of low-cost MnO2 cathodes in aqueous cells has the potential to be an enabling technology for low-cost (<$50/kWh) grid-scale batteries. This rechargeability is imparted by modifying the MnO2 with Bi. In this talk we detail using Bi doping for structural stabilization of MnO2 cathodes for Li-ion and Na-ion batteries in dry, non-aqueous electrolyte. We do this by preparing a series of Bi-doped layered MnO2 compounds, which also contain K ions and crystal water. These phyllomanganates or birnessite-type compounds have the general formula KxBiy-MnO2 • nH2O. The materials are structurally characterized by synchrotron X-ray powder diffraction (XPD) and confocal Raman microscopy. It is found that incorporation of Bi in the structure increases the crystallinity of the material by ordering the interlayer cations. This ordering results in the emergence of a structural superlattice in the material, which has been reported previously for birnessite inserted with other heavy, multivalent cations such as as Sr2+, Ba2+, and Ca2+.We selected three Bi doping levels to study in Li-ion and Na-ion batteries: undoped (y = 0), low-doping (y = 0.013 or 1.3%), and high doping (y = 0.043 or 4.3%). Both doped materials had capacity over 200 mAh/g and allowed for far more stable cell cycling than the undoped Kx-MnO2. The cells made with 4.3% doping of Bi were by far more stable. These cycled at 175-190 mAh/g specific capacity through 100 cycles with a nominal voltage of 2.9 V. Operando XRD experiments to characterize the cathodes within sealed coin cells showed that high-level doping (4.3%) promoted dehydration of the KxBiy-MnO2 interlayer, which had a distance of 6.4 Å. This showed that loss of the crystal water from the interlayer was key to achieving maximum stability during cycling. Lower Bi doping (1.3%) did not cause loss of the crystal water once the cathode was wetted with electrolyte. Previous reports have suggested that Bi doping of 20% results in stabilized Li-ion cycling in layered MnO2. However, these reports involved largely amorphous active material. Our results showed that Bi doping of only 1.3% still provided a large stability benefit, and the high crystallinity of our material allowed it to be structurally characterized, both in the as-prepared state and operando during battery cycling. Results from Na-ion cells will also be presented.Stabilized MnO2-based cathodes that cycle with good capacity and somewhat lower cell voltage than traditional Li-ion cells are a promising strategy for low-cost batteries for the grid. The possibility of using Na as the working ion is also useful for large-scale deployment of batteries to balance renewable power. Acknowledgments This work was supported by the U.S. Department of Energy (DOE) Office of Electricity Delivery and Energy Reliability, Dr. Imre Gyuk, Energy Storage Program Manager. This research used resources of the Advanced Photon Source beamline 6-BM, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research also used resources at beamlines 7-BM (QAS) and 28-ID-2 (XPD) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.

Promoting Hydrogen Evolution and Oxidation by Reconstructing Hydrogen-Bonding Network of Interfacial Water

The hydrogen evolution and oxidation reactions (HER/HOR) at the electrode-water control the performance of water electrolyzers and hydrogen fuel cells, two important devices for deep decarbonization of our economy (1). Platinum (Pt) catalyzes the HER/HOR with exceptional activity and stability across a wide pH range. However, its activity progressively decreases by about two orders of magnitude as the pH increases from 0 to 13 (2, 3). The lack of understanding of this pH dependence reflects our fundamental knowledge gaps in electrochemistry and has hindered the advancement of alkaline electrolyzers and fuel cells.Herein, we promoted the HER/HOR of Pt in base by introducing N-methylimidazoles in the Pt-water interface. In situ spectroscopic characterization of the interface together with computations showed that the N-methylimidazoles form strong hydrogen-bonding with neighboring water molecules thereby reconstructing the H-bond network of interfacial water. We accordingly established a unified mechanism by which the HER/HOR in acid and base proceeds via diffusion of protons and hydroxides, respectively through the H-bond network of interfacial water by the Grotthuss mechanism. This mechanism accounts for the pH-dependent HER/HOR kinetics of platinum, a long-standing puzzle. Utilization of N-methylimidazoles as the HER/HOR probes and promoters not only leads to the elucidation of the HER/HOR mechanism but also holds great promise for applications. We have demonstrated 40% performance improvement of an anion exchange membrane water electrolyzer by adding 10-5 M 1,2-dimethylimidazole into the 0.1 M potassium hydroxide solution fed into its Pt cathode. Acknowledgements This work was supported by the Office of Naval Research (ONR) grant N000141712608 (Q.J.)This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory Contract DE-SC0012704. Beamline operations were supported in part by the Synchrotron Catalysis Consortium Grant DE-SC0012335. V. R. Stamenkovic, D. Strmcnik, P. P. Lopes and N. M. Markovic, Nat. Mater., 16, 57 (2017). J. Durst, A. Siebel, C. Simon, F. Hasché, J. Herranz and H. A. Gasteiger, Energy Environ. Sci., 7, 2255 (2014). W. Sheng, Z. Zhuang, M. Gao, J. Zheng, J. G. Chen and Y. Yan, Nat. Commun., 6 (2015). Figure 1