Xuemei Han

Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach

Originally unfavored nitrogen-to-ammonia electroconversion is now preferred over competing reaction using reticular chemistry. Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF’s water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor–abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries.

Spinning liquid marble and its dual applications as microcentrifuge and miniature localized viscometer

Liquid marble offers an attractive droplet manipulation approach by isolating microdroplet in a nonstick encapsulating shell formed via the spontaneous coating of hydrophobic particles onto the liquid surface. While liquid marble prepared using magnetic nanoparticles enables precise spatiotemporal actuation of microdroplets, these manipulations are generally limited to simple and linear spatial maneuver of microdroplets. Herein, we demonstrate the unique and three-dimensional spinning of microliter-sized liquid marble (LM) and its subsequent dual applications as (1) the worlds smallest centrifuge and (2) a miniature and localized viscometer. Our LM is responsive to an applied rotating magnetic field, with its spinning speed programmable between 0 and 1300 rpm. This spinning generates an unprecedented centrifugal force of >2g in a LM of ∼1 mm radius. Such centrifugal force facilitates an outward and radial hydrodynamic flow in the enclosed microdroplet, enabling LM to serve as a microcentrifuge for the sedimentation of nanoparticles with >85% separation efficiency. Furthermore, we apply spinning LM as an ultrasensitive spin-to-viscosity transducer to quantify the viscosity of the external suspended liquid in the relative viscosity (η/ηwater) range of 1-70 using ≤1 mL liquid sample. Collectively, the ensemble of benefits offered by spinning LM creates enormous opportunities in the development of multifunctional micromagneto-mechanical devices as promising surface-sensitive microsensor, miniature centrifugal pump, and even microreactor with directed heat and mass transfer mechanism.

Identifying Enclosed Chemical Reaction and Dynamics at the Molecular Level Using Shell-Isolated Miniaturized Plasmonic Liquid Marble

Current microscale tracking of chemical kinetics is limited to destructive ex situ methods. Here we utilize Ag nanocube-based plasmonic liquid marble (PLM) microreactor for in situ molecular-level identification of reaction dynamics. We exploit the ultrasensitive surface-enhanced Raman scattering (SERS) capability imparted by the plasmonic shell to unravel the mechanism and kinetics of aryl-diazonium surface grafting reaction in situ, using just a 2-μL reaction droplet. This reaction is a robust approach to generate covalently functionalized metallic surfaces, yet its kinetics remain unknown to date. Experiments and simulations jointly uncover a two-step sequential grafting process. An initial Langmuir chemisorption of sulfonicbenzene diazonium (dSB) salt onto Ag surfaces forms an intermediate sulfonicbenzene monolayer (Ag-SB), followed by subsequent autocatalytic multilayer growth of Ag-SB3. Kinetic rate constants reveal 19-fold faster chemisorption than multilayer growth. Our ability to precisely decipher molecular-level reaction dynamics creates opportunities to develop more efficient processes in synthetic chemistry and nanotechnology.

Dynamic Rotating Liquid Marble for Directional and Enhanced Mass Transportation in Three-Dimensional Microliter Droplets

The ability of an artificial microdroplet to mimic the rotational behaviors of living systems is crucial for dynamic mass transportation but remains challenging to date. Herein, we report dynamic microdroplet rotation using a liquid marble (RLM) and achieve precise control over mass transportation and distribution in a three-dimensional (3D) microdroplet. RLM rotates synchronously with an external magnetic field, creating circular hydrodynamic flow and an outward centrifugal force. Such spin-induced phenomena direct a spiral movement of entrapped molecules and accelerate their diffusion and homogenization in the entire liquid. Moreover, we demonstrate the rotation rate-controlled (between 0 and 1300 rpm) modulation of shell-catalyzed reaction kinetics from 0.13 to 0.62 min-1. The directed acceleration of reactants toward a catalytically active shell surface is 3-fold faster than conventional stir bar-based convective flow. RLM as an efficient magnetohydrodynamics transducer will be valuable for dynamical control over mass transportation in microdroplet-based chemical, biological, and biomedical studies.

Driving CO2 to a Quasi-Condensed Phase at the Interface between a Nanoparticle Surface and a Metal–Organic Framework at 1 bar and 298 K

We demonstrate a molecular-level observation of driving CO2 molecules into a quasi-condensed phase on the solid surface of metal nanoparticles (NP) under ambient conditions of 1 bar and 298 K. This is achieved via a CO2 accumulation in the interface between a metal-organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. Using real-time surface-enhanced Raman scattering spectroscopy, a >18-fold enhancement of surface coverage of CO2 is observed at the interface. The high surface concentration leads CO2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (>105 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO2 conversion and ambient solid-gas operation.

Microchemical Plant in a Liquid Droplet: Plasmonic Liquid Marble for Sequential Reactions and Attomole Detection of Toxin at Microliter Scale

Miniaturizing the continuous multistep operations of a factory into a microchemical plant offers a safe and cost-effective approach to promote high-throughput screening in drug development and enforcement of industrial/environmental safety. While particle-assembled microdroplets in the form of liquid marble are ideal as microchemical plant, these platforms are mainly restricted to single-step reactions and limited to ex situ reaction monitoring. Herein, we utilize plasmonic liquid marble (PLM), formed by encapsulating liquid droplet with Ag nanocubes, to address these issues and demonstrate it as an ideal microchemical plant to conduct reaction-and-detection sequences on-demand in a nondisruptive manner. Utilizing a two-step azo-dye formation as our model reaction, our microchemical plant allows rapid and efficient diazotization of nitroaniline to form diazonium nitrobenzene, followed by the azo coupling of this intermediate with target aromatic compound to yield azo-dye. These molecular events are tracked in situ via SERS measurement through the plasmonic shell and further verified with in silico investigation. Furthermore, we apply our microchemical plant for ultrasensitive SERS detection and quantification of bisphenol A (BPA) with detection limit down to 10 amol, which is 50 000-fold lower than the BPA safety limit. Together with the protections offered by plasmonic shell against external environments, these collective advantages empower PLM as a multifunctional microchemical plant to facilitate small-volume testing and optimization of processes relevant in industrial and research contexts.