Jiajun He

Hierarchical N-Doped Carbon as CO2 Adsorbent with High CO2 Selectivity from Rationally Designed Polypyrrole Precursor

Carbon capture and sequestration from point sources is an important component in the CO2 emission mitigation portfolio. In particular, sorbents with both high capacity and selectivity are required for reducing the cost of carbon capture. Although physisorbents have the advantage of low energy consumption for regeneration, it remains a challenge to obtain both high capacity and sufficient CO2/N2 selectivity at the same time. Here, we report the controlled synthesis of a novel N-doped hierarchical carbon that exhibits record-high Henrys law CO2/N2 selectivity among physisorptive carbons while having a high CO2 adsorption capacity. Specifically, our synthesis involves the rational design of a modified pyrrole molecule that can co-assemble with the soft Pluronic template via hydrogen bonding and electrostatic interactions to give rise to mesopores followed by carbonization. The low-temperature carbonization and activation processes allow for the development of ultrasmall pores (d < 0.5 nm) and preservation of nitrogen moieties, essential for enhanced CO2 affinity. Furthermore, our described work provides a strategy to initiate developments of rationally designed porous conjugated polymer structures and carbon-based materials for various potential applications.

Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 °C with record-high surface area (4073 m2 g–1), large pore volume (2.26 cm–3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium–sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.

Advancing Adsorption and Membrane Separation Processes for the Gigaton Carbon Capture Challenge

Reducing CO2 in the atmosphere and preventing its release from point-source emitters, such as coal and natural gas-fired power plants, is a global challenge measured in gigatons. Capturing CO2 at this scale will require a portfolio of gas-separation technologies to be applied over a range of applications in which the gas mixtures and operating conditions will vary. Chemical scrubbing using absorption is the current state-of-the-art technology. Considerably less attention has been given to other gas-separation technologies, including adsorption and membranes. It will take a range of creative solutions to reduce CO2 at scale, thereby slowing global warming and minimizing its potential negative environmental impacts. This review focuses on the current challenges of adsorption and membrane-separation processes. Technological advancement of these processes will lead to reduced cost, which will enable subsequent adoption for practical scaled-up application.

High-performance oxygen reduction and evolution carbon catalysis: From mechanistic studies to device integration

The development of high-performance and low-cost oxygen reduction and evolution catalysts that can be easily integrated into existing devices is crucial for the wide deployment of energy storage systems that utilize O2-H2O chemistries, such as regenerative fuel cells and metal-air batteries. Herein, we report an NH3-activated N-doped hierarchical carbon (NHC) catalyst synthesized via a scalable route, and demonstrate its device integration. The NHC catalyst exhibited good performance for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), as demonstrated by means of electrochemical studies and evaluation when integrated into the oxygen electrode of a regenerative fuel cell. The activities observed for both the ORR and the OER were comparable to those achieved by state-of-the-art Pt and Ir catalysts in alkaline environments. We have further identified the critical role of carbon defects as active sites for electrochemical activity through density functional theory calculations and high-resolution TEM visualization. This work highlights the potential of NHC to replace commercial precious metals in regenerative fuel cells and possibly metal-air batteries for cost-effective storage of intermittent renewable energy.

Revisiting film theory to consider approaches for enhanced solvent-process design for carbon capture

Application of carbon capture at the gigaton-scale necessary for significant reduction in atmospheric CO2 requires a portfolio of technologies for applications that may span point-source capture to more dilute systems such as CO2 removal from the atmosphere. We argue that for absorption separation processes there is a strong coupling between the solvent and process properties, which are uniquely dependent upon the starting concentration of CO2. We revisit Whitmans film theory and consider mass-transfer correlations to determine the most critical solvent and process parameters that influence the flux of CO2 from the gas to the liquid phase, within which it is ultimately captured. Finally, results of this work indicate, for instance, that increasing the kinetics of a reacting solvent with CO2 has a greater impact on direct air capture (DAC) systems, than natural gas- or coal-fired power plant emissions. In addition, the solvent kinetics is a more influential parameter than the Henrys law solubility coefficient for DAC systems, while the reverse may be found for more concentrated CO2 gas mixtures.

Molecular simulations of nitrogen-doped hierarchical carbon adsorbents for post-combustion CO2 capture

A present challenge in the mitigation of anthropogenic CO2 emissions involves the design of less energy- and water-intensive capture technologies. Sorbent-based capture represents a promising solution, as these materials have negligible water requirements and do not incur the heavy energy penalties associated with solvent regeneration. However, to be considered competitive with traditional technologies (i.e., MEA capture), these sorbents must exhibit a high CO2 loading capacity and high CO2/N2 selectivity. It has been reported that ultramicroporous character and surface nitrogen functionality are of great importance to the enhancement of CO2 capacity and CO2/N2 selectivity. However, the role of pore size in combination with surface functionality in the enhancement of these properties remains unclear. To investigate these effects, grand canonical Monte Carlo (GCMC) simulations were carried out on pure and N-functionalized 3-layer graphitic slit-pore models and compared to experimental results for two high performing materials reported elsewhere. We show that the quaternary, pyridinic, and especially the oxidized pyridinic group lend to enhanced performance, with the latter providing exceptional CO2 loading (4.31 mmol g-1) and CO2/N2 selectivity (138.3 : 1). Increasing surface nitrogen content resulted in enhanced loading and excellent CO2/N2 selectivity (45.8 : 1-55.9 : 1), provided that the sorbent has significant ultramicroporous character. Additionally, we elucidate a threshold pore width, under which N-functionalization becomes increasingly influential on performance parameters, and show how this threshold changes with application (PC vs. NGCC capture). Finally, we propose that an alternative functionality - the nitroso group - may be responsible for the enhanced performance of some recent materials reported in the literature.

Molybdenum disulfide catalyzed tungsten oxide for on-chip acetone sensing

Acetone sensing is critical for acetone leak detection and holds a great promise for the noninvasive diagnosis of diabetes. It is thus highly desirable to develop a wearable acetone sensor that has low cost, miniature size, sub-ppm detection limit, great selectivity, as well as low operating temperature. In this work, we demonstrate a cost-effective on-chip acetone sensor with excellent sensing performances at 200 °C using molybdenum disulfide (MoS2) catalyzed tungsten oxide (WO3). The WO3 based acetone sensors are first optimized via combined mesoscopic nanostructuring and silicon doping. Under the same testing conditions, our optimized mesoporous silicon doped WO3 [Si:WO3(meso)] sensor shows 2.5 times better sensitivity with ∼1000 times smaller active device area than the state-of-art WO3 based acetone sensor. Next, MoS2 is introduced to catalyze the acetone sensing reactions for Si:WO3(meso), which reduces the operating temperature by 100 °C while retaining its high sensing performances. Our miniaturiz...