Xingxu Lu

Scalable continuous flow synthesis of ZnO nanorod arrays in 3-D ceramic honeycomb substrates for low-temperature desulfurization

Scalable and cost-effective synthesis and assembly of technologically important nanostructures in three-dimensional (3D) substrates hold keys to bridge the demonstrated nanotechnologies in academia with industrially relevant scalable manufacturing. In this work, using ZnO nanorod arrays as an example, a hydrothermal-based continuous flow synthesis (CFS) method is successfully used to integrate the nano-arrays in multi-channeled monolithic cordierite. Compared to the batch process, CFS enhances the average growth rate of nano-arrays by 125%, with the average length increasing from 2 μm to 4.5 μm within the same growth time of 4 hours. The precursor utilization efficiency of CFS is enhanced by 9 times compared to that of batch process by preserving the majority of precursors in recyclable solution. Computational fluid dynamic simulation suggests a steady-state solution flow and mass transport inside the channels of honeycomb substrates, giving rise to steady and consecutive growth of ZnO nano-arrays with an average length of 10 μm in 12 h. The monolithic ZnO nano-array-integrated cordierite obtained through CFS shows enhanced low-temperature (200 °C) desulfurization capacity and recyclability in comparison to ZnO powder wash-coated cordierite. This can be attributed to exposed ZnO {100} planes, better dispersion and stronger interactions between sorbent and reactant in the ZnO nanorod arrays, as well as the sintering-resistance of nano-array configurations during sulfidation–regeneration cycles. With the demonstrated scalable synthesis and desulfurization performance of ZnO nano-arrays, a promising, industrially relevant integration strategy is provided to fabricate metal oxide nano-array-based monolithic devices for various environmental and energy applications.

Scalable Integration of Highly Uniform MnxCo3−xO4 Nanosheet Array onto Ceramic Monolithic Substrates for Low-Temperature Propane Oxidation

The redox reaction between KMnO4 and Co(NO3)2 was designed and readily utilized for the scalable integration of spinel MnxCo3−xO4 nanosheet arrays in three‐dimensional ceramic honeycombs by controlling the reaction temperature. The Co2+ can reduce MnO4− to form Mn–Co spinel oxide nanosheet arrays uniformly on the channel surface of cordierite honeycomb. The novel platinum group metal free oxide nanosheet array integrated ceramic honeycomb monolith shows good low‐temperature catalytic activity for propane oxidation, with the 50 % conversion temperature achieved at 310 °C, which is a much lower temperature than that over the wash‐coated commercial Pt/Al2O3. These integrated Mn–Co composite oxide nanoarrays may hold great promise for the construction of advanced monolithic catalyst for high‐performance and low‐cost emission control.

Mesoporous Perovskite Nanotube-Array Enhanced Metallic-State Platinum Dispersion for Low Temperature Propane Oxidation

Plagued by low surface area and limited oxidation activity at low temperature, perovskite‐type LaMnO3 based catalysts also suffer from poor hydrothermal stability. In this communication, mesoporous nanotube arrays of LaMnO3‐Pt were successfully derived from core/shell nanorod arrays with significantly increased surface area through diluted acid etching. Surface Mn4+ population is boosted to compensate La cation deficiency and enhance low temperature reducibility of nanotube arrays, enabling surface dispersion of abundant metallic‐state Pt nanoparticles. As a result, significantly enhanced catalytic propane oxidation was achieved in such a new class of perovskite/Pt nanotube array integrated structured catalysts.

Template-Guided Programmable Janus Heteronanostructure Arrays for Efficient Plasmonic Photocatalysis

Janus heteronanostructures (HNs), as an important class of anisotropic nanomaterials, could facilitate synergistic coupling of diverse functions inherited by their comprised nanocomponents. Nowadays, synthesizing deterministically targeted Janus HNs remains a challenge. Here, a general yet scalable technique is utilized to fabricate an array of programmable Janus HNs based on anodic aluminum oxide binary-pore templates. By designing and employing an overetching process to partially expose four-edges of one set of nanocomponents in a binary-pore template, selective deposition and interfacing of the other set of nanocomponents is successfully achieved along the exposed four-edges to form a densely packed array of Janus HNs on a large scale. In combination with an upgraded two-step anodization, the synthesis provides high degrees of freedom for both nanocomponents of the Janus HNs, including morphologies, compositions, dimensions, and interfacial junctions. Arrays of TiO2-Au and TiO2/Pt NPs-Au Janus HNs are designed, fabricated, and demonstrated about 2.2 times photocurrent density and 4.6 times H2 evolution rate of that obtained from their TiO2 counterparts. The enhancement was mainly determined as a result of localized surface plasmon resonance induced direct hot electron injection and strong plasmon resonance energy transfer near the interfaces of TiO2 nanotubes and Au nanorods. This study may represent a promising step forward to pursue customized Janus HNs, leading to novel physicochemical effects and device applications.

Direct Synthesis of Conformal Layered Protonated Titanate Nanoarray Coatings on Various Substrate Surfaces Boosted by Low-Temperature Microwave-Assisted Hydrothermal Synthesis

Layered protonated titanates (LPTs) are promising support materials for catalytic applications because their high surface area and cation exchange capacity provide the possibility of achieving a high metal dispersion. However, the reported LPT nanomaterials are mainly limited to free-standing nanoparticles (NPs) and usually require high temperature and pressure conditions with extended reaction time. In this work, a high-throughput microwave-assisted hydrothermal method was developed for the direct synthesis of conformal LPT nanoarray coatings onto the three-dimensional honeycomb monoliths as well as other substrate surfaces at low temperature (75-95 °C) and pressure (1 atm). Using TiCl3 as the titanium source, H2O2 as the oxidant, and hydrochloric acid as the pH controller, a peroxotitanium complex (PTC) was formed and identified to play an essential role for the formation of LPT nanoarrays. The gaseous O2 released during the decomposition of PTC promotes the mass transfer of the precursors, making this method applicable to substrates with complex geometries. With the optimized conditions, a growth rate of 42 nm/min was achieved on cordierite monolith substrates. When loaded with Pt NPs, the LPT nanoarray-based monolithic catalysts showed excellent low-temperature catalytic activity for CO and hydrocarbon oxidation as well as satisfactory hydrothermal stability and mechanical robustness. The low temperature and pressure requirements of this facile hydrothermal method overcome the size- and pressure-seal restrictions of the reactors, making it feasible for scaled production of LPT nanoarray-based devices for various applications.