▲First authors: WEI Qinhong, LI Hangjie, LIU Grasshopper; Correspondence should be addressed to CHUN Fanli, YANG Guohui, PENG Xiaobo

Correspondence should be addressed to National University of Toyama, Japan, Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, National Institute for Materials Research, Japan, and Zhejiang Normal University, China.

Paper DOI: 10.1038/s41467-020-17941-8

Full text brief

Recently, a collaborative team of Professor Noritatsu Tsubaki of National University of Toyama, Japan, Researcher Yang Guohui of Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences and Dr Peng Xiaobo of National Institute for Materials Research (NIMR), Japan, has successfully achieved the design and construction of an autocatalytic reactor coupled with catalysts and reactors through metal 3D printing technology. The design breaks the convention by not requiring a catalyst to be loaded inside the tube. The iron-based, cobalt-based and nickel-based 3D autocatalytic reactors it developed not only have the ability to withstand high temperature and high pressure, but also assume the role of catalysts, and show extremely broad catalytic applications in typical C1 reactions such as Fischer-Tropsch Synthesis, CO2 Hydrogenation, and Dry Reforming of Methane. In addition, the theory of morphology control of 3D autocatalytic reactors opens up new research directions for future autocatalytic synthesis. This work, entitled "Metal 3D Printing Technology for Functional Integration of Catalytic System", was recently published in Nature Communications, and has been applied for international publication. This work has been applied for an international patent.

Research background

Catalysts and reactors are two of the most important elements in catalytic reactions. However, for a long time the design of catalysts and reactors have always been developed relatively independently in their own fields. The integrated coupling and synergy of catalysts and reactors are also rarely reported. 3D printing, as an additive mode of making things, has shown a strong development trend in biotechnology, pharmaceuticals, and mechanical manufacturing, but its development in the chemical and chemical fields is very slow. Metal 3D printing, as an important branch of 3D printing technology, has inherent advantages for the integrated coupling of catalysts and reactors:

(1) The metal itself has catalytic ability and is resistant to high temperature and pressure.

(2) Energy transfer efficiency, much higher than conventional catalytic reaction systems.

(3) Eliminate the need for binder moulding of conventional solid catalysts and improve catalyst stability.

(4) Computer controlled printing to eliminate the error of hand in catalyst and reactor fabrication.

(5) Highly flexible and free design of the shape of the printed product.

Metal 3D printing technology, therefore, offers a whole new way of thinking about the design of catalysts and reactors for petrochemicals, C1 chemistry, or other catalytic reactions.

Highlights of this article

(1) This study reports, for the first time, the preparation of autocatalytic reactors with tunable species and morphology using metal 3D printing.

(2) An iron-based autocatalytic reactor, which exhibits good pressure resistance and reactivity in Fischer-Tropsch synthesis and carbon dioxide hydrogenation, and characterization experiments have demonstrated that a catalytically active layer on the inner wall of the reactor is essential for the reaction to proceed.

(3) Cobalt-based autocatalytic reactor exhibiting good liquid fuel selectivity in Fischer-Tropsch synthesis.

(4) Nickel-based autocatalytic reactor showing excellent high temperature resistance and catalytic performance in the reaction of carbon dioxide reforming methane.

(5) Conformal studies of autocatalytic reactors demonstrate that the highly free design of 3D printing can modulate the catalytic function of the reaction system.

graphic resolution

▲ Figure 1. 3D printing for self-catalytic reactor (SCR) and other typical applications. The inset: (left) SCR for Fischer-Tropsch synthesis; (middle) SCR for CO2 hydrogenation; (right) SCR for CO2 reforming of CH4. (left) SCR for Fischer-Tropsch synthesis; (middle) SCR for CO2 hydrogenation; (right) SCR for CO2 reforming of CH4.

3D printing is an additive manufacturing technology that has been extensively researched in biotechnology, prosthetics, pharmaceuticals, and mechanical engineering (Figure 1). Metal 3D printing technology, was applied in this study. The technology uses metal powder as raw material to achieve rapid prototyping of autocatalytic reactors by layer-by-layer printing. The printed iron-based Fe-SCR, cobalt-based Co-SCR and nickel-based Ni-SCR autocatalytic reactors can be applied to catalytic reactions such as Fischer-Tropsch synthesis, carbon dioxide hydrogenation and Dry Reforming of Methane, respectively.

Figure 2. Catalytic performance of SCRs. a, The physical SCRs after polishing the outer surface.

b, Fe-SCR for Fischer-Tropsch synthesis. c, Fe-SCR for CO2 hydrogenation. d, Co-SCR for Fischer-Tropsch synthesis. e, Ni-SCR for CO2 reforming of CH4. CO2 hydrogenation. d, Co-SCR for Fischer-Tropsch synthesis. e, Ni-SCR for CO2 reforming of CH4.

▲ Figure 3. Geometrical structures of Co-SCRs. a, Co-SCR-1; b, longitudinal section of Co-SCR-1; c, cross-section of Co-SCR-1; d, cross-section of Co- SCR-2; e, cross-section of Co-SCR-3; f, cross-section of Co-SCR-4; g, cross-section of Co-SCR; h, cross-section of Co-SCR-5; i, cross-section of Co- SCR-6.

▲ Figure 4.