Design and synthesis of ordered, metal-free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed-dimensional (2D/3D) metal-free van der Waals (vdW) heterostructures based on triazine (C3 N3 ) linkers grow as large area, transparent yellow-orange membranes on copper surfaces from solution. The membranes have an indirect band gap (Eg,opt = 1.91 eV, Eg,elec = 1.84 eV) and are moderately porous (124 m2 g-1 ). The material consists of a crystalline 2D phase that is fully sp2 hybridized and provides structural stability, and an amorphous, porous phase with mixed sp2 -sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one-pot reaction mixture: unprecedented for metal-free frameworks and a direct consequence of on-catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal-free, light-induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h-1 g-1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of "wet" chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.

Faculty of Chemical Engineering Department of Analytical Chemistry University of Chemistry and Technology Prague Technická 3 160 00 Prague 6 Czech Republic

Faculty of Science Department of Analytical Chemistry Charles University Hlavova 8 128 43 Prague 2 Czech Republic

Faculty of Science Department of Organic Chemistry Charles University Hlavova 8 128 43 Prague 2 Czech Republic

Faculty of Science Department of Physical and Macromolecular Chemistry Charles University Hlavova 8 128 43 Prague 2 Czech Republic

Humboldt Universität zu Berlin Department of Physics Physics of Macromolecules Newtonstr 15 12489 Berlin Germany

Institute of Organic Chemistry and Biochemistry of the CAS Flemingovo nám 2 166 10 Prague 6 Czech Republic

J Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic v v i Dolejškova 2155 3 182 00 Prague 8 Czech Republic

Leibniz Institute of Polymer Research Dresden Hohe Str 6 01069 Dresden Germany

Materials Chemistry Department Institute of Inorganic Chemistry AS CR v v i 250 68 Řež Czech Republic

Technische Universität Berlin Institute of Chemistry Hardenbergstr 40 10623 Berlin Germany

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