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In this work, we reveal the role of non-covalent interactions, which are known to play important roles in supramolecular phenomena, in achieving efficient perovskite surface and grain boundary passivation. By using a series of pseudohalides, we find that trifluoroacetate (TFA^-) provides the strongest binding to iodide vacancies by means of non-covalent hydrogen bonding and dispersion interactions. By exploiting additional non-covalent dispersion and hydrophobic interactions in aromatic 3,3-diphenylpropylammonium (DPA⁺), we present a dual-ion passivation strategy that not only minimizes the non-radiative recombination center and local chemical inhomogeneities but also induces preferentially oriented growth of α-FAPbI₃ lattice. Further, this leads to anmore » outstanding power conversion efficiency (PCE) of 25.63% with an exceptional open-circuit voltage of 1.191 V in a perovskite solar cell with a small area, while perovskite solar mini modules with aperture areas of 25 and 64cm² achieved PCE of 22.47% (quasi-steady-state [QSS]-certified 20.50%) and 20.88%, respectively, with outstanding stability under high-humidity conditions.« less

Inorganic halide perovskite nanocrystals (PNCs) have demonstrated promising potential for solar cell applications. However, the lability of photoactive CsPbI3 phase under ambient conditions, coupled with considerable amounts of surface defects induced during solidification process, have impeded achieving high performances and longevities of the PNC-based solar cells. Post-treatment of the PNCs with organic ligands has been proposed as an efficient strategy for surface passivation, which, however, still relies on the binding actions of typical functional groups towards surface defects (especially, carboxylates onto iodine vacancies). Herein, we uncover that thiolate, a deprotonated form of thiol, renders distinctive binding feasibility towards iodine vacanciesmore » at the CsPbI3 PNC surface, compared with those of typical functional groups. By treating the PNC solid with deprotonated cysteine as a ligand, the surface defects are comprehensively passivated. The solar cells with the modified PNC films demonstrate an excellent PCE of 15.5 % and improved device longevity (77 % of initial PCE over 2 months) under ambient conditions. Our work not only elucidates the chemical principles of thiol on the binding with PNC surface, but also corroborates the power of thiolate as a promising strategy to develop high performances and improved longevity of solar cells.« less

Many technologically relevant materials for advanced energy storage and catalysis feature reduced transition-metal (TM) oxides that are often nontrivial to prepare because of the need to control the reducing nature of the atmosphere in which they are synthesized. In this report, we show that an ab initio predictive synthesis strategy can be used to produce multi-gram-scale products of various MgV_xO_y-type phases (δ-MgV₂O₅, spinel MgV₂O₄, and MgVO₃) containing V³⁺ or V⁴⁺ relevant for Mg-ion battery cathodes. Characterization of these phases using ²⁵Mg solid-state NMR spectroscopy illustrates the potential of ²⁵Mg NMR for studying reversible magnesiation and local charge distributions. Rotor-assisted populationmore » transfer (RAPT) is used as a much-needed signal-to-noise enhancement technique. The ab initio guided synthesis method is seen as a step forward towards a predictive synthesis strategy for targeting specific complex TM oxides with variable oxidation states of technological importance.« less

Abstract Many technologically relevant materials for advanced energy storage and catalysis feature reduced transition‐metal (TM) oxides that are often nontrivial to prepare because of the need to control the reducing nature of the atmosphere in which they are synthesized. Herein, we show that an ab initio predictive synthesis strategy can be used to produce multi‐gram‐scale products of various MgV _x O _y ‐type phases (δ‐MgV ₂ O ₅ , spinel MgV ₂ O ₄ , and MgVO ₃ ) containing V ³⁺ or V ⁴⁺ relevant for Mg‐ion battery cathodes. Characterization of these phases using ²⁵ Mg solid‐state NMRmore » spectroscopy illustrates the potential of ²⁵ Mg NMR for studying reversible magnesiation and local charge distributions. Rotor‐assisted population transfer (RAPT) is used as a much‐needed signal‐to‐noise enhancement technique. The ab initio guided synthesis method is seen as a step forward towards a predictive synthesis strategy for targeting specific complex TM oxides with variable oxidation states of technological importance.« less

Understanding the effect of chemical composition on the strength of magnetic interactions is key to the design of magnets with high operating temperatures. The magnetic divalent first-row transition metal (TM) thiocyanates are a class of chemically simple layered molecular frameworks. Here, we report two new members of the family, manganese(II) thiocyanate, Mn(NCS)₂, and iron(II) thiocyanate, Fe(NCS)₂. Using magnetic susceptibility measurements on these materials and on cobalt(II) thiocyanate and nickel(II) thiocyanate, Co(NCS)₂ and Ni(NCS)₂, respectively, we identify significantly stronger net antiferromagnetic interactions between the earlier TM ions—a decrease in the Weiss constant, θ, from 29 K for Ni(NCS)₂ to -115 Kmore » for Mn(NCS)₂—a consequence of more diffuse 3d orbitals, increased orbital overlap, and increasing numbers of unpaired $$t_{2_g}$$ electrons. We elucidate the magnetic structures of these materials: Mn(NCS)₂, Fe(NCS)₂, and Co(NCS)₂ order into the same antiferromagnetic commensurate ground state, while Ni(NCS)₂ adopts a ground state structure consisting of ferromagnetically ordered layers stacked antiferromagnetically. We show that significantly stronger exchange interactions can be realized in these thiocyanate frameworks by using earlier TMs.« less

We report that paramagnetic solid-state NMR of lanthanide (Ln) containing materials can be challenging due to the high electron spin states possible for the Ln ƒ electrons, which result in large paramagnetic shifts, and these difficulties are compounded for ¹⁷O due to the low natural abundance and quadrupolar character. In this work, we present examples of ¹⁷O NMR experiments for lanthanide oxides and strategies to overcome these difficulties. In particular, we record and assign the ¹⁷O NMR spectra of monoclinic Sm₂O₃ and Eu₂O₃ for the first time, as well as performing density functional theory (DFT) calculations to gain further insightmore » into the spectra. The temperature dependence of the Sm³⁺ and Eu³⁺ magnetic susceptibilities are investigated by measuring the ¹⁷O shift of the cubic sesquioxides over a wide temperature range, which reveal non-Curie temperature dependence due to the presence of low-lying electronic states. This behaviour is reproduced by calculating the electron spin as a function of temperature, yielding shifts which agree well with the experimental values. Using the understanding of the magnetic behaviour gained from the sesquioxides, we then explore the local oxygen environments in 15 at% Sm- and Eu-substituted CeO₂, with the ¹⁷O NMR spectrum exhibiting signals due to environments with zero, one and two nearest neighbour Ln ions, as well as further splitting due to oxygen vacancies. Finally, we extract an activation energy for oxygen vacancy motion in these systems of 0.35 ± 0.02 eV from the Arrhenius temperature dependence of the ¹⁷O T1 relaxation constants, which is found to be independent of the Ln ion within error. Finally, the relation of this activation energy to literature values for oxygen diffusion in Ln-substituted CeO₂ is discussed to infer mechanistic information which can be applied to further develop these materials as solid-state oxide-ion conductors.« less

We show that vacancy creation and relativistic spin–orbit coupling play a crucial role in promoting fast Mg-ion conduction of Mg ₃ Bi ₂ .