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. 2026 Mar 26;148(13):13654–13662. doi: 10.1021/jacs.5c19788

A Heterogeneous Manganese Catalyst for the Selective Hydrogenation of Nitroarenes

Jianglin Duan †, Wu Li †, Yujing Ren ‡,*, Kathrin Junge †,*, Matthias Beller †,*
PMCID: PMC13067263  PMID: 41883094

Abstract

Catalytic hydrogenations of nitroarenes are fundamental processes in organic chemistry, allowing for atom-efficient and clean synthesis of valuable amines. Recently, earth-abundant metals have attracted considerable interest in this field. Surprisingly, despite more than a century of developments in heterogeneous catalysis, in the present study, we describe for the first time a specific manganese-based single-atom catalyst that allows the selective hydrogenation of various nitroarenes. The corresponding amines were obtained with a high selectivity, especially for nitrostyrene. In the hydrogenation process, the addition of H2O was found to promote the activity of Mn1–N-C/Al2O3. Mechanistic control experiments indicated that the heterolytic activation of hydrogen may be a contributing factor. This work provides an effective approach for the design of completely new Mn-based heterogeneous hydrogenation catalysts.

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Introduction

In modern industrial development, catalysis serves as a fundamental cornerstone in the chemical and energy sectors. As the core of catalysis, the catalyst plays a crucial role in increasing reaction rate, controlling selectivity, and reducing energy consumption. Today, approximately 90% of industrial chemical transformations worldwide rely on catalytic processes, highlighting the application of catalysts as a pivotal force in modern chemical engineering, energy, environmental protection, pharmaceuticals, and fine chemicals. − Among all catalysts, platinum group metal (PGM) catalysts often exhibit outstanding catalytic performance and are widely used in many important catalytic processes. − For example, heterogeneous Pt-based catalysts have attracted much attention in the steam reforming reaction (e.g., Pt/α-MoC), while molecular Pd-based catalysts are widely used in cross-coupling reactions. However, the limited availability and cost of precious metals restrict their practical application. In this context, the development of nonprecious metal materials with high efficiency, low cost, and robust properties in industrial catalytic processes continues to be of great importance.

Comparing the many transformations of PGM catalysts, hydrogenation reactions stand out as one of the most versatile tools in the petrochemical, fine chemical, and environmental industries. In fact, it is estimated that approximately 25% of chemical processes involve at least one hydrogenation step. − Among these transformations, the hydrogenation of nitroarenes to anilines is a well-established process in both industry and academic laboratories. Industrially, this reaction is typically achieved using commercial noble-metal catalysts (e.g., Lindlar and NanoSelect catalysts), enabling the production of anilines that serve as key intermediates for pharmaceuticals, agrochemicals, dyes, and polymers. Academically, the nitroarene hydrogenation reaction has been extensively investigated since its first report in 1842, evolving into a model transformation for studying reaction mechanisms, chemoselectivity control, and catalyst design. Despite its apparent maturity, this classical reduction continues to attract significant scientific and economic interest, particularly driven by the urgent need to replace traditional PGM-based catalysts with earth-abundant, non-noble-metal alternatives. − For the synthesis of advanced amine building blocks, which are valuable intermediates in modern synthesis, achieving high chemoselectivity in such reactions is crucial. Apart from supported Au nanoparticles, notable examples of iron- − and cobalt-based − heterogeneous catalysts for general and selective hydrogenation of nitroarenes to amines have been disclosed.

Compared with other active catalyst metals, manganese species are relatively nontoxic, and Mn is the third most abundant transition metal in the Earth’s crust, after Fe and Ti. − Despite these advantages, Mn remains underutilized in heterogeneous catalysis. Although Kida prepared a Mn/graphene catalyst for hydrogenolysis of the C–OH bond in hydroxymethylfurfural, to the best of our knowledge, no heterogeneous catalysts with active manganese centers have been reported for the selective hydrogenation of nitroarenes. Interestingly, in the past decade, molecularly defined Mn complexes have emerged as a new class of hydrogenation catalysts, and this field became a hot topic in contemporary homogeneous catalysis (Figure A). −

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Selected examples of active Mn-based hydrogenation catalysts. (A) Homogeneous Mn-based catalysts for selective hydrogenations (e.g., nitriles, ketones, aldehydes, esters, and alkynes). (B) Heterogeneous Mn single-atom catalyst for selective hydrogenation of nitroarenes.

Although most supported manganese particles do not allow catalytic hydrogenation due to their intrinsic inertness to hydrogen activation, the success of homogeneous Mn complexes in hydrogenation makes it likely that it is possible. Meanwhile, recent studies on Mn–N–C materials in electrocatalytic fields have demonstrated that well-defined Mn–N x coordination environments can effectively stabilize atomically dispersed Mn centers. In this context, we had the idea to use single-atom Mn catalysts (Mn-SACs). − SACs have recently emerged as a platform for bridging different subfields of catalysis (Das, Waiba et al.). Due to the fact that all active metal atoms are isolated on the support, SACs not only allow for maximum efficiency in atom utilization compared with conventional heterogeneous counterparts but also resemble the catalytic properties of homogeneous metal complexes.

Inspired by this and based on our previous work on homogeneous Mn catalysis, , we present here the first Mn-SAC (Mn1-N-C/Al2O3) for selective hydrogenation reactions (Figure B). In the optimal catalyst material, defined Mn1-N4 single-atom sites were successfully anchored on the nitrogen-doped carbon surface after pyrolysis. Mechanistic studies reveal that the presence of H2O promotes heterolytic cleavage of H2 and the overall hydrogenation reaction. As a result, a wide range of substrates and high selectivity can be achieved in the hydrogenation of nitroarenes.

Results and Discussion

Preparation and Characterization of Mn1-N-C/Al2O3

At the start of this project, three different Mn­(II) salts (Mn­(OAc)2·4H2O, MnCl2·4H2O, and Mn­(NO3)2·4H2O) were mixed with three nitrogen-containing ligands (melamine, 1,10-phenanthroline, and phenylalanine). The latter were selected based on availability, nitrogen content, and previous use in pyrolysis processes with other metals. ,, After physical immobilization of both components on inert carbon or metal oxides, e.g., γ-Al2O3, TiO2, and nanodiamond (ND), the resulting solids were pyrolyzed at 400–800 °C (Table S1). It is worth mentioning that the introduction of γ-Al2O3 or TiO2 is beneficial for the dispersion of Mn species during the pyrolysis process. The general procedure for the most active material, Mn1-N-C/Al2O3, is illustrated in the Supporting Information. From the N2 adsorption–desorption result (Figure S1), the S BET of Mn1-N-C/Al2O3 is ∼135 m2/g (Table S2). Inductively coupled plasma (ICP) analysis showed that the Mn loading in Mn1-N-C/Al2O3 is 2.86 wt % (Table S3). According to the total element analysis result, no other known hydrogenation metal, including Ru, Rh, Pd, Ir, Pt, Fe, Co, Ni, and Cu, was detected in Mn1-N-C/Al2O3.

The X-ray diffraction (XRD) pattern of Mn1-N-C/Al2O3 displays a characteristic peak of γ-Al2O3 (Figure A), in the absence of any metallic Mn or Mn oxide phase. Also, no noticeable presence of Mn species was detected in the scanning electron microscopy (SEM) images (Figure S2). Consistently, the scanning transmission electron microscopy (STEM) and corresponding energy dispersive spectrometer (EDS) analysis of Mn1-N-C/Al2O3 reveal a clear and uniform distribution of C, N, O, Al, and Mn species on the γ-Al2O3 support (Figures B and S3). These structural characterization results suggest a high dispersion of the Mn species. To investigate the dispersion of Mn, aberration-corrected HAADF-STEM (AC-HAADF-STEM) characterization was performed. As shown in Figures C and S4, isolated and easily distinguishable bright spots were observed, which are attributed to Mn1 single atoms. Summarizing various analytical methods, the successful synthesis of Mn1-N-C/Al2O3 SAC can be assumed.

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Characterizations of Mn1–N-C/Al2O3 catalysts: (A–C) The XRD patterns, EDS-mapping, and AC-HAADF-STEM of Mn1-N-C/Al2O3 catalysts. (D) XAFS analysis of Mn1-N-C/Al2O3. (I) The XANES spectra of Mn K-edge in Mn1-N-C/Al2O3 catalysts and (II) oxidation states of Mn species. (III, IV) The Fourier-transformed k 2-weighted EXAFS spectra in R-space and the corresponding fitting curves of Mn1-N-C/Al2O3 catalysts.

Next, X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) characterizations were performed to elucidate the chemical environment of the Mn1 species. As displayed in Figure S5, Mn1-N-C/Al2O3 exhibited a doublet with 2p3/2 binding energy at 641.1 eV, indicating an oxidation state of Mn of about +2. From the result of Mn K-edge X-ray absorption near edge structure (XANES) spectra (Figure D-I), the absorption edge of Mn1-N-C/Al2O3 is located at the position between Mn foil and Mn2O3, like MnO. In addition, the result of the linear correlation shows that the average oxidation state of Mn1 single atoms is around 2.08 (Figure D-II), which is in good agreement with the XPS result. Notably, both Mn1-N-C/Al2O3 showed a distinct pre-edge peak at 6545 eV (1s to 4p z transition), indicating the possible four-coordinated structure of the Mn1 single atom. On this basis, the Mn K-edge extended X-ray absorption fine structure (EXAFS) of Mn1-N-C/Al2O3 was investigated. As shown in Figure D-III, the scattering oscillation of Mn1–N-C/Al2O3 showed a prominent peak at 1.6 Å, which is attributed to the coordination of Mn to the light element (e.g., N, O). No distinct Mn–Mn scattering peak at about 2.2 Å was detected, indicating the single-atom dispersion of Mn, which is consistent with the AC-HAADF-STEM result. These findings were further confirmed by wavelet-transform analysis (Figure S6). Finally, least-squares EXAFS curve fitting was performed. As shown in Figure D-IV and Table S4, each isolated Mn atom is coordinated with four nitrogen atoms with a Mn1–N4 structure.

Catalytic Performance and Mechanism Investigation

With Mn1-N-C/Al2O3 SAC in hand, the selective hydrogenation of nitroarenes, which is an important methodology to synthesize fine chemical intermediates, e.g., flavors, pharmaceuticals, and agrochemicals, was chosen as a test case. Specifically, 3-nitrostyrene (3-NS) bearing an easily reducible vinyl group next to the nitro moiety was used as a challenging model compound for the catalytic hydrogenation to the corresponding 3-aminostyrene (3-AS). Investigating the influence of key reaction parameters (temperature, pressure, solvent) on this benchmark reaction (Figure S7 and Table S5) revealed an interesting effect of traces of water on the catalytic activity of the Mn1-N-C/Al2O3 catalyst (see below).

At the optimized conditions (160 °C, 50 bar, 1 mL DMF, H2O to 3-NS ratio at ∼7.4), Mn1-N-C/Al2O3 exhibited good catalytic performance, allowing the complete hydrogenation of 3-NS with a selectivity of the desired product, 3-AS, above 99% (Table , entry 1). Even with further prolonging of the reaction, this selectivity remained stable (Figure S8), with no byproducts detected. In contrast, applying the optimized condition of our Mn1–N-C/Al2O3 catalyst for commercial noble-metal catalysts, such as Rh/C, Pd/C, and Pt/C, lower yields of 3-NS and poor chemoselectivity were obtained for this challenging hydrogenation process (Table , entries 2–4 and Table S6). Using the ratio of catalytic activity per unit time to metal price as the evaluation criteria, Mn1-N-C/Al2O3 is superior to the commercial catalysts mentioned. Besides, all other tested Mn­(II) salts or complexes, including MnO, manganese phthalocyanine (Mn-Pc), MnSO4, and Mn­(CH3COO)2, showed hardly any activity under these conditions (Table , entries 5–8). As for the other transition-metal-based catalysts, although the Mn1-N-C/Al2O3 exhibited relatively lower activity than Fe­(Co/Ni/Cu)-N-C/Al2O3 catalysts, exceptional selectivity was acquired on the Mn1–N-C/Al2O3 in the hydrogenation of 3-NS. Then, we choose both turnover number (TON) and turnover frequency (TOF) as the comparison indexes to make a comparison between Mn1-N-C/Al2O3 and its homogeneous counterparts. As shown in Table S7, the intrinsic TON on Mn1-N-C/Al2O3 is calculated as 60.5. Also, the TOF value is determined as 0.21 h–1. Both activity indexes are comparable to the homogeneous Mn complex and Fe-based heterogeneous hydrogenation catalysts (Table S8). After the TON evaluation, via treating at 400 °C in an Ar atmosphere for 1 h, the Mn1-N-C/Al2O3 catalyst was effectively regenerated, without leaching any Mn species into the solution (Tables S9 and 10). The decrease of the catalytic activity might be due to the adsorption of reactants or intermediates on the Mn1-N-C/Al2O3 surface, which can be effectively removed during the thermal treatment.

1. Selective Hydrogenation of 3-NS: Screening of Various Commercial Catalysts and Comparison with Mn1-N-C/Al2O3 .

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entry catalyst conv. (%) 1b (%) 1c (%)
1 Mn1-N-C/Al2O3 99 99 /
2 5%-Pt/C 30 9 21
3 5%-Rh/C 78 31 47
4 10%-Pd/C 60 7 53
5 MnO / / /
6 Mn-Pc <1 / <1
7 MnSO4 / / /
8 Mn(CH3COO)2 / / /
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a

Reaction conditions: Entries 1, 5–8: 0.3 mmol of 3-NS, 50 mg of catalyst, 1 mL of DMF and H2O (H2O to 3-NS ratio at ∼7.4) for 18 h at 160 °C, 50 bar H2. Entries 2–4: 10 mg of 5%-Pt/C, 5%-Rh/C catalyst and 5 mg of 10%-Pd/C, 3 min at 160 °C, 50 bar H2.

After that, the role of trace amounts of water in 3-NS hydrogenation was investigated. As shown in Figure A and Table S11, the introduction of water remarkably improves the catalytic activity on the Mn1-N-C/Al2O3 catalyst. The optimal H2O to 3-NS ratio was 7.4, which indicated the necessity of external water addition. With a further increase of the H2O content, the hydrogenation activity obviously declines, suggesting the overdose of H2O produces side effects. When the molar ratio of H2O to 3-NS substrate is larger than 46.3, the catalytic activity is obviously lower than that of the water-free system. On this basis, the kinetic experiments were conducted to explore the catalytic behavior of H2O in the catalytic system. As shown in Figure B and Table S12, the reaction order of the benchmark reaction is unchanged after the introduction of H2O, indicating that the addition of H2O does not affect the activation of the catalyst material. As for the other reactant (H2), the reaction order increased from 0.5 to 1.0 by adding trace H2O into the system (H2O to 3-NS ratio at ∼7.4, Figure C and Table S13). This result demonstrates that the H2 activation on Mn1-N-C/Al2O3 SAC likely follows a heterolytic cleavage mode, such as the known homogeneous Mn­(I)-based pincer complexes.

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Mechanistic experiments on 3-NS hydrogenation over Mn1-N-C/Al2O3 SAC. (A) Relationship between H2O content and catalytic performance. (B) The 3-NS reaction order and (C) the H2 reaction order over Mn1-N-C/Al2O3 SAC. Reaction conditions: 50 mg of catalyst, 1 mL of DMF, and 40 μL of H2O (corresponding content for A) or without H2O, for 5 h at 160 °C, 50 bar of H2. (D) The H2-D2O isotopic exchange experiment on the Mn1-N-C/Al2O3 catalyst at 160 °C. (E) The hydrogenation activity comparison of 3-nitrostyrene on Mn1-N-C/Al2O3. (F) Deuterated products in the phenylacetylene hydrogenation reaction with Mn1-N-C/Al2O3 SAC. Reaction conditions: 50 mg of catalyst, 1 mL of DMF, and 40 μL of D2O for 48 h at 160 °C, 50 bar of H2.

Then, for an in-depth understanding of the H2 activation process, the H2-D2 and H2-D2O isotopic exchange experiments were conducted. As shown in Figure S10, the mass spectrometry data exhibits that the intensity of HD (m/z = 3) gradually increases from 160 to 185 °C, accompanied by the declining of H2 (m/z = 2) and D2 (m/z = 4) intensities, which confirms the activated dissociation of H2 on Mn1-N-C/Al2O3. Subsequently, the result of the H2-D2O isotopic exchange test shows that the introduction of a D2O pulse leads to the production of HD (m/z = 3) and HDO (m/z = 19) (Figure D). In contrast, the N–C/Al2O3 barely shows any capability for the H2 activation in H2-D2(D2O) isotopic exchange experiments (Figures S11 and S12), in good agreement with the catalytic performance evaluation results (Table S14). The former HD generation demonstrates that D2O is involved in H2 dissociation, and the later HDO appearance implies that the H2 follows a heterolytic activation mode on the Mn1–N4 single-atom site, in which the formation of HDO is derived from dissociated H+ and D2O. In the meantime, given the circumstances that the 2,6-di-tert-butylpyridine can selectively poison Brønsted acid, whereas pyridine displays universal toxicity for Brønsted acid and Lewis acid, we used both 2,6-di-tert-butylpyridine and pyridine as the toxic agents in the control experiments to investigate the role of generated H+ (Brønsted acid) in the hydrogenation of 3-NS (Figure E, see the Supporting Information for details). The blank experiment demonstrates that both 2,6-di-tert-butylpyridine and pyridine would not coordinate to Mn1 single atoms, thereby causing the decrease of activity (Table S15). With the introduction of 2,6-di-tert-butylpyridine, the catalytic activity apparently decreases, comparable to the no-water system. Pyridine addition would not further affect the hydrogenation activity. This result indicates that the in situ-generated H+ (Brønsted acid), which is produced from the heterolytic cleavage of H2, is the contributing factor for the improved catalytic activity. This catalytic mechanism is quite different from the H2O-promoted Fe­(Co/Ni/Cu)–N-C/Al2O3 hydrogenation system (Figure S13), the H2O-assisted adsorption strength inversion between nitro and amino groups on the Co1–N-C catalyst, and the way of using H2O to produce active hydroxyl species in CO atmosphere on α-MoC1–x -supported metal catalysts. Furthermore, it has been reported that the addition of H2O can promote hydrogen spillover. , On this basis, an isotope control experiment using D2O was carried out. Considering that the hydrogen atoms in the resulting amino group are too reactive, they can easily be replaced by hydrogen atoms from H2O, phenylacetylene was chosen as the probe molecule (Figure F). Indeed, the use of D2O instead of H2O in the hydrogenation of phenylacetylene resulted in the formation of β-D-styrene, which clearly shows that water takes part in the hydrogenation reaction. Our proposed H2O-promoted hydrogenation process is also different from the recently reported H2O-mediated proton–electron transfer on Pt1/humic acid catalyst. Specifically, in the Pt1/humic acid system, H2O is indispensable for enabling a biomimetic PCET pathway, where proton transfer through a hydrogen-bond network is intrinsically coupled with electron delivery from the Pt single atom, and hydrogenation is essentially inaccessible in the absence of H2O.

In the meantime, the attenuated total reflectance infrared spectroscopy (ATR-IR) characterization was performed to explore the adsorption behavior of the 3-NS substrate on the Mn1-N-C/Al2O3 surface. As shown in Figure S14, the pure 3-NS produced two bands at 1344 and 1523 cm–1, which are attributed to asymmetric stretching and symmetric stretching vibrations of the nitro group, respectively. With the introduction of the Mn1-N-C/Al2O3 sample, one can clearly see that the 3-NS adsorbs on the catalyst surface with two nitro group bands shifting to 1350 and 1529 cm–1, which is similar to the adsorption behavior on γ-Al2O3. Further introducing hydrogen and increasing the temperature to 140 °C, the appearance of the new bands at 1461 cm–1 (–NOH) and 1494 cm–1 (−NH2) was observed on the Mn1-N-C/Al2O3 catalyst (Figure S15). In contrast, the same procedure on the γ-Al2O3 support did not bring about any change in the nitro adsorption bands (Figure S16). It is worth mentioning that the Al atoms in γ-Al2O3 serve as Lewis acids, and the oxygen atoms in the nitro group act as Lewis bases. The preferential adsorption of the nitro group on γ-Al2O3 can be regarded as the interaction between the Lewis acid and base, even in the presence of other reducible groups. Furthermore, we also test the 3-NS reaction order on the Mn–N–C sample, which shows a 0.8 value, much higher than the Mn1-N-C/Al2O3 catalyst (Figure S17 and Table S16). This result further suggests that γ-Al2O3 is reasonable for the enrichment and activation of nitro groups. Besides, the result of 3-NS adsorption content shows that both γ-Al2O3 and Mn1-N-C/Al2O3 samples can effectively adsorb 3-NS (Table S17), in good agreement with the ATR-IR characterization and kinetics experiment results. Taking these results together, it can be reasonably deduced that H2 is activated on the Mn single atoms and the nitro group is preferentially adsorbed on the γ-Al2O3 for further surface hydrogenation process in Mn1-N-C/Al2O3.

In summary, the synergistic effect between Mn1-N-C and Al2O3 for the hydrogenation of nitroarenes can be clearly illustrated. First, the nitro group is preferentially adsorbed on the Al2O3 surface. Then, under anhydrous conditions, H2 dissociation on Mn1-N-C/Al2O3 likely proceeds via a homogeneous Mn–N cooperative pathway, which is similar to Co–N­(P)–C and Ni–N–C SAC systems. , With the introduction of trace H2O, the hydrogen is activated on the Mn1 single atoms via the heterolytic activation mode. Considering that the isolated Mn­(II) atom is a Lewis acid site, and the fact that H2O can serve as a Lewis base site, the trace H2O facilitates the heterolytic cleavage of the H2 molecule to the H+ and H– species, analogous to the reported H2O-promoted H-shuttling mechanism on Co–N–C. The generated H+ is interacting with H2O to produce H3O+, improving the catalytic hydrogenation activity through the proton transfer process on Mn1-N-C/Al2O3 SAC. Followed by further transfer of H– species for nitro group reduction, the 3-NS was transformed into 3-AS.

Practical Application Potential

To showcase the general applicability of Mn1-N-C/Al2O3 SAC, various functionalized nitroarenes were hydrogenated. As shown in Figure A, a series of nitroarenes, which contain alkyl, olefinyl, hydroxyl, alkoxy, carbonyl, and biphenyl groups, can be effectively converted into the corresponding substituted anilines with satisfactory yields (3b–5b, 7b, 8b, and 16b–20b). As for halide substituents, the hydrogenation of chloro-nitroarenes proceeded with high yields (11b and 12b). However, iodo-nitroarene showed poorer selectivity with this catalytic system (9b). Compared with the iodol analogue, the bromo-nitroarene shows improved catalytic performance, consistent with the weaker C–Br bond interaction (13b). Meanwhile, when the nitroarenes contain strong electron-withdrawing groups, including cyano- and para-trifluoromethyl-, good yields of the corresponding anilines were also achieved (6b and 10b). Besides, the Mn1-N-C/Al2O3 catalyst showed excellent selectivity for the hydrogenation of heterocyclic nitroarenes (15b). Notably, in contrast to traditional PGM-based catalysts, the Mn1-N-C/Al2O3 SAC displayed excellent poison-resistant capability for the selective hydrogenation of sulfur-containing nitroarenes (14b). Nevertheless, there are some limitations observed with respect to alkyne- and aldehyde-containing substrates on Mn1-N-C/Al2O3. In the case of terminal 3-nitrophenylacetylene, both functional groups were reduced, affording 3-aminostyrene as the sole product after 18 h. And the hydrogenation of 4-nitrobenzaldehyde resulted in a complex mixture of reduced products (Table S18).

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Substrate scope and reusability studies. (A) Isolated yield (#GC yield), 0.3 mmol of substrates, 50 mg of Mn1-N-C/Al2O3 catalyst, 1 mL of DMF, and 40 μL of H2O for 48 h at 160 °C, 50 bar of H2 (*reaction time for 8 h and #for 18 h). (B) Recycling experiments. 0.3 mmol of 3-NS, 100 mg of catalyst, 2 mL of DMF and H2O (H2O to 3-NS ratio at ∼7.4) for 8 h at 160 °C, 50 bar of H2. (C) XRD pattern and (D) AC-HAADF-STEM of the used Mn1-N-C/Al2O3 catalysts.

While all substrates were studied under the standard reaction conditions, we also performed test reactions at a shorter reaction time (8 h) with six selected substrates. As shown in Figure A, similar conversions and yields were observed for most of them (5b, 7b, 8b, 11b, 14b, 15b). Finally, the stability and reusability of our optimal catalyst material were tested, which is a key feature for any application of heterogeneous catalysts. Fortunately, in the recycling experiments, Mn1-N-C/Al2O3 SAC showed barely any decrease in activity and selectivity over 6 cycles (Figure B, see also the Supporting Information for details). The Mn1-N-C/Al2O3 catalyst used was characterized by XRD, HAADF-STEM, and XPS. As shown in the XRD spectra (Figure C), the structure of the recycled material is similar to the fresh one, indicating the stability of Mn1-N-C/Al2O3. In the HAADF-STEM images (Figures D and S18), the Mn species of the used Mn1-N-C/Al2O3 sample can be clearly seen as isolated bright dots, showing that there is no aggregation of Mn1 single atoms on the support surface. The STEM and corresponding EDS analysis of the used Mn1-N-C/Al2O3 show a clear and uniform distribution of C, N, O, Al, and Mn species on the support (Figure S19). Regarding the oxidation state, no change in the binding energy of Mn 2p3/2 was observed during the reaction (Figure S20). All of these results indicate that Mn1-N-C/Al2O3 SAC is of high stability.

Conclusions

In conclusion, we report here the first development of a heterogeneous Mn catalyst for selective hydrogenation reactions in organic synthesis. Using a pyrolysis preparation method, specific Mn1-N4 sites on a nitrogen–carbon-covered γ-Al2O3 surface were constructed and characterized in detail. The resulting Mn1-N-C/Al2O3 SAC exhibits a good catalytic performance in the hydrogenation of 20 nitroarenes. The corresponding amines were obtained with high selectivity, especially for nitrostyrene. In the hydrogenation process, the addition of H2O promotes the activity of the Mn1-N-C/Al2O3. Mechanistic control experiments suggest heterolytic activation of hydrogen. This work provides an effective approach for the design of completely new Mn-based heterogeneous hydrogenation catalysts. Here, we make it clear that we do not aim for the best TON but rather want to demonstrate that Mn can be used as a heterogeneous hydrogenation catalyst.

Supplementary Material

ja5c19788_si_001.pdf (9.6MB, pdf)

Acknowledgments

The authors wish to acknowledge the support of the National Key R&D Program of China (No. 2023YFA1506603). J. Duan thanks the support of the China Scholarship Council (No. 202306290026). We thank Dr. R. Qu for the helpful discussion.We thank S. Ahrens and Dr. R. Kusy for assistance with figure preparation.

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.5c19788.

  • Methods and procedures of catalysts preparation, characterization, evaluation, as well as supporting figures and tables (PDF)

The manuscript was written through the contributions of all authors. All authors have given approval to the final version of the manuscript.

The authors declare no competing financial interest.

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