Linear Adsorption Enables NO Selective Electroreduction to Hydroxylamine on Single Co Sites

Zhou, Jin; Han, Shuhe; Yang, Rong; Li, Tieliang; Li, Wenbin; Wang, Yuting; Yu, Yifu; Zhang, Bin

doi:10.1002/ange.202305184

Cited by 3 publications

(4 citation statements)

References 37 publications

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“…For all the catalysts as the potential decreases from 0.7 V to −0.3 V, an absorption peak appeared around 1400 cm −1 and was ascribed to the N−H stretching. 35 In addition to this peak, a broad band between 1450 and 1800 cm −1 was also observed. Deconvoluting this band on the spectra obtained at −0.1 V on Cu 50 Ni 50 -SSA/C (Figure 4a) unfolded three distinct bands centered at 1712, 1620, and 1531 cm −1 (Supporting Information, Figure S17).…”

Section: ■ Results and Discussionmentioning

confidence: 88%

“…In the aim to elucidate the preferential adsorption and reduction capabilities of the catalysts for NO, a key intermediate species in the reaction, in situ electrochemical ATR–FTIR was employed (Figure a–d). For all the catalysts as the potential decreases from 0.7 V to −0.3 V, an absorption peak appeared around 1400 cm –1 and was ascribed to the N–H stretching . In addition to this peak, a broad band between 1450 and 1800 cm –1 was also observed.…”

Section: Resultsmentioning

confidence: 88%

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Phase-dependent Electrocatalytic Nitrate Reduction to Ammonia on Janus Cu@Ni Tandem Catalyst

Lou,

Zheng,

Zhou

et al. 2024

ACS Catal.

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Electrosynthesis of NH 3 from nitrate anion (NO 3 − ) reduction (NO 3 − RR) is a cascade reaction, which is considered a great potential alternative to the Haber−Bosch route to reduce CO 2 emissions and alleviate the adverse effects of excessive NO 3 − contamination in the environment. Frequently, solid solution alloys (SSAs) with a single-phase active site may struggle to fully utilize their benefits during the entire process of nitrate (NO 3 − ) reduction, which involves multiple intermediate reactions. In this study, we showed that by separating Cu and Ni in a Janus Cu@Ni catalyst structure, we can achieve high performance in NO 3− RR, yielding a high Faradaic efficiency (92.5%) and a production rate of NH 3 (1127 mmol h −1 g −1 ) at −0.2 V versus RHE, compared to CuNi SSA (82.6%, 264 mmol h −1 g −1 ). Here, we demonstrate that a Janus Cu@Ni catalyst with shortrange ordered catalytic sites favors the adsorption of NO through a bridge-bond mode. Simultaneously, a hydrogen spillover process was observed, in which Ni dissociates H 2 O to generate *H which spontaneously migrates to adjacent catalytic sites to hydrogenate the *NO x intermediates. This facilitates N−O bond cleavage, resulting in the NH 3 production rate nearly 5 times higher than that of CuNi SSA, where NO was linearly bonded on its surface. The study of this catalytic effect, a cooperative tandem enhancement, provides insights into the design of multifunctional heterogeneous catalysts for electrochemical NH 3 synthesis.

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Section: ■ Results and Discussionmentioning

confidence: 88%

Section: Resultsmentioning

confidence: 88%

Phase-dependent Electrocatalytic Nitrate Reduction to Ammonia on Janus Cu@Ni Tandem Catalyst

Lou,

Zheng,

Zhou

et al. 2024

ACS Catal.

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“…Manufacturing nitrogenous chemicals emit about 400 million metric tons of CO 2 annually, which is incompatible with carbon neutrality and sustainability goals. − Hydroxylamine (HA, NH 2 OH) is a key compound in various fields, such as the semiconductor industry, material synthesis, photographic development, and biomedicine research, as well as a potential hydrogen carrier. − Currently, the synthesis of HA is dominated by NH 3 oxidation or NO hydrogenation under harsh conditions with large energy consumption and carbon emission (Scheme ). − Noble metal catalysts and complicated equipment are also required to improve the conversion efficiency and the HA yield. Therefore, the development of novel HA synthesis routes is of great importance to meet the demands of green chemistry.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Hydroxylamine via Ketone-Mediated Nitrate Electroreduction

Jia,

Wu,

Tan

et al. 2024

J. Am. Chem. Soc.

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Hydroxylamine (HA, NH2OH) is a critical feedstock in the production of various chemicals and materials, and its efficient and sustainable synthesis is of great importance. Electroreduction of nitrate on Cu-based catalysts has emerged as a promising approach for green ammonia (NH3) production, but the electrosynthesis of HA remains challenging due to overreduction of HA to NH3. Herein, we report the first work on ketone-mediated HA synthesis using nitrate in water. A metal–organic-framework-derived Cu catalyst was developed to catalyze the reaction. Cyclopentanone (CP) was used to capture HA in situ to form CP oxime (CP-O) with CN bonds, which is prone to hydrolysis. HA could be released easily after electrolysis, and CP was regenerated. It was demonstrated that CP-O could be formed with an excellent Faradaic efficiency of 47.8%, a corresponding formation rate of 34.9 mg h–1 cm–2, and a remarkable carbon selectivity of >99.9%. The hydrolysis of CP-O to release HA and CP regeneration was also optimized, resulting in 96.1 mmol L–1 of HA stabilized in the solution, which was significantly higher than direct nitrate reduction. Detailed in situ characterizations, control experiments, and theoretical calculations revealed the catalyst surface reconstruction and reaction mechanism, which showed that the coexistence of Cu0 and Cu+ facilitated the protonation and reduction of *NO2 and *NH2OH desorption, leading to the enhancement for HA production.

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“…Differently, the peak intensities of *H 2 O, *OH, and N–H were greatly reduced for the ed -Pb catalyst, indicating the suppressed H 2 and NH 4 + products (Figure B). Meanwhile, new adsorption peaks of C 2 H 2 O 4 (∼1294 cm –1 ) and NH 2 OH (∼1132 cm –1 ) appeared and continuously attenuated with increasing operating time, which suggested the conversion of these two reactants on the Pb site. , Notably, the stretching mode of the CN signal that appeared (∼1501 cm –1 ) further confirmed the formation of oxime, which depended on the coupling of glyoxylic acid (from H 2 C 2 O 4 ) and NH 2 OH . However, no obvious signal of glycine could be observed, indicating the poor capability of the Pb site for oxime hydrogenation to produce glycine.…”

mentioning

confidence: 95%

Tandem Dual-Site PbCu Electrocatalyst for High-Rate and Selective Glycine Synthesis at Industrial Current Densities

Li,

Wan,

Wang

et al. 2024

Nano Lett.

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Direct electrosynthesis of high-value amino acids from carbon and nitrogen monomers remains a challenge. Here, we design a tandem dualsite PbCu electrocatalyst for efficient amino acid electrosynthesis. Using oxalic acid (H 2 C 2 O 4 ) and hydroxylamine (NH 2 OH) as the raw reactants, for the first time, we have realized the flow-electrosynthesis of glycine at the industrial current density of 200 mA cm −2 with Faradaic efficiency over 78%. In situ ATR-FTIR spectroscopy characterizations reveal a favorable tandem pathway on the dual-site catalyst. Specifically, the Pb site drives the highly selective electroreduction of H 2 C 2 O 4 to form glyoxylic acid, and the Cu site accelerates the fast hydrogenation of oxime to form a glycine product. A glycine electrosynthesis (GES)-formaldehyde electrooxidation (FOR) assembly is further established, which synthesizes more valuable chemicals (HCOOH, H 2 ) while minimizing energy consumption. Altogether, we introduce a new strategy to enable the one-step electrosynthesis of high-value amino acid from widely accessible monomers.

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Linear Adsorption Enables NO Selective Electroreduction to Hydroxylamine on Single Co Sites

Cited by 3 publications

References 37 publications

Phase-dependent Electrocatalytic Nitrate Reduction to Ammonia on Janus Cu@Ni Tandem Catalyst

Phase-dependent Electrocatalytic Nitrate Reduction to Ammonia on Janus Cu@Ni Tandem Catalyst

Synthesis of Hydroxylamine via Ketone-Mediated Nitrate Electroreduction

Tandem Dual-Site PbCu Electrocatalyst for High-Rate and Selective Glycine Synthesis at Industrial Current Densities

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