JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2025
·
IF 6
Guo-Cui Mao,Jin-Peng Wang,Hui-Lin Jiang,Bao-Xia Dong,Yun-Lei Teng
We found that the activated LiBH 4 or Ni/LiBH 4 can effectively assist CO 2 hydrogenation into C1 and C2 products at low temperature (100–300 ℃). After CO 2 hydrogenation over the activated LiBH 4 or Ni/LiBH 4 , CH 4 with approximately 100 % selectivity was formed in the gas phase products. CH 3 OH, HCOO − , and high-value CH 3 CH 2 OH were observed in aqueous solution of spent LiBH 4 or Ni/LiBH 4 after CO 2 hydrogenation. CO 2 conversion and CH 4 production are able to be further improved by doping 5–20 wt% Ni into the activated LiBH 4 . The LiBH 4 sample shows a 61.34 % CO 2 conversion at 200 ℃, while the 20 %Ni/LiBH 4 composite displays an 80.14 % CO 2 conversion under the same conditions. The experimental and theoretical results suggest that the synergistic effect from Ni and LiBH 4 results in high CO 2 conversion at low temperature. This new method for CO 2 conversion to C1, C2 products using the activated Ni/LiBH 4 composite may enlighten the materials design for CO 2 utilization.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Science
·
2022
·Vol. 9
·期 16
·2105292
·
IF 17.521
Yawen Jiang,Xinyu Wang,Delong Duan,Chaohua He,Jun Ma,Wenqing Zhang,Hengjie Liu,Ran Long,Zibiao Li,Tingting Kong,Xian Jun Loh,Li Song,Enyi Ye,Yujie Xiong
Structural reconstruction is a process commonly observed for Cu-based catalysts in electrochemical CO 2 reduction. The Cu-based precatalysts with structural complexity often undergo sophisticated structural reconstruction processes, which may offer opportunities for enhancing the electrosynthesis of multicarbon products (C 2+ products) but remain largely uncertain due to various new structural features possibly arising during the processes. In this work, the Cu 2 O superparticles with an assembly structure are demonstrated to undergo complicated structure evolution under electrochemical reduction condition, enabling highly selective CO 2 -to-C 2+ products conversion in electrocatalysis. As revealed by electron microscopic characterization together with in situ X-ray absorption spectroscopy and Raman spectroscopy, the building blocks inside the superparticle fuse to generate numerous grain boundaries while those in the outer shell detach to form nanogap structures that can efficiently confine OH − to induce high local pH. Such a combination of unique structural features with local reaction environment offers two important factors for facilitating C−C coupling. Consequently, the Cu 2 O superparticle-derived catalyst achieves high faradaic efficiencies of 53.2% for C 2 H 4 and 74.2% for C 2+ products, surpassing the performance of geometrically simpler Cu 2 O cube-derived catalyst and most reported Cu electrocatalysts under comparable conditions. This work provides insights for rationally designing highly selective CO 2 reduction electrocatalysts by controlling structural reconstruction.
研究领域:
材料科学
·
电化学
·
环境科学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Lei Xiong,Xianbiao Fu,Jun Zhang,Shuang Liu,Shanshan Li,Shaojie Lu,Dong Wang,Qin Yue
Cu shows unique characteristics for electrochemical CO 2 reduction reaction (CO 2 RR) to hydrocarbons and oxygenates due to the moderate adsorption energy of the key intermediate *CO. However, it remains a challenge to selectively control CO 2 RR towards C 1 (e.g., CH 4 ) or C 2+ (e.g., C 2 H 4 and C 2 H 5 OH) through simple interface engineering. Herein, a series of inverse catalysts, composed of CeO 2 nanoparticles over Cu substrate (Cu-CeO 2 -x), are subtly designed to tackle the issues. It is verified CeO 2 decoration induces highly active Cu/CeO 2 interfacial sites that enhance the adsorption and conversion of CO 2 and *CO intermediates into C 2+ or CH 4 , while the Cu sites are conducive to *CO generation. With the increase of CeO 2 deposition, the C 2+ and CH 4 selectivity present a volcano-type and increasing tendency with maximum faradic efficiency of 62.6% and 51.3%, respectively. In-situ infrared spectroscopy and theoretical calculations reveal that moderate CeO 2 loading allows the Cu/CeO 2 interfacial sites to cooperate efficiently with the Cu sites to promote the coupling of *CO/*CHO intermediates, thus enhancing the C 2+ selectivity. In contrast, excessive CeO 2 loading suppresses the C─C coupling but boosts unilaterally the hydrogenation, thus promoting the CH 4 production. This work provides effective strategies to regulate the CO 2 RR selectivity by modulating metal/oxide interfaces.
研究领域:
材料科学
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2024
·
IF 5.4
Xiang Li,Zhitao Liu,Liyuan Zeng,Wanyi Ye,Guangxing Yang,Qiao Zhang,Shengjun Du,Zhiting Liu,Feng Peng
The CO2 electrochemical reduction (CO2ER) to produce valuable multicarbon products represents a promising approach for enhancing CO2 conversion. While previous research has investigated the impact of Cu electrode surface topography on C2 production, it is important to note that other parameters were also altered concurrently with changes in roughness. To isolate the specific effect of surface texture on CO2 electroreduction, this study prepared Cu layers with varying textures using the sputtering method with a varied sputtering time. To characterize the surface features of the sputtered Cu layers, the developed interfacial area ratio (Sdr), known as areal parameter, was introduced, with the aim of correlating it with C2 product selectivity. The results of this study indicate that the improved selectivity of C2 products can be attributed to higher Sdr values, primarily due to a rougher and finer surface texture that increases the local concentration of CO and OH–. This research underscores the significance of surface topography and offers perspectives for designing efficient Cu electrodes for the CO2ER.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Xuewei Hao,Jiaming Wu,Xintong Cai,Keyan Li,Chunshan Song,Xinwen Guo
The development of photocatalysts for efficient CO 2 conversion to chemicals especially C 2+ products remains a challenge. In this work, Ag nanoparticles (NPs) decorated GaN photocatalysts were synthesized by in-situ nitridation of Ga 2 O 3 combined with chemical deposition of Ag. The photocatalytic performance of Ag/GaN photocatalysts was optimized by tuning the loading amount and ripening time of Ag NPs, among which 0.3Ag/GaN exhibited best photocatalytic CO 2 reduction performance. The production rates of CO and CH 4 reached 421 and 80 μmol g −1 h −1 , respectively, and especially, it also produced C 2 H 6 with a production rate of 79 μmol g −1 h −1 . The introduction of Ag NPs not only significantly promotes visible light absorption as well as charge generation and separation, but also elevates surface temperature of the photocatalyst due to photothermal effect, resulting from localized surface plasmon resonance (LSPR) effect of Ag NPs. Moreover, the addition of Ag NPs enhances the adsorption of both CO 2 and the *CO intermediate, facilitating the CO 2 activation and subsequent C−C coupling process. This study provides new ideas for the design and preparation of photocatalysts capable of converting CO 2 into value-added chemicals.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Bing Chang,Fengtao Zhang,Zhaojun Min,Nan Wang,Qingchun Xia,Jing Fan,Maohong Fan,Jianji Wang
Cu-based catalysts, especially co-sites of Cu 0 and Cu Ⅰ , are the best competitors for electrochemical CO 2 fixation to produce multi-carbon (C2 + ) products. However, it is challenging to construct highly stable Cu Ⅰ sites due to the changeability of its valence state and electronic structure in the electroreduction process, and the mechanism is also elusive. Herein, a 2D conductive Cu Ⅱ -MOF film (Cu Ⅱ HHTP@Cu 0 ) is prepared on Cu (1 0 0) foil by in-situ electrochemical assembly. After pre-reduction, the in-situ produced Cu 2 O clusters are confined in the cavities of the film created by the local breaking of the MOF framework to construct a unique Cu Ⅰ -Cu Ⅱ HHTP@Cu 0 catalyst, so that a novel strategy is proposed to stablize highly dispersed Cu Ⅰ sites during electrochemical reduction, thus protecting the Cu 2 O clusters from further reduction and ensuring the coexistence of Cu Ⅰ (1 1 1)-Cu 0 (1 0 0) sites. As such, the current density of CO 2 electrochemical reduction catalyzed by this catalyst exceeds 300 mA cm −2 , the duration overs 50 h, and the C2 selectivity achieves 72.6 %. In-situ spectroscopy and theoretical calculations reveal that the optimized microenvironment of the Cu Ⅰ (1 1 1) sites reduces the energy barrier of *OCCOH coupling, and Cu 0 (1 0 0) sites increase the coverage of *CO, thus boosting the production of C2 products.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Surfaces and Interfaces
·
2024
·
IF 5.7
Pengfei Zhu,Mengrong Geng,Shuang Qin,Heyang Cao,Zhenhong He,Xinhua Gao,Chuanyi Wang
The conversion of CO 2 into chemical products or fuels of great value always remains an outstanding challenge. Here, we report a heterojunction Fe@C/Ni 2 P composite catalyst obtained by preparing MIL-100(Fe) derived Fe@C confined Ni 2 P nanoparticles, which is applied to photothermal catalytic CO 2 hydrogenation with H 2 O. Without adding any sacrificial agents or co-catalysts, the optimal Fe@C/Ni 2 P sample shows higher yields for CO 2 -to-C 2 H 6 and CO 2 -to-CO yield of 5.83 μmol g −1 h −1 and 179.9 μmol g −1 h −1 than that of pristine Fe@C and Ni 2 P, respectively. The experimental results indicated that the obtained Fe@C/Ni 2 P can act as catalytic sites to adsorb, activate, and convert CO 2 under low-intensity LED light irradiation (420 nm) with a temperature of 200 ℃. The physical structure, photochemical properties and energy band structure of the Fe@C/Ni 2 P composite catalysts were investigated by XRD, XPS, FT-IR, TEM, BET, respectively. Furthermore, the reaction pathway of Fe@C/Ni 2 P photothermal catalytic CO 2 hydrogenation with H 2 O to C2 products and CO were systematically analyzed by in situ infrared spectroscopy (DRIFTS).
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Carbon Energy
·
2024
·
IF 19.5
Fangfang Chang,Zhenmao Zhang,Yan Zhang,Yongpeng Liu,Lin Yang,Xiaolei Wang,Zhengyu Bai,Qing Zhang
Electrochemical CO 2 reduction reaction (CO 2 RR) offers a promising strategy for CO 2 conversion into value-added C 2+ products and facilitates the storage of renewable resources under comparatively mild conditions, but still remains a challenge. Herein, we propose the strategy of surface reconstruction and interface integration engineering to construct tuneable Cu 0 –Cu + –Cu 2+ sites and oxygen vacancy oxide derived from CeO 2 /CuO nanosheets (OD-CeO 2 /CuO NSs) heterojunction catalysts and promote the activity and selectivity of CO 2 RR. The optimized OD-CeO 2 /CuO electrocatalyst shows the maximum Faradic efficiencies for C 2+ products in the H-type cell, which reaches 69.8% at −1.25 V versus a reversible hydrogen electrode (RHE). Advanced characterization analysis and density functional theory (DFT) calculations further confirm the fact that the existence of oxygen vacancies and Cu 0 –Cu + –Cu 2+ sites modified with CeO 2 is conducive to CO 2 adsorption and activation, enhances the hydrogenation of *CO to *CHO, and further promotes the dimerization of *CHO, thus promoting the selectivity of C 2+ generation. This facile interface integration and surface reconstruction strategy provides an ideal strategy to guide the design of CO 2 RR electrocatalysts.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Small
·
2024
·
IF 13
Yi-Ran Du,Xiao-Qiang Li,Xian-Xia Yang,Guo-Yi Duan,Yong-Mei Chen,Bao-Hua Xu
In this study, the copper-nickel (Cu–Ni) bimetallic electrocatalysts for electrochemical CO 2 reduction reaction(CO 2 RR) are fabricated by taking the finely designed poly(ionic liquids) (PIL) containing abundant Salen and imidazolium chelating sites as the surficial layer, wherein Cu–Ni, PIL–Cu and PIL–Ni interaction can be readily regulated by different synthetic scheme. As a proof of concept, Cu@Salen-PIL@Ni(NO 3 ) 2 and Cu@Salen-PIL(Ni) hybrids differ significantly in the types and distribution of Ni species and Cu species at the surface, thereby delivering distinct Cu–Ni cooperation fashion for the CO 2 RR. Remarkably, Cu@Salen-PIL@Ni(NO 3 ) 2 provides a C2+ faradaic efficiency (FE C2+ ) of 80.9% with partial current density ( j C 2+ ) of 262.9 mA cm −2 at −0.80 V (versus reversible hydrogen electrode, RHE) in 1 m KOH in a flow cell, while Cu@Salen-PIL(Ni) delivers the optimal FE C2+ of 63.8% at j C2+ of 146.7 mA cm −2 at −0.78 V. Mechanistic studies indicates that the presence of Cu–Ni interfaces in Cu@Salen-PIL@Ni(NO 3 ) 2 accounts for the preserve of high-valence Cu(I) species under CO 2 RR conditions. It results in a high activity of both CO 2 -to-CO conversion and C–C coupling while inhibition of the competitive HER.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 25
·15082-15089
·
IF 10.7
Zongmiao Li,Zhu Liu,Shiju Li,Yuhou Pei,Di Li,Jiale Mao,Rong Zhou,Chuntian Qiu,Yingying Lu,Bing Zhang
Electrochemical conversion of carbon dioxide (CO2RR) into high-value multi-carbon (C2+) chemicals and fuels is of great significance for carbon neutrality, and so far Cu-based materials are still the dominant electrocatalysts with practical application potential for C2+ products during the CO2RR. However, Cu-based catalysts usually face problems such as an unstable valence state and lattice structure, low efficiency, and a narrow potential window for C2+ products which affect the comprehensive performance of the catalysts. Herein, we develop a simple co-precipitation-hydrothermal method for introducing zirconium dioxide (ZrO2) into copper oxide (CuO) to improve the selectivity of C2+ products via in situ reconstruction. The optimized CuO–ZrO2-1.0 catalyst exhibits a high faradaic efficiency of 82.3% for C2+ products with an industrial partial current density over 200 mA cm−2, which presents a more than 1.7-fold improvement compared to that of CuO, also exceeding that of lots of Cu-based catalysts previously reported. DFT and in situ characterization studies reveal that the introduction of ZrO2 can induce the electronic distribution and stabilize the Cu+ species during the in situ reconstruction process which contributes to moderate adsorption and enhanced coupling of *CO intermediates to obtain C2+ products.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ADVANCED MATERIALS
·
2020
·Vol. 32
·期 39
·2002382
·
IF 27.398
Changming Zhao,Gan Luo,Xiaokang Liu,Wei Zhang,Zhijun Li,Qian Xu,Qinghua Zhang,Huijuan Wang,Deming Li,Fangyao Zhou,Yunteng Qu,Xiao Han,Zezhou Zhu,Geng Wu,Jing Wang,Junfa Zhu,Tao Yao,Yafei Li,Henny J.M. Bouwmeester,Yuen Wu
Electrochemical reduction of CO to value-added products holds promise for storage of energy from renewable sources. Copper can convert CO into multi-carbon (C 2+ ) products during CO electroreduction. However, developing a Cu electrocatalyst with a high selectivity for CO reduction and desirable production rates for C 2+ products remains challenging. Herein, highly lattice-disordered Cu 3 N with abundant twin structures as a precursor electrocatalyst is examined for CO reduction. Through in situ activation during the CO reduction reaction (CORR) and concomitant release of nitrogen, the obtained metallic Cu° catalyst particles inherit the lattice dislocations present in the parent Cu 3 N lattice. The de-nitrified catalyst delivers an unprecedented C 2+ Faradaic efficiency of over 90% at a current density of 727 mA cm −2 in a flow cell system. Using a membrane electrode assembly (MEA) electrolyzer with a solid-state electrolyte (SSE), a 17.4 vol% ethylene stream and liquid streams with concentration of 1.45 m and 230 × 10 −3 m C 2+ products at the outlet of the cathode and SSE-containment layer are obtained.
研究领域:
材料科学
·
电化学
·
能源存储与转化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Canyan Yang,Ruichen Wang,Chao Yu,Jinhua Xiao,Zhiwei Huang,Bihong Lv,Huawang Zhao,Xiaomin Wu,Guohua Jing
Cu-based catalysts inevitably undergo surface reconstruction during the electrochemical carbon dioxide reduction reaction (CO 2 RR) process. Thus, it is a challenge to construct stable Cu + -Cu 0 sites of Cu-based catalysts. In this study, we report a simple and facile engineering strategy for stable Cu + -Cu 0 sites and oxygen defects derived from the boron-doped copper composite catalyst (B-Cu x O) as an efficient CO 2 RR electrocatalyst. The 5 % B-Cu x O exhibited 48.44 % C 2+ products Faraday efficiency (FE) for 12 h at −1.0 V vs reversible hydrogen electrode (RHE) in H-cell, which was far superior to Cu x O (23.85 %). Combining density functional theory (DFT) and in situ Attenuated Total Reflection Fourier Transform Infrared spectroscopy ( in situ ATR-FTIR), a higher electronic depletion on the catalyst surface inhibited the electrons accumulation around Cu sites, thereby maintaining the positive charge and inhibiting the complete reduction of Cu + . Moreover, the high oxygen defects in 5 % B-Cu x O could effectively activate CO 2 into *CO. We emphasized that Cu + functioned as the primary active site by facilitating adsorption and dimerization of *CO, whereas Cu 0 assisted in optimizing CO 2 activation.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）