Cu掺杂WN松枝状自支撑纳米阵列的制备及其碱性析氢性能的研究

doi:10.12422/j.issn.1006-396X.2024.04.008

石油化工高等学校学报 ›› 2024, Vol. 37 ›› Issue (4): 57-65.DOI: 10.12422/j.issn.1006-396X.2024.04.008

Cu掺杂WN松枝状自支撑纳米阵列的制备及其碱性析氢性能的研究

李乐乐¹^,²(), 申丽莎², 涂志明², 卢卓信², 谭弘毅², 杨轶², 闫常峰¹^,²

^1.中国科学技术大学能源科学与技术学院，安徽合肥 230026
^2.中国科学院广州能源研究所，广东广州 510640

收稿日期:2024-03-11 修回日期:2024-04-07 出版日期:2024-08-25 发布日期:2024-08-07
通讯作者: 闫常峰
作者简介:李乐乐（1996⁃），男，硕士研究生，从事电解水制氢催化剂合成方面的研究；E⁃mail：lilele@mail.ustc.edu.cn。
基金资助:
国家自然科学基金项目(52276222);中国科学院国际伙伴计划项目(118GJHZ2022029MI);广州市科技计划项目(2024A04J4818);安徽省重点研发项目(2023t07020022)

Preparation of Cu⁃Doped WN Nanoarrays and Study on Their Hydrogen Evolution Performance

Lele LI¹^,²(), Lisha SHEN², Zhiming TU², Zhuoxin LU², Hongyi TAN², Yi YANG², Changfeng YAN¹^,²

^1.School of Energy Science and Engineering，University of Science and Technology of China，Hefei Anhui 230026，China
^2.Guangzhou Institute of Energy Conversion，Chinese Academy of Science，Guangzhou Guangdong 510640，China

Received:2024-03-11 Revised:2024-04-07 Published:2024-08-25 Online:2024-08-07
Contact: Changfeng YAN

摘要/Abstract

摘要：

以偏钨酸铵、乙酸铜等为原料，通过控制掺杂比，采用简单的水热法，合成了形貌不同的前驱体，随后结合高温退火法，在碳纸上成功实现了Cu掺杂WN松枝状自支撑纳米阵列（Cu?WN?5∶1）的原位生长；利用SEM、TEM、XRD、XPS等测试手段对样品的形貌和结构进行表征分析，进而利用电化学测试方法评估了催化剂的析氢性能。结果表明，W和Cu的掺杂比（n（W）/n（Cu））对催化剂的析氢性能具有重大影响；当n（W）/n（Cu）为5∶1时，催化剂具有最优的析氢活性；Cu元素的成功掺杂改变了WN的电子结构，增加了其活性位点的数量，加速催化过程中的电荷转移速率，从而提升了材料的HER活性；Cu?WN?5∶1在KOH浓度为1.0 mol/L、电流密度为10 mA/cm²时所需的过电位为195 mV，Tafel斜率为192 mV/dec，说明Cu?WN?5∶1具有较快的电化学析氢反应动力学速率；该材料在KOH浓度为1.0 mol/L的条件下持续反应36 h，表现出优异的长期稳定性。

关键词: 氮化钨, 过渡金属掺杂, 碱性析氢, 电催化, 阵列结构

Abstract:

Using ammonium metatungstate and copper acetate as raw materials,the precursors with different morphology were synthesized by a simple hydrothermal method by controlling the doping ratio.Then,combined with high temperature annealing method,the in?situ growth of Cu?WN?5∶1 was successfully realized on carbon paper.The morphology and structure of the samples were characterized by SEM,TEM,XRD and XPS,and then the hydrogen evolution performance of the catalyst was evaluated by electrochemical testing methods.The results show that the doping ratio of W and Cu (n(W)/n(Cu)） has a significant effect on the hydrogen evolution performance of the catalyst,in which the optimal hydrogen precipitation activity is achieved when n(W)/n(Cu) is 5∶1.The successful doping of Cu increases the number of active sites by changing the electronic structure of WN,accelerates the charge transfer rate in the catalytic process,which in turn improves the HER activity of the material.The required overpotential of Cu?WN?5∶1 at 1.0 mol/L KOH with a current density of 10 mA/cm² is 195 mV,and the Tafel slope is 192 mV/dec,which indicates that Cu?WN?5∶1 has a fast kinetic rate of electrochemical hydrogen precipitation reaction;the material has been continuously reacted for 36 h under the condition of 1.0 mol/L KOH,and it exhibits excellent long?term stability.

Key words: Tungsten nitride, Transition metal doping, Alkaline electrocatalytic hydrogen evolution, Electrocatalysis, Array structures

中图分类号:

TQ116.2+1

李乐乐, 申丽莎, 涂志明, 卢卓信, 谭弘毅, 杨轶, 闫常峰. Cu掺杂WN松枝状自支撑纳米阵列的制备及其碱性析氢性能的研究[J]. 石油化工高等学校学报, 2024, 37(4): 57-65.

Lele LI, Lisha SHEN, Zhiming TU, Zhuoxin LU, Hongyi TAN, Yi YANG, Changfeng YAN. Preparation of Cu⁃Doped WN Nanoarrays and Study on Their Hydrogen Evolution Performance[J]. Journal of Petrochemical Universities, 2024, 37(4): 57-65.

图/表 7

图1 不同掺杂比Cu?WO3前驱体和高温氮化后产物的SEM

Fig.1 SEM of Cu‐WO3 precursors and high temperature nitriding products with different doping ratios

图2 Cu?WO3?5∶1的XRD和TEM图

Fig.2 XRD and TEM characterization of Cu?WO3?5∶1

图3 Cu?WN?5∶1的XRD和XPS图

Fig.3 XRD and XPS characterization of Cu?WN?5∶1

图4 Cu?WN?5∶1的SEM、TEM图和元素分布图（a） SEM图（b） TEM图（c）元素分布图

Fig.4 SEM,TEM and elemental map of Cu?WN?5∶1

图5 各种催化剂的LSV曲线和Tafel斜率

Fig.5 Hydrogen evolution polarization curve and Tafel slope diagram of various catalysts

图6 催化剂的电化学阻抗和双电层电容对比

Fig.6 Comparison of electrochemical impedance and double layer capacitance of catalysts

图7 Cu?WN?5∶1的稳定性测试结果

Fig.7 Stability test result of Cu?WN?5∶1

参考文献 27

1	ZHOU S H，SHI L，LI Y Z，et al.Metal‐organic framework‐based electrocatalysts for acidic water splitting［J/OL］.Advanced Functional Materials：2400767（2024⁃03⁃13）［2024⁃04⁃18］.https：//onlinelibrary.wiley.com/doi/abs/10.1002/adfm.202400767.
2	曲虎，陆诗建，杨佳朋，等.双碳背景下油田清洁能源利用工艺可行性探讨［J］.低碳化学与化工，2024，49（4）：79⁃89.
	QU H，LU S J，YANG J P，et al.Feasibility diseussion on clean energy utilication process in oilfields under background ofcarbon peaking and carbon neutrality［J］.Low⁃Carbon Chemistry and Chemical Engineering，2024，49（4）：79⁃89.
3	刘佳，张士明，宋兆阳，等.加氢裂化复合分子筛催化剂研究进展［J］.当代化工，2024，53（3）：664⁃671.
	LIU J，ZHANG S M，SONG Z Y，et al.Research progress of composite molecular sieve catalysts in hydrocracking［J］.Contemporary Chemical Industry，2024，53（3）：664⁃671.
4	宋学实，曲微丽，赵磊，等.质子交换膜燃料电池氧还原Pt基催化剂研究进展［J］.石油化工高等学校学报，2023，36（4）：25⁃33.
	SONG X S，QU W L，ZHAO L，et al.Research progress of Pt⁃based catalysts for oxygen reduction in proton exchange membrane fuel cells［J］.Journal of Petrochemical Universities，2023，36（4）：25⁃33.
5	ZHANG Y M，YAN R，XU X H，et al.Next generation noble metal‐engineered catalysts：From structure evolution to structure‐reactivity correlation in water splitting［J］.Advanced Functional Materials，2024，34（4）：2308813.
6	KAZEMI A，MANTEGHI F，TEHRANI Z.Metal electrocatalysts for hydrogen production in water splitting［J］.ACS Omega，2024，9（7）：7310⁃7335.
7	JIAO Y Q，YAN H J，TIAN C G，et al.Structure engineering and electronic modulation of transition metal interstitial compounds for electrocatalytic water splitting［J］.Accounts of Materials Research，2022，4（1）：42⁃56.
8	SEENIVASAN S，IM H，LIM T，et al.Schottky switch derived by metallic W₅N₄ \|catalyst junction：Switch⁃on to enhance catalytic activity and durability in water splitting reaction［J］.Applied Catalysis B：Environmental，2024，340：123233.
9	LEE M G，YANG J W，KWON H R，et al.Crystal facet and phase engineering for advanced water splitting［J］.Crystengcomm，2022，24（33）：5838⁃5864.
10	LIU Y Q，ZHANG Z H，ZHANG L，et al.Manipulating the d⁃band centers of transition metal phosphides through dual metal doping towards robust overall water splitting［J］.Journal of Materials Chemistry A，2022，10（41）：22125⁃22134.
11	MA K W，CHANG X R，WANG Z H，et al.Tunable d⁃band center of a NiFeMo alloy with enlarged lattice strain enhancing the intrinsic catalytic activity for overall water⁃splitting［J］.Nanoscale，2023，15（12）：5843⁃5854.
12	刘倩倩，达志坚，吕令玮，等.催化裂化催化剂铁中毒问题剖析［J］.石油炼制与化工，2022，53（5）：1⁃6.
	LIU Q Q，DA Z J，LÜ L W，et al.Analysis on iron poisoning of fcc catalyst［J］.Petroleum Processing and Petrochemicals，2022，53（5）：1⁃6.
13	YAO Y H，ZHANG Z Y，JIAO L F.Development strategies in transition metal borides for electrochemical water splitting［J］.Energy & Environmental Materials，2022，5（2）：470⁃485.
14	CAO L M，ZHANG J，DING L W，et al.Metal⁃organic frameworks derived transition metal phosphides for electrocatalytic water splitting［J］.Journal of Energy Chemistry，2022，68：494⁃520.
15	ZHANG Q，LUO F，LONG X，et al.N，P doped carbon nanotubes confined WN⁃Ni Mott⁃Schottky heterogeneous electrocatalyst for water splitting and rechargeable zinc⁃air batteries［J］.Applied Catalysis B：Environmental，2021，298：120511.
16	KANNIMUTHU K，SANGEETHA K，SAM SANKAR S，et al.Investigation on nanostructured Cu⁃based electrocatalysts for improvising water splitting：A review［J］.Inorganic Chemistry Frontiers，2021，8（1）：234⁃272.
17	ZHANG Y S，YAN J，HUANG W M.Using free⁃energy weakening strategy to control the d⁃band center over the Cu and Co based electrocatalyst for boosting hydrogen production［J］.Journal of Electroanalytical Chemistry，2023，936：117367.
18	许雪容，彭祥.层状双金属氢氧化物电催化剂的合成与应用研究进展［J］.石油化工高等学校学报，2022，35（5）：1⁃11.
	XU X R，PENG X.Research progress in preparation and application of layered double hydroxides electrocatalysts［J］.Journal of Petrochemical Universities，2022，35（5）：1⁃11.
19	穆晓雪，丁巍，张晓帆，等.Fe改性MoNi/γ⁃Al₂O₃催化剂的制备与表征［J］.辽宁石油化工大学学报，2022，42（4）：6⁃10.
	MU X X，DING W，ZHANG X F，et al.Preparation and characterization of iron modified MoNi/γ⁃Al₂O₃ catalysts［J］.Journal of Liaoning Petrochemical University，2022，42（4）：6⁃10.
20	LIU L，CHEN Y，CHEN J J，et al.Self⁃supporting electrode fabricated by flowing synthesis for efficient hydrogen evolution reaction［J］.ACS Sustainable Chemistry & Engineering，2023，11（14）：5506⁃5514.
21	ZHAO Y，WEI S Z，XIA L B，et al.Sintered Ni metal as a matrix of robust self⁃supporting electrode for ultra⁃stable hydrogen evolution［J］.Chemical Engineering Journal，2022，430（Part 4）：133040.
22	YANG Z K，ZHAO C M，QU Y T，et al.Trifunctional self⁃supporting cobalt⁃embedded carbon nanotube films for ORR，OER，and HER triggered by solid diffusion from bulk metal［J］.Advanced Materials，2019，31（12）：e1808043.
23	XIE C，CHEN W，DU S Q，et al.In⁃situ phase transition of WO₃ boosting electron and hydrogen transfer for enhancing hydrogen evolution on Pt［J］.Nano Energy，2020，71：104653.
24	LIU L，ZHAO Y Z，WANG Y，et al.Single⁃atom Co doped in ultrathin WO₃ arrays for the enhanced hydrogen evolution reaction in a wide pH range［J］.ACS Applied Materials & Interfaces，2021，13（45）：53915⁃53924.
25	YAN H J，TIAN C G，WANG L，et al.Phosphorus⁃modified tungsten nitride/reduced graphene oxide as a high⁃performance，non⁃noble⁃metal electrocatalyst for the hydrogen evolution reaction［J］.Angewandte Chemie （International ed.in English），2015，54（21）：6325⁃6329.
26	WANG M F，CHENG X M，NI Y H.Simple vapor⁃solid⁃reaction route for porous Cu₂O nanorods with good HER catalytic activity［J］.Dalton Transactions，2019，48（3）：823⁃832.
27	WU A P，GU Y，YANG B R，et al.Porous cobalt/tungsten nitride polyhedra as efficient bifunctional electrocatalysts for overall water splitting［J］.Journal of Materials Chemistry A，2020，8（43）：22938⁃22946.

[1]	王嘉曼, 熊靖, 师金鸽, 韦岳长, 霍开玲. TiO₂催化剂催化CO₂还原的研究进展[J]. 石油化工高等学校学报, 2024, 37(4): 1-11.
[2]	毕艳琴, 陈亮亮, 段春阳, 赵增华. Ce-CoFe-P@CC纳米复合催化体系的OER性能[J]. 石油化工高等学校学报, 2024, 37(3): 49-57.
[3]	杜坤, 郭佳欣, 马紫昂, 毛晶, 凌涛, 赵巍. 中性环境下电催化析氧反应研究进展[J]. 石油化工高等学校学报, 2023, 36(5): 1-14.
[4]	武玉泰, 王佳琦, 李丹, 胡旭, 王永胜, 郝广平. 双金属⁃氮掺杂炭催化剂的制备及其电催化CO₂性能[J]. 石油化工高等学校学报, 2023, 36(3): 1-10.
[5]	张瑀净, 张宝山, 孙洁. 电解水制氢技术及其催化剂研究进展[J]. 石油化工高等学校学报, 2022, 35(6): 19-27.
[6]	范琳, 杨磊, 车晓甄, 李夺, 潘立卫, 钟和香. CO₂电化学还原制CO金属催化剂的研究进展[J]. 石油化工高等学校学报, 2022, 35(6): 48-58.
[7]	许雪容, 彭祥. 层状双金属氢氧化物电催化剂的合成与应用研究进展[J]. 石油化工高等学校学报, 2022, 35(5): 1-11.
[8]	杨扬, 孟超, 胡涵, 吴明铂. NiCo₂O₄/Ru复合催化剂的制备及锌空电池的应用[J]. 石油化工高等学校学报, 2022, 35(5): 64-70.
[9]	宋楗, 韩乔, 杨占旭. NiMoP/C复合材料的制备及其电催化析氢性能[J]. 石油化工高等学校学报, 2022, 35(1): 1-9.
[10]	荣冰莹，刘贺，惠宇，宋丽娟，钟伟. 多吡啶铁配合物制备及电催化质子还原性能[J]. 石油化工高等学校学报, 2020, 33(2): 1-6.
[11]	张强, 李保山, 孙桂大, 周志军. W₂N/Ti ₂-Al₂O₃ 催化剂的制备表征及噻吩HDS活性[J]. 石油化工高等学校学报, 2007, 20(2): 18-22.

Cu掺杂WN松枝状自支撑纳米阵列的制备及其碱性析氢性能的研究

Preparation of Cu⁃Doped WN Nanoarrays and Study on Their Hydrogen Evolution Performance

HTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 27

相关文章 11

编辑推荐

Metrics